TW201428056A - Active energy ray-curable composition, cured coating film of same, and article having said cured coating film - Google Patents

Abstract

Provided are: an active energy ray-curable composition characterized in containing a (meth)acrylate (A) bonded with a polyoxyalkylene chain having an average number of repeating units of 4-20 via a structure having an isocyanurate ring and a urethane bond, the (meth)acrylate (A) having a (meth)acryloyl group at the end of the polyoxyalkylene chain on the opposite side from the urethane bond a cured coating film thereof and an article having this cured coating film. This active energy ray-curable composition can impart an excellent soft feel to the surface of various articles and makes it possible to obtain a coating film having high adhesiveness with a base coat. Examples of the article include: the main body of household appliances such as refrigerators, televisions, and air conditioners the casing of information terminals such as remote controls, portable telephones, smart phones, and personal computers and molded plastic parts such as car interior materials.

Description

Active energy ray-curable composition, cured coating film thereof, and article having the same

The present invention relates to an active energy ray-curable composition which can impart a soft feeling to the surface of various articles and which can provide a coating film having high adhesion to the undercoat layer, and an article using the same.

In recent years, plastic molded products have been widely used in the body of home appliances such as refrigerators, televisions, and air conditioners, as well as housings for remote terminals, mobile phones, smart phones, computers, and the like. These plastic molded articles may also be used as they are directly formed, but they are often coated for design. In the past, the design is often visually identifiable, such as color, gloss, and the like. However, for example, the touch feeling of softness such as softness when touched by a finger is applied by coating.

As a material which imparts the above-mentioned softness, an isocyanate compound obtained by reacting a polyester polyol having two or more hydroxyl groups in one molecule and hexamethylene diisocyanate is further contained, and further contains a methyl group having a hydroxyl group. An active energy ray-curable urethane (meth) acrylate obtained by an acrylate reaction, and a composition for an active energy ray-curable top coat of a photopolymerization initiator (for example, see Patent Document 1). However, the active energy ray-curable top coat composition has a problem that the adhesion to the undercoat layer is insufficient in the stratification of the plastic molded article.

Therefore, there is a need for an active energy ray-curable composition which imparts flexibility to the surface of a plastic molded article and which has high adhesion to the undercoat layer.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2007-131700

The problem to be solved by the present invention is to provide an active energy ray-curable composition capable of imparting an excellent touch feeling to the surface of various articles and having a coating film having high adhesion to the undercoat layer and using the same. Its items.

As a result of intensive studies to solve the aforementioned problems, the inventors of the present invention found that by using an active energy ray-curable composition containing a (meth) acrylate having a hetero-cyanate ring and a polyoxyalkylene chain, various The surface of the article imparts a soft feeling and a coating film having high adhesion to the undercoat layer can be obtained, thereby completing the present invention.

That is, the present invention relates to an active energy ray-curable composition and an article using the same, which comprises a structure having a hetero-cyanate ring and a urethane bond, and an average number of repeating units of the bond 4 a polyoxyalkylene chain of -20, and a (meth) acrylate group (meth) acrylate (A) at the end of the polyoxyalkylene chain opposite to the urethane bond.

The active energy ray-curable composition of the present invention can impart a soft feeling to the surface of various articles and can provide a coating film having high adhesion to the undercoat layer. Therefore, it is possible to impart softness to the surface of a wide range of plastic molded articles such as the main body of a home appliance such as a refrigerator, a television, or an air conditioner, and a casing of an information terminal such as a remote controller, a mobile phone, a smart phone, or a computer.

The active energy ray-curable composition of the present invention contains a polyoxyalkylene chain having a structure of a hetero-cyanate ring and a urethane bond, and an average number of repeating units of 4 to 20 is bonded, and The (meth) acrylate (A) having a (meth) acrylonitrile group at the end of the polyoxyalkylene chain opposite to the urethane bond. Further, the polyoxyalkylene chain may be bonded to a (meth)acryloyl group at the terminal thereof through a divalent organic group such as a urethane bond.

In the present invention, "(meth)acryl fluorenyl" means one or two of a propylene fluorenyl group and a methacryl fluorenyl group, and "(meth) acrylate" means acrylate and methacrylic acid. One or both of the esters, "(meth)acrylic" means either or both of acrylic acid and methacrylic acid.

The (meth) acrylate (A) is a polyoxyalkylene chain having an isomeric cyanate ring and an average repeating unit number of 4 to 20 in its structure.

Examples of the method for producing the (meth) acrylate (A) include the following methods (1) to (3).

(1) A method of subjecting an isocyanate group of a polyisocyanate compound (a1) having an isomeric cyanate ring to a hydroxyl group of a polyoxyalkylene mono(meth)acrylate (a2).

(2) After the isocyanate group of the polyisocyanate compound (a1) and the hydroxyl group of one of the two hydroxyl groups of the polyoxyalkylene (polyalkylene glycol) are subjected to a urethanization reaction, the remaining hydroxyl group is A method in which an alkyl ester is subjected to an esterification reaction.

(3) A method of reacting the remaining hydroxyl group with the compound (a3) having an isocyanate group and a (meth)acryloyl group after the amination treatment of the above (2).

Further, the urethanation reaction and the esterification reaction by the methods (1) to (3) can be carried out by a known method. For example, the urethanization reaction is preferably carried out in the presence of a urethane catalyst. Examples of the urethane-based catalyst include an amine compound such as triethylamine, dibutyltin dilaurate, dioctyltin dilaurate, octyltin trilaurate, and dioctyldiruthenate. An organotin compound such as tin tin, dibutyltin diacetate, dioctyltin diacetate or tin dioctoate, or an organometallic compound such as zinc octoate (zinc 2-ethylhexanoate).

Further, in the method of the above (2) or (3), the urethanization reaction in which only the polyisocyanate compound (a1) and the polyoxyalkylene are involved is a problem in that a polyurethane is produced. The control of the reaction is difficult. However, in the method (1), since the above-mentioned (meth) acrylate (A) is more easily obtained because the above problem is not obtained, it is preferable.

The polyisocyanate compound (a1) is not particularly limited as long as it has an isomeric cyanate ring in its structure, and examples thereof include a trimer of a diisocyanate. Examples of the diisocyanate include hexamethylene diisocyanate, phenyl diisocyanate, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and isophorone diisocyanate. Further, a polyisocyanate obtained by reacting a trimer of the diisocyanate with a polyhydric alcohol can also be used as the polyisocyanate compound (a1). Examples of the polyhydric alcohol include aliphatic diols such as 2,2,4-trimethyl-1,3-pentanediol, 1,3-hexanediol, and 1,6-hexanediol. A 2-mer of an unsaturated aliphatic alcohol or the like. Further, these polyisocyanate compounds (a1) may be used singly or in combination of two or more kinds.

Among the polyisocyanate compounds (a1), from the viewpoint of obtaining a soft feeling which is more excellent in touch, a trimer containing hexamethylene diisocyanate is preferred.

The polyoxyalkylene mono(meth)acrylate (a2) is a compound having a polyoxyalkylene chain having an average repeating unit number of 4 to 20 and one (meth)acryl fluorenyl group, and, for example, the following formula (1) A compound shown.

(In the formula (1), R represents a hydrogen atom or a methyl group, A represents an alkylene group, and n represents an average number of repeats, and the range is 4 to 20. Further, A is one type or two or more types, and two or more types are used. In the case, the repeating unit can be configured to be random or configured as a block.

Further, in the polyoxyalkylene mono(meth)acrylate (a2), in the compound represented by the above formula (1), A is preferably an alkyl group having 1 to 6 carbon atoms, and A is More preferably, the propyl group is a polyoxypropylene mono(meth)acrylate, and the A is an ethylidene group-polyoxyethylene mono(meth)acrylate.

Further, in the above formula (1), the range of n of the average number of repetitions of the alkylene oxide is preferably from 5 to 14, more preferably from 6 to 13.

Specific examples of the polyoxyalkylene mono(meth)acrylate (a2) include an average repeating unit of "BLEMMER AP-400" (hereinafter referred to as "PO") manufactured by Nippon Oil Co., Ltd. Number n=6), "BLEMMER AP-550" (the number of repeating units of PO is n=9), "BLEMMER AP-800" (the average number of repeating units of PO is n=13), "BLEMMER AE-200" (oxygen) The average number of repeating units of ethylene (hereinafter referred to as "EO") is n = 4.5), "BLEMMER AE-400" (the average number of repeating units of EO is n = 10), and the like. Further, the polyoxyalkylene mono(meth)acrylates (a2) may be used singly or in combination of two or more.

Examples of the compound (a3) having an isocyanate group and a (meth)acryl fluorenyl group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-(bis(methyl)acryl oxime. Alkyloxymethyl)ethyl isocyanate or the like.

When the (meth) acrylate (A) is produced by the method of the above (1), the polyisocyanate compound (a1) has an isocyanate group (NCO) and the polyoxyethylene mono(meth) acrylate (a2). The equivalent ratio (NCO/OH) of the hydroxyl group (OH) is preferably in the range of 0.8 to 1.1, more preferably in the range of 0.9 to 1.05, and particularly preferably in the range of 0.95 to 1.02.

In the active energy ray-curable composition of the present invention, in addition to the (meth) acrylate (A), an active energy ray-curable monomer (B) which is a component of other components may be blended.

Examples of the active energy ray-curable monomer (B) include N-(2-hydroxyethyl)(meth)acrylamide, N-isopropyl(meth)acrylamide, (A) Acetyl hydrazinomorpholine, dimethylaminopropyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, tetrahydrofuran (meth) acrylate Methyl ester, isodecyl (meth)acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Further, the active energy ray-curable monomers (B) may be used singly or in combination of two or more.

Further, after the active energy ray-curable composition of the present invention is applied to a substrate, it can be made into a cured coating film by irradiation with an active energy ray. The active energy ray means free radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, gamma rays, and the like. When the ultraviolet ray is used as the active energy ray to form a cured coating film, the photopolymerization initiator (C) is added to the active energy ray-curable composition of the present invention, and the curing property is preferably improved. Further, if necessary, a photosensitizer may be further added to improve the hardenability. On the other hand, when free radiation such as electron beam, alpha ray, beta ray, gamma ray is used, since it can be rapidly hardened without using a photopolymerization initiator (C) or a photosensitizer, no special addition is required. Photopolymerization initiator (C) or photo sensitizer.

The photopolymerization initiator (C) may, for example, be an intramolecular cleavage type photopolymerization initiator or a dehydrogenation type photopolymerization initiator. As an intramolecular cleavage type photopolymerization initiator, for example, diethoxyacetophenone, 2-hydroxyl -2-methyl-1-phenylpropan-1-one, benzyl dimethyl acetal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinyl (4-thiomethyl benzene) Acetophenone-based compound such as propan-1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone; benzoin, benzoin Benzoin of methyl ether, benzoin isopropyl ether, etc.; 2,4,6-trimethylbenzoin diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)- a mercaptophosphine oxide compound such as phenylphosphine oxide; diphenylethylenedione or methylphenylglyoxylate.

On the other hand, examples of the dehydrogenation type photopolymerization initiator include benzophenone, o-benzyl benzoyl benzoic acid methyl-4-phenylbenzophenone, and 4,4'-dichloro Benzophenone, hydroxybenzophenone, 4-benzylindolyl-4'-methyl-diphenyl sulfide, benzoated benzophenone, 3,3',4,4'-tetra (t-butyl a benzophenone compound such as peroxycarbonyl)benzophenone or 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4-di a thioxanthone compound such as methylthioxanthone, 2,4-diethylthioxanthone or 2,4-dichlorothioxanthone; Michler's ketone, 4,4'-diethylaminobiphenyl An aminobenzophenone-based compound such as ketone; 10-butyl-2-chloroacridone, 2-ethylhydrazine, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators (C) may be used singly or in combination of two or more.

In addition, examples of the photosensitizer include an amine such as an aliphatic amine or an aromatic amine, a urea such as o-methylthiourea, sodium diethyl dithiophosphate, or s-benzylisothiourea. A sulfur compound such as p-tosylate or the like.

The amount of the photopolymerization initiator and the photosensitizer to be used is preferably 0.05 to 20 parts by mass, and preferably 0.5 to 10 parts by mass per 100 parts by mass of the non-volatile component in the active energy ray-curable aqueous coating material of the present invention. The quality % is better.

Further, in the active energy ray-curable composition of the present invention, in order to impart a good touch, it is preferred to blend the cerium oxide particles (D). Examples of the cerium oxide particles (D) include dry cerium oxide and wet cerium oxide. Among these, from the viewpoint of further improving the feeling of touch, dry cerium oxide is preferred, and dry cerium oxide surface-modified with an organic compound is more preferable. The average particle diameter of the cerium oxide particles is preferably in the range of 1 to 20 μm, and more preferably in the range of 5 to 15 μm. Furthermore, the average particle diameter is laser diffraction. The scattering particle size analyzer is a measurer.

Further, in the active energy ray-curable composition of the present invention, it is preferred to blend the fluorenone-based surface conditioner (E) in order to impart a good touch. Examples of the surface conditioning agent (E) include a polyoxyalkylene-modified acrylic resin, a polyether-denatured polydimethylsiloxane, and the like.

In the active energy ray-curable composition of the present invention, an organic solvent, an antistatic agent, an antifoaming agent, a viscosity adjusting agent, a light stabilizer, a weathering stabilizer, a heat stabilizer, a UV absorber, an antioxidant, and a leveling can be used. Additives such as a solvent, an organic pigment, an inorganic pigment, and a pigment dispersant are blends other than the above components (A) to (E).

In addition, the application method of the active energy ray-curable composition of the present invention varies depending on the article to be coated, and examples thereof include a gravure coater, a roll coater, a two-roll coater, a knife coater, and an air knife coating. Machine, curtain coater, contact coater, spray coater, Wheeler coater, spin coater, dipping, screen printing, spraying, applicator, bar coater, etc.

Further, in order to adjust the viscosity of the active energy ray-curable composition of the present invention to be suitable for the coating method, the organic solvent is diluted. Better release. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; methanol, ethanol, isopropanol, tert-butanol, propylene glycol monomethyl ether, propylene glycol n-propyl ether, and ethylene glycol monobutyl ether. An alcohol solvent such as diacetone alcohol; an ester solvent such as ethyl acetate, butyl acetate, isobutyl acetate, n-propyl acetate, propylene glycol monomethyl ether acetate; methyl ethyl ketone, methyl isobutyl ketone, A ketone solvent such as diisobutyl ketone or cyclohexanone. These solvents may be used singly or in combination of two or more.

As the active energy ray which hardens the active energy ray-curable composition of the present invention, as described above, it is free radiation such as ultraviolet rays, electron beams, α rays, β rays, γ rays, etc., as a specific energy source or curing device, for example. Examples include germicidal lamps, ultraviolet fluorescent lamps, carbon arc lamps, xenon lamps, high-pressure mercury lamps for rewriting, medium-pressure or high-pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, metal halide lamps, and ultraviolet light using natural light as a light source. Or use an electron beam of a scanning type, a curtain type electron beam accelerator, or the like.

The active energy ray-curable composition of the present invention imparts softness to the surface of various articles.

The active energy ray-curable composition of the present invention can be directly applied to an article to be coated, but in order to further improve the adhesion to the object to be coated, after applying the undercoat layer suitable for the object to be coated, It is preferred to apply the active energy ray-curable composition of the present invention.

As the undercoat layer coating material, for example, a one-liquid type in which an acrylic resin or the like is diluted with an organic solvent, a solution in which a polyol is diluted with an organic solvent, and a solution in which a polyisocyanate is diluted with an organic solvent can be used. All kinds of things.

Examples of the material of the article to be coated include polycarbonate (hereinafter abbreviated as "PC"), acrylonitrile-butadiene-styrene copolymer (hereinafter abbreviated as "ABS"), and PC-ABS. Various resins of polymer alloys, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polydecylamine (PA), polypropylene (PP), etc.; glass fibers are added to the resins Fiber-reinforced plastic (FRP) of fillers, etc.; various metals such as iron, copper, zinc, aluminum, magnesium, and the like.

The article of the present invention is a cured coating film having the active energy ray-curable composition of the present invention, and examples thereof include a main body of a home appliance such as a refrigerator, a television, and an air conditioner, and a remote controller, a mobile phone, and a smart phone. A plastic molded product such as an outer casing of an information terminal such as a computer or an automobile interior material.

[Examples]

The invention will now be described in further detail by way of specific examples.

(Synthesis Example 1: Synthesis of Polyfunctional Acrylate (1))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port, 178.72 parts by mass of a hexamethylene diisocyanate 3-polymer (NCO: 23.5% by mass) and 1.35 parts by mass of dibutylhydroxytoluene were added. 0.14 parts by mass of formazan and 0.14 parts by mass of dioctyltin diruthenate were heated to 60 ° C while stirring under air. Next, polypropylene glycol monoacrylate ("BLEMMER AP-400" manufactured by Nippon Oil Co., Ltd., average number of repeating units of PO n = 6 and hydroxyl value = 115) of 497.58 parts by mass was added dropwise over 1 hour. After the completion of the dropwise addition, the urethane was carried out by heating the reaction vessel to 80 ° C and stirring for 5 hours. The esterification reaction was carried out, and the mixture was diluted with ethyl acetate to a nonvolatile content of 80% by mass to obtain a solution of the polyfunctional acrylate (1).

(Synthesis Example 2: Synthesis of multifunctional acrylate (2))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port, 178.72 parts by mass of a hexamethylene diisocyanate 3-polymer (NCO: 23.5 mass%) and 1.49 parts by mass of dibutylhydroxytoluene were added. 0.16 parts by mass of formazan and 0.16 parts by mass of dioctyltin diruthenate were heated to 60 ° C while stirring under air. Next, polypropylene glycol monoacrylate ("BLEMMER AP-550" manufactured by Nippon Oil Co., Ltd., average number of repeating units of PO n = 9 and hydroxyl value = 93) of 615.29 parts by mass was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 80% by mass to obtain a polyfunctional acrylate ( 2) solution.

(Synthesis Example 3: Synthesis of multifunctional acrylate (3))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port, 178.72 parts by mass of a hexamethylene diisocyanate 3-polymer (NCO: 23.5 mass%) and 2.2 parts by mass of dibutylhydroxytoluene were added. 0.22 parts by mass of formazan and 0.22 parts by mass of dioctyltin diruthenate were heated to 60 ° C while stirring under air. Next, propylene glycol monoacrylate ("BLEMMER AP-800" manufactured by Nippon Oil Co., Ltd., the average number of repeating units of PO n = 13 and hydroxyl value = 62) of 922.93 parts by mass was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 80% by mass to obtain a polyfunctional acrylate ( 3) solution.

(Synthesis Example 4: Synthesis of polyfunctional acrylate (4))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port, 178.72 parts by mass of a hexamethylene diisocyanate 3-polymer (NCO: 23.5 mass%) and 1.0 part by mass of dibutylhydroxytoluene were added. 0.10 parts by mass of formazan and 0.10 parts by mass of dioctyltin diruthenate were heated to 60 ° C while stirring under air. Next, polyethylene glycol monoacrylate ("BLEMMER AE-200" manufactured by Nippon Oil Co., Ltd., average number of repeating units of EO n = 4.5, hydroxyl value = 171) 334.63 parts by mass was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 80% by mass to obtain a polyfunctional acrylate ( 4) solution.

(Synthesis Example 5: Synthesis of multifunctional acrylate (5))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port, 178.72 parts by mass of a hexamethylene diisocyanate 3-polymer (NCO: 23.5 mass%) and 1.6 parts by mass of dibutylhydroxytoluene were added. 0.16 parts by mass of formazan and 0.16 parts by mass of dioctyltin diruthenate were heated to 60 ° C while stirring under air. Next, polyethylene glycol monoacrylate ("BLEMMER AE-400" manufactured by Nippon Oil Co., Ltd., average number of repeating units of EO n = 10, hydroxyl value = 95.6) 598.56 parts by mass was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 80% by mass to obtain a polyfunctional acrylate ( 5) solution.

(Synthesis Example 6: Synthesis of multifunctional acrylate (6))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port, 178.72 parts by mass of a hexamethylene diisocyanate 3-polymer (NCO: 23.5% by mass) and 2.8 parts by mass of dibutylhydroxytoluene were added. 0.28 parts by mass of toluene and 0.28 parts by mass of dioctyltin dicaprate were heated to 60 ° C while stirring under air. Next, it took 1 hour to add polyethylene glycol monoacrylate ("BLEMMER AE-400", Nippon Oil Co., Ltd., EO average repeating unit number n = 10, hydroxyl value = 95.6) 299.28 parts by mass and polypropylene glycol single Acrylate ("BLEMMER AP-400" manufactured by Nippon Oil Co., Ltd., the average number of repeating units of PO n = 6 and hydroxyl value = 115) 248.79 parts by mass. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 80% by mass to obtain a polyfunctional acrylate ( 6) solution.

(Synthesis Example 7: Synthesis of multifunctional acrylate (7))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port, 178.72 parts by mass of a hexamethylene diisocyanate 3-polymer (NCO: 23.5 mass%) and 1.2 parts by mass of dibutylhydroxytoluene were added. Toluene 0.12 parts by mass of 0.12 parts by mass of dioctyltin dicaprylate was heated to 60 ° C while stirring under air. Next, 12.67 parts of propylene glycol was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanation reaction, and it was confirmed that the isocyanate group content of the mixture in the container was 14.6% or less, and the temperature was lowered to 60 ° C. Then, it took 1 hour to add polyethylene glycol monoacrylate (made by Nippon Oil Co., Ltd.). "BLEMMER AE-400", EO average repeating unit number n = 10, hydroxyl value = 95.6) 399.04 parts by mass. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 80% by mass to obtain a polyfunctional acrylate ( 7) solution. Further, the isocyanate group content rate is measured in accordance with JIS Test Method K 1603-1.

(Synthesis Example 8: Synthesis of polyfunctional acrylate (R1))

A reaction product of lactone triol and hexamethylene diisocyanate was added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port ("DURANATE E402-100", NCO, manufactured by Asahi Kasei Chemicals Co., Ltd.) : 9.0 mass%) 466.67 parts by mass, 1.2 parts by mass of dibutylhydroxytoluene, 0.12 parts by mass of formazan, and 0.12 parts by mass of dioctyltin diruthenate, and the temperature was raised to 60 ° C while stirring under air. . Next, 118.32 parts by mass of 2-hydroxyethyl acrylate was added dropwise over 1 hour. After completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 60% by mass to obtain a polyfunctional acrylate ( Solution of R1).

(Synthesis Example 9: Synthesis of polyfunctional acrylate (R2))

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port, 178.72 parts by mass of a hexamethylene diisocyanate 3-polymer (NCO: 23.5% by mass) and 0.8 parts by mass of dibutylhydroxytoluene were added. 0.08 parts by mass of formazan and 0.08 parts by mass of dioctyltin diruthenate were heated to 60 ° C while stirring under air. Secondly, it takes 1 hour to add polypropylene glycol monoacrylate (Nippon Oil has Limited company "BLEMMER AP-150", PO average repeating unit number n = 3, hydroxyl value = 239) 239.42 parts by mass. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 80% by mass to obtain a polyfunctional acrylate ( Solution of R2).

(Synthesis Example 10: Synthesis of polyfunctional acrylate (R3))

111 parts by mass of isophorone diisocyanate, 1.5 parts by mass of dibutylhydroxytoluene, 0.15 parts by mass of formazan, and dinonanoic acid II were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air introduction port. 0.15 parts by mass of octyl tin was heated to 60 ° C while stirring under air. Next, polypropylene glycol monoacrylate ("BLEMMER AP-550" manufactured by Nippon Oil Co., Ltd., average number of repeating units of PO n = 9 and hydroxyl value = 93) 615.3 parts by mass was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction mixture was heated to 80 ° C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate to give a nonvolatile content of 80% by mass to obtain a polyfunctional acrylate ( Solution of R3).

(Example 1: Preparation of active energy ray-curable composition (1))

112.5 parts by mass of a solution (nonvolatile content: 80% by mass) of the polyfunctional acrylate (1) obtained in Synthesis Example 1 (90 parts by mass of the polyfunctional acrylate (1)), and a photopolymerization initiator (BASF Japan) was added thereto. 3 parts by mass of "IRGACURE 184" and 1-hydroxycyclohexyl phenyl ketone manufactured by Co., Ltd., 10 parts by mass of cerium oxide particles ("ACEMATT 3300" manufactured by Evonik Co., Ltd., average particle diameter: 9.5 μm), and polyoxyalkylene denaturation Acrylic resin (BYK-3550, BYK Japan Co., Ltd., non-volatile 52 % by mass; hereinafter referred to as "surface conditioner (1)"), 0.77 parts by mass (0.4 parts by mass of active ingredient) and polyether-denatured polydimethyl siloxane (BYK-333, manufactured by BYK Japan Co., Ltd.) The non-volatile matter was 97% by mass or more; hereinafter referred to as "surface conditioning agent (2)"), 0.3 parts by mass, and uniformly mixed to obtain an active energy ray-curable composition (1).

(Examples 2 to 7: Preparation of active energy ray-curable composition (2) to (7))

The active energy ray-curable compositions (2) to (7) were prepared in the same manner as in Example 1 except that the composition shown in Table 1 or Table 2 below was changed.

(Comparative Examples 1 to 3: Preparation of Active Energy Ray Curable Compositions (R1) to (R3))

The active energy ray-curable compositions (R1) to (R3) were prepared in the same manner as in Example 1 except that the composition shown in Table 2 below was changed.

The composition of the active energy ray-curable compositions (1) to (7) and (R1) to (R3) obtained above is shown in Tables 1 and 2.

[Preparation of primer coating agent (A)]

Acrylic resin (ACRYDIC A-166, manufactured by DIC Co., Ltd., non-volatile content: 45 mass%) as a diluent (diacetone alcohol / methyl isobutyl ketone / ethyl acetate / butyl acetate = 30 / 30 / 20 /20 (% by mass) was diluted to make the viscosity of the "viscosity cup NK-2" manufactured by ANEST IWATA Co., Ltd. for 8 to 9 seconds (23 ° C) to obtain an undercoat material (A).

[Preparation of primer coating agent (B)]

Polyisocyanate (BURNOCK DN-980S, manufactured by DIC Corporation, NCO: 21.0% by mass) was blended with acrylic resin (ACRYDIC WXU-880, manufactured by DIC Co., Ltd., nonvolatile content: 50% by mass, hydroxyl number = 10). ), the equivalent ratio (OH/NCO) of the hydroxyl group (OH) to the isocyanate group (NCO) is 1, and the diluent (diacetone alcohol / methyl isobutyl ketone / ethyl acetate / butyl acetate = 30 / 30) /20/20 (% by mass)) was diluted to make the viscosity of the "viscosity cup NK-2" manufactured by ANEST IWATA Co., Ltd. for 8 to 9 seconds (23 ° C) to obtain a primer coating agent (B).

[Production of substrate for evaluation]

On the surface of the resin sheet (thickness: 1 mm) of the ABS as the substrate, the primer coating material (A) or (B) prepared as described above was spray-coated, and left at room temperature (25 ° C) for 10 minutes, at 80 The mixture was dried at ° C for 20 minutes to form undercoat layers (A) and (B) having a film thickness of 10 μm on the substrate.

(Example 8: Evaluation of active energy ray-curable composition (1))

The active energy ray-curable composition (1) obtained in Example 1 was used as a diluent (diacetone alcohol / methyl isobutyl ketone / ethyl acetate / butyl acetate = 30 / 30 / 20 / 20 (% by mass) After diluting until the viscosity of the sprayable coating is applied, the surface of the undercoat layers (A) and (B) of the substrate for evaluation obtained above is spray-coated. Thereafter, after standing at room temperature (25 ° C) for 10 minutes, it was preliminarily dried at 60 ° C for 10 minutes in a drier, and then irradiated with ultraviolet rays having an irradiation amount of 0.8 J/cm ² using a high-pressure mercury lamp outputting 80 W/cm to prepare a film. A hardened coating film for evaluation of 30 μm thick.

[Adhesion test and evaluation]

The hardened coating film for evaluation obtained above was measured in accordance with the checkerboard test method of JISK-5400. Adding a 1mm wide dent to the hardened coating film to make the number of checkerboards 100, attaching the celluloid tape to cover all the checkerboards, and quickly stripping them, and depending on the adhesion and residual The number of checkerboards was evaluated by the following criteria.

◎: 90~100

○: 80~89

△: 50~79

×: 49 or less

[Evaluation of softness]

The surface of the cured coating film for evaluation obtained by the above-mentioned finger was touched with a finger, and the softness was evaluated based on the following tactile sensation by the following criteria.

5: Elastic and silky touch

4: slightly lower elasticity but smooth touch

3: No elasticity, a sense of grip with a grip

2: Non-elastic, sticky touch

1: There is a sticky touch

(Examples 9 to 14: Evaluation of active energy ray-curable composition (2) to (7))

The active energy ray-curable compositions (2) to (7) obtained in Examples 2 to 7 were used instead of the active energy ray-curable composition (1) obtained in Example 1 used in Example 8, except In the same manner as in Example 8, except that the cured coating film for evaluation was produced, the adhesion and the flexibility were evaluated.

(Comparative Examples 4 to 6: Evaluation of Active Energy Ray Curable Compositions (R1) to (R3))

The active energy ray-curable compositions (R1) to (R3) obtained in Comparative Examples 1 to 3 were used instead of the active energy ray-curable composition (1) obtained in Example 1 used in Example 8, except In the same manner as in Example 8, except that the cured coating film for evaluation was produced, the adhesion and the flexibility were evaluated.

The evaluation results of the above Examples 8 to 14 and Comparative Examples 4 to 6 are shown in Tables 3 and 4.

It is understood that Examples 1 to 7 of the active energy ray-curable composition of the present invention have very high adhesion to the undercoat layer. Further, it is also known that the cured coating film has a good touch feeling softness (Examples 8 to 14).

On the other hand, Comparative Example 1 is an example in which a polyfunctional acrylate having no isomeric cyanate ring and a polyoxyalkylene chain in its structure is used, and it is understood that it is completely immiscible with the undercoat layer, and the adhesion is good. Poor, softness is also insufficient (Comparative Example 4).

Comparative Example 2 is an example in which a polyfunctional acrylate having an average repeating unit number n of a polyoxyalkylene chain of less than 4 of the lower limit of the present invention is used, and it is found that the undercoat layer is not completely adhered to the undercoat layer, and the adhesion is poor. The softness was also insufficient (Comparative Example 5).

Comparative Example 3 is an example in which a polyfunctional acrylate having no isomeric cyanate ring in its structure was used, and it was found that the adhesion to the undercoat layer was extremely high, but the flexibility was insufficient (Comparative Example 6).

Claims (6)

An active energy ray-curable composition comprising a polyoxyalkylene chain having a structure of a hetero-cyanate ring and a urethane bond, and having an average number of repeating units of 4 to 20, and The urethane bond is a (meth) acrylate group (meth) acrylate (A) having a polyoxyalkylene chain on the opposite side. The active energy ray-curable composition of claim 1, wherein the (meth) acrylate (A) is a polyisocyanate (a1) having an iso-cyanate ring and a poly-oxidation having an average repeating number of 4 to 20 The mono(meth)acrylate (a2) is obtained by reaction. The active energy ray-curable composition of claim 2, wherein the polyoxyalkylene mono(meth)acrylate (a2) is a polyoxypropylene mono(meth)acrylate and/or a polyoxyethylene mono(methyl) group. Acrylate. The active energy ray-curable composition of claim 2 or 3, wherein the polyisocyanate (a1) is a terpolymer comprising hexamethylene diisocyanate. A hardened coating film obtained by irradiating an active energy ray-curable composition according to any one of claims 1 to 4 with an active energy ray. An article having a cured coating film as claimed in claim 5.