KR20150136467A - Active-energy-ray-curable composition, cured coating film thereof, and article having said cured coating film - Google Patents

Abstract

A polyoxyalkylene chain having an average number of repeating units of 4 to 20 is bonded through a urethane bond and a structure having an isocyanurate ring, and a (meth) acryloyl group is bonded to the terminal of the polyoxyalkylene chain on the opposite side of the urethane bond (Meth) acrylate (A) having a diol group and a (meth) acrylate (B) having a caprolactone structure. This active energy ray-curable composition can impart soft feeling to the surface of various articles and can obtain a coating film having high adhesion with a plastic substrate. Examples of the article include plastic articles such as a main body of a home appliance such as a refrigerator, a television, and an air conditioner, a casing of an information terminal such as a remote control, a mobile phone, a smart phone, and a PC, and an automobile interior material.

Description

TECHNICAL FIELD [0001] The present invention relates to an active energy ray curable composition, an active energy ray curable composition, a cured coating film thereof, and an article having the cured coating film (ACTIVE-ENERGY-RAY-CURABLE COMPOSITION, CURED COATING FILM THEREOF, AND ARTICLE HAVING SAID CURED COATING FILM)

The present invention relates to an active energy ray curable composition capable of imparting softness to the surface of various articles and capable of obtaining a coating film having high adhesiveness with a base material and an article using the same.

2. Description of the Related Art In recent years, plastic molded articles have been widely used in the body of home appliances such as refrigerators, televisions, air conditioners, and the casings of information terminals such as remote controllers, cellular phones, smart phones, and PCs. In these plastic molded articles, molded parts are sometimes used as they are, but they are often painted to give designability. Conventionally, a lot of designs can be visually perceived such as color, gloss, and the like. In recent years, however, it has been examined to give a touch such as soft feel, which is felt softly when touched with a finger, have.

Examples of the material imparting soft feel property include a polyester polyol having two or more hydroxyl groups in one molecule and an isocyanate compound obtained by reacting hexamethylene diisocyanate with an active energy obtained by further reacting with a (meth) acrylate having a hydroxyl group There has been proposed a composition for an active energy ray-curable top coat containing a radiation-curable urethane (meth) acrylate and a photopolymerization initiator (see, for example, Patent Document 1). However, the active energy ray-curable top coat composition has a problem of insufficient tactile sensation such as high elasticity and low grip feeling required for soft-paced character.

Thus, there has been a demand for an active energy ray curable composition which can impart soft feel to the surface of a plastic molded article and has high adhesion with a plastic molded article.

Japanese Patent Application Laid-Open No. 2007-131700

An object of the present invention is to provide an active energy ray curable composition and a product using the active energy ray curable composition which are capable of imparting excellent feel and soft feel to surfaces of various articles and obtaining a coating film having high adhesion with a base material.

The inventors of the present invention have made extensive studies in order to solve the above problems and found that (meth) acrylate having an isocyanurate ring and polyoxyalkylene chain and (meth) acrylate having a caprolactone structure By using the energy ray curable composition, it has been found that a coating film having high compatibility with a base material can be imparted to the surface of various articles with softness and softness can be obtained, thereby completing the invention.

That is, the present invention relates to a polyoxyalkylene chain having an isocyanurate ring and a polyoxyalkylene chain having an average number of repeating units of 4 to 20 bonded via a urethane bond, and the terminal of the polyoxyalkylene chain on the opposite side of the urethane bond (Meth) acryloyl group having a (meth) acryloyl group and a (meth) acrylate (B) having a caprolactone structure, and an article using the active energy ray curable composition will be.

The active energy ray curable composition of the present invention can impart softness to the surface of various articles and can obtain a coating film having high adhesion with a substrate. Therefore, softness can be imparted to the surface of a wide range of plastic molded articles such as a main body of a home appliance such as a refrigerator, a television, and an air conditioner, and a casing of an information terminal such as a remote control, a mobile phone, a smart phone and a PC.

The active energy ray curable composition of the present invention has a structure having an isocyanurate ring and a polyoxyalkylene chain having an average number of repeating units of 4 to 20 bonded through a urethane bond, (Meth) acrylate (A) having a (meth) acryloyl group at the end of an alkylene chain and (meth) acrylate (B) having a caprolactone structure. The polyoxyalkylene chain and the terminal (meth) acryloyl group may be bonded through a divalent organic group such as a urethane bond.

In the present invention, the term "(meth) acryloyl" refers to one or both of an acryloyl group and a methacryloyl group, and "(meth) acrylate" refers to one or both of acrylate and methacrylate (Meth) acrylic acid "refers to one or both of acrylic acid and methacrylic acid.

First, the (meth) acrylate (A) will be described. The (meth) acrylate (A) has an isocyanurate ring and a polyoxyalkylene chain having an average number of repeating units of 4 to 20 in its structure.

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

(1) A method in which an isocyanate group of a polyisocyanate compound (a1) having an isocyanurate ring and a hydroxyl group of a polyoxyalkylene mono (meth) acrylate (a2) are subjected to urethanization reaction.

(2) After the urethane reaction of the isocyanate group of the polyisocyanate compound (a1) and one hydroxyl group of two hydroxyl groups of the polyoxyalkylene (polyalkylene glycol), the remaining hydroxyl groups and (meth) acrylic acid are esterified Lt; / RTI >

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

The urethanization reaction and the esterification reaction carried out 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 urethanization catalyst. Examples of the urethanization catalyst include amine compounds such as triethylamine, dibutyltin dilaurate, dioctyltin dilaurate, octyltin dilaurate, dioctyltin dineodecanate, dibutyltin di Organic tin compounds such as acetate, dioctyltin diacetate and tin dioctylate, and organometallic compounds such as zinc octylate (zinc 2-ethylhexanoate).

Further, in the above-mentioned method (2) or (3), there is a problem that polyurethane occurs due to the urethanation reaction involving only the triisocyanate compound (a1) and polyoxyalkylene. However, in the method (1), there is no such a problem, so that the (meth) acrylate (A) is more easily obtained.

The polyisocyanate compound (a1) may be any as long as it has an isocyanurate ring in its structure, and examples thereof include triisocyanates of diisocyanate. Examples of the diisocyanate include hexamethylene diisocyanate, phenylenediisocyanate, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, and the like. A polyisocyanate obtained by reacting a trihydrate of these diisocyanates with a polyol can also be used as the polyisocyanate compound (a1). Examples of the polyol include aliphatic diols such as 2,2,4-trimethyl-1,3-pentanediol, 1,3-hexanediol and 1,6-hexanediol, dimers of unsaturated aliphatic alcohols, . These polyisocyanate compounds (a1) may be used alone or in combination of two or more.

Among the above polyisocyanate compounds (a1), it is preferable to include trihydrate of hexamethylene diisocyanate, since soft feel properties with better tactile properties can be obtained.

The polyoxyalkylene mono (meth) acrylate (a2) is a compound having a polyoxyalkylene chain having an average number of repeating units of 4 to 20 and a (meth) acryloyl group, and may be, for example, 1). ≪ / RTI >

(In the general formula (1), R represents a hydrogen atom or a methyl group, A represents an alkylene group, n represents an average number of repeating units, and the range is from 4 to 20. A is one or more And in the case of two or more kinds, the repeating units may be arranged in a random phase or in a block state)

Among the compounds represented by the general formula (1), the polyoxyalkylene mono (meth) acrylate (a2) is preferably an alkylene group in which A is an alkylene group having 1 to 6 carbon atoms, and A is a poly Oxypropylene mono (meth) acrylate, and polyoxyethylene mono (meth) acrylate wherein A is an ethylene group.

In the general formula (1), the range of n representing the average number of repeating oxyalkylene groups is preferably from 5 to 14, and more preferably from 6 to 13.

As specific examples of the polyoxyalkylene mono (meth) acrylate (a2), an average number of repeating units of "Blenda AP-400" (oxypropylene (hereinafter abbreviated as "PO" (average number of repeating units of PO is n = 9), "Brenma AP-800" (average number of repeating units of PO = n = 13), "Brenma AE-200" (The average number of repeating units of oxyethylene (hereinafter abbreviated as " EO ") n = 4.5) and Brenma AE-400 (the average number of repeating units of EO n = 10). These polyoxyalkylene mono (meth) acrylates (a2) may be used alone or in combination of two or more.

Examples of the compound (a3) having an isocyanate group and a (meth) acryloyl group include 2- (meth) acryloyloxyethyl isocyanate, 1,1- (bis (meth) acryloyloxymethyl) ethyl Isocyanate and the like.

When the (meth) acrylate (A) is produced by the above method (1), the isocyanate group (NCO) of the polyisocyanate compound (a1) and the polyoxyethylene mono (meth) acrylate (NCO / OH) with respect to the hydroxyl group (OH) contained in the resin (A) is preferably in the range of 0.8 to 1.1, more preferably 0.9 to 1.05, and still more preferably 0.95 to 1.02.

Next, the (meth) acrylate (B) will be described. The (meth) acrylate (B) has a caprolactone structure and a (meth) acryloyl group in its structure.

Examples of the (meth) acrylate (B) include caprolactone-modified alkyl (meth) acrylate (BA) represented by the following formula (2) Urethane (meth) acrylate (BU) obtained by urethanization of a polyhydric alcohol, a polyester (meth) acrylate (BE) obtained by esterification reaction of the above (meth) acrylate (BA) and a polycarboxylic acid compound, (Meth) acrylate (BM) obtained by esterifying (meth) acrylic acid with a compound in which part or all of the compound is modified with caprolactone.

(In the general formula (2), R represents a hydrogen atom or a methyl group, m represents an integer of 1 to 6, and n represents an average number of repeating units,

Among these, (meth) acrylate (B) is preferably (meta) acrylate having an average number of repeating units of caprolactone structure of 2 to 10 because adhesion and softening property are improved.

Specific examples of the caprolactone-modified alkyl (meth) acrylate (BA) include "Prakuselu FA-2D" (m = 2, n = 2 in the general formula (2)) of Dyeru K.K., (M = 2, n = 10 in the general formula (2)) and the like can be given . These polycaprolactone-modified alkyl (meth) acrylates (BA) may be used alone or in combination of two or more.

Examples of the polyisocyanate compound used in the production of the (meth) acrylate (BU) include tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylene bis (dimethylmethylene) di Aromatic diisocyanate compounds such as isocyanate; Hexamethylene diisocyanate, lysine diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane , 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and other aliphatic or alicyclic diisocyanate compounds.

As the polyisocyanate compound, there may be mentioned a prepolymer having an isocyanate group obtained by subjecting the above diisocyanate compound to an addition reaction with a polyhydric alcohol; A compound having an isocyanurate ring obtained by cyclization of the above diisocyanate compound; A polyisocyanate compound having an urea bond or a buret bond obtained by reacting the above diisocyanate compound with water can also be used.

These polyisocyanate compounds may be used alone or in combination of two or more.

The urethane formation reaction in the production of the (meth) acrylate (BU) can be carried out by the known method described above as a method for producing the (meth) acrylate (A).

Examples of the polycarboxylic acid compound used in the production of (meth) acrylate (BE) include aliphatic polycarboxylic acid compounds such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, ; And aromatic polycarboxylic acid compounds such as phthalic acid and trimellitic acid.

As the polycarboxylic acid compound, a prepolymer having a carboxyl group obtained by reacting the above polycarboxylic acid compound with a polyhydric alcohol can also be used.

The esterification reaction in the production of the (meth) acrylate (BE) can be carried out by a known method.

As the polyhydric alcohol used in the production of the (meth) acrylate (BM)

Trimethylol propane, pentaerythritol, ditrimethylol propane, dipentaerythritol, tripentaerythritol, diglycerin, polyglycerin, and the like.

The esterification reaction in the production of the (meth) acrylate (BM) can be carried out by a known method.

Specific examples of the (meth) acrylate (BM) include "Kayalladium DPCA-60" (caprolactone-modified dipentaerythritol hexaacrylate, average number of repeating units of caprolactone 1) manufactured by Nihon Kayaku Co., , "Kayalladium DPCA-120" (caprolactone-modified dipentaerythritol hexaacrylate, caprolactone having an average number of repeating units of 2), and the like.

The active energy ray curable composition of the present invention is not particularly limited as long as it contains the above (meth) acrylate (A) and the above (meth) acrylate (B) The ester group concentration in the solid content of the composition is preferably in the range of 1.2 to 6.5 mmol / g, more preferably in the range of 1.8 to 6 mmol / g.

In the present invention, the ester group concentration in the solid content of the composition means,

(M) of the ester group in the (meth) acrylate + (m) of the ester group in the (meth) acrylate (B) Mol) " / " mass (g) of solid content of composition ". The photopolymerization initiator is not included in the solid content of the composition.

In addition to the (meth) acrylate (A) and the (meth) acrylate (B), the active energy ray curable composition of the present invention may contain other active energy ray curable monomer (C). In this case, the ester group concentration in the solid content of the composition means,

(M) of the ester group in the (meth) acrylate + (m) of the ester group in the (meth) acrylate (B) (M) of the ester group in the active energy ray-curable monomer (C) / (mass) (g) of the solid content of the composition. The photopolymerization initiator is not included in the solid content of the composition.

Examples of the active energy ray-curable monomer (C) include N- (2-hydroxyethyl) (meth) acrylamide, N-isopropyl (meth) acrylamide, (meth) acryloylmorpholine, (Meth) acrylamide, diethyl (meth) acrylamide, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl Acrylate, 4-hydroxybutyl (meth) acrylate, and the like. These active energy ray-curable monomers (C) may be used alone or in combination of two or more.

Further, the active energy ray curable composition of the present invention can be made into a cured coating film by applying an active energy ray after coating the base material. This active energy ray refers to ionizing radiation such as ultraviolet rays, electron rays, alpha rays, beta rays, and gamma rays. When ultraviolet rays are irradiated as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (D) to the active energy ray curable composition of the present invention to improve the curability. Further, if necessary, a photosensitizer may be further added to improve the curability. On the other hand, when ionizing radiation such as electron beam,? -Ray,? -Ray or? -Ray is used, it hardens quickly without using a photopolymerization initiator (D) or a photosensitizer. You do not have to.

Examples of the photopolymerization initiator (D) include an intramolecular cleavage type photopolymerization initiator and a hydrogen-drawing type photopolymerization initiator. Examples of the intramolecular isotactic photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- Acetophenone compounds such as 2-morpholino (4-thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; Benzoin such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoindienylphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzyl, methylphenylglyoxyester and the like.

Examples of the hydrogen-withdrawing photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl- Benzophenone based compounds such as diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl- compound; Thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler-ketone and 4,4'-diethylaminobenzophenone; Butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators (D) may be used alone or in combination of two or more.

Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, urea such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate And the like.

The amount of the photopolymerization initiator and photosensitizer used is preferably 0.05 to 20 parts by mass, more preferably 0.5 to 10% by mass, based on 100 parts by mass of the nonvolatile component in the active energy ray-curable aqueous coating composition of the present invention.

The active energy ray curable composition of the present invention preferably contains silica particles (E) in order to impart good tactile sensation. Examples of the silica particles (E) include dry silica and wet silica. Of these, dry silica is preferable, and dry silica surface-modified with an organic compound is more preferable because tactile feel is improved. The average particle diameter of the silica particles is preferably in the range of 1 to 20 mu m, more preferably in the range of 5 to 15 mu m. The average particle diameter was measured by a laser diffraction / scattering particle size analyzer.

The active energy ray curable composition of the present invention is preferably blended with the silicon surface-adjusting agent (F) in order to impart better tactile sensation. Examples of the surface modifier (E) include a polysiloxane-modified acrylic resin and a polyether-modified polydimethylsiloxane.

The active energy ray curable composition of the present invention may contain an organic solvent, an antistatic agent, a defoaming agent, a viscosity adjusting agent, a light stabilizer, a weather stabilizer, a heat stabilizer, an ultraviolet absorber, Leveling agents, organic pigments, inorganic pigments, pigment dispersants and the like can be used.

The coating method of the active energy ray-curable composition of the present invention is not limited to a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, , A wheeler coater, a spin coater, dipping, a screen printing, a spray, an applicator, and a bar coater.

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

As described above, the active energy ray for curing the active energy ray-curable composition of the present invention is ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays and gamma rays, but specific energy sources or curing devices include, Or a curtain type electron beam accelerator using a light source such as a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high pressure mercury lamp for copying, a medium pressure or high pressure mercury lamp, an ultra high pressure mercury lamp, And the like.

The active energy ray-curable composition of the present invention can impart softness to surfaces of various articles.

The active energy ray curable composition of the present invention may be applied directly to an article to be coated, and may be coated with a primer coating material suitable for the object to be coated with the active energy ray curable composition of the present invention.

Examples of the primer porcelain include a one-component type in which an acrylic resin or the like is diluted with an organic solvent, and a two-component type in which 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.

As the material of the object to be coated, polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (hereinafter abbreviated as ABS), polymer glass of PC-ABS, polymethyl methacrylate ( PMMA), polyethylene terephthalate (PET), polyamide (PA), and polypropylene (PP); Fiber reinforced plastic (FRP) in which a filler such as glass fiber is put into these resins; Iron, copper, zinc, aluminum, and magnesium, and alloys thereof.

The article of the present invention has a cured coating film of the active energy ray-curable composition of the present invention. However, the article of the present invention is not limited to the curable coating film of the active energy ray curable composition of the present invention, A casing of a terminal, and a plastic molded article such as an automobile interior material.

[Example]

Hereinafter, the present invention will be described in more detail with reference to specific examples.

(Synthesis Example 1: Synthesis of (meth) acrylate (A-1)

Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and an air inlet, 178.72 parts by mass of hexamethylene diisocyanate trimer (NCO: 23.5 mass%), 1.55 parts by mass of dibutylhydroxytoluene, And 0.15 parts by mass of dioctyltin dinneodecanate were charged and the temperature was raised to 60 占 폚 while stirring with air. Subsequently, 598.56 parts by mass of polyoxyethylene monoacrylate ("Brenma AE-400" manufactured by Nichiyu Corporation, average number of repeating units of EO = 10, hydroxyl value = 95.6) was added dropwise over one hour. After completion of the dropwise addition, the inside of the reaction vessel was heated to 80 DEG C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate so as to have a nonvolatile content of 80% by mass to obtain a solution of (meth) acrylate (A- (Ester group concentration in solid content: 1.3 mmol / g).

(Synthesis Example 2: Synthesis of (meth) acrylate (B-1)

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and an air inlet, 178.72 parts by mass of hexamethylene diisocyanate trimer (NCO: 23.5% by mass), 1.06 parts by mass of dibutylhydroxytoluene, And 0.11 parts by mass of dioctyltin dinodecanate were charged and the temperature was raised to 60 占 폚 while stirring with air. Subsequently, 351.1 parts by mass of polycaprolactone-modified hydroxyethyl monoacrylate ("PRACUSERU FA-2D" manufactured by Daicel Chemical Industries, Ltd .; the average number of repeating units of caprolactone n = 2 and hydroxyl group = 163.0) And added. After completion of the dropwise addition, the inside of the reaction vessel was heated to 80 DEG C and stirred for 5 hours to carry out a urethanization reaction, and diluted with ethyl acetate so as to have a nonvolatile content of 80% by mass to obtain a solution of (meth) acrylate (B-1) (Ester group concentration in solid content: 5.8 mmol / g).

(Synthesis Example 3: Synthesis of (meth) acrylate (B-2)

A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and an air inlet was charged with 131.18 parts by mass of 4,4'-dicyclohexylmethane diisocyanate, 1.0 part by mass of dibutylhydroxytoluene, 0.1 parts by mass of methoquinone, And 0.1 part by mass of dioctyltin dinodecanate, and the temperature was raised to 60 ° C while stirring with air. Subsequently, 351.1 parts by mass of polycaprolactone-modified hydroxyethyl monoacrylate ("PRACUSERU FA-2D" manufactured by Daicel Chemical Industries, Ltd .; the average number of repeating units of caprolactone n = 2 and hydroxyl group = 163.0) And added. After completion of the dropwise addition, the inside of the reaction vessel was heated to 80 DEG C and stirred for 5 hours to carry out the urethanization reaction, and diluted with ethyl acetate so as to have a nonvolatile content of 80% by mass to obtain a solution of (meth) acrylate (B-2) (Ester group concentration in solid content: 6.3 mmol / g).

(Synthesis Example 4: Synthesis of (meth) acrylate (B-3)

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and an air inlet, 178.72 parts by mass of hexamethylene diisocyanate trimer (NCO: 23.5 mass%), 1.8 parts by mass of dibutylhydroxytoluene, And 0.2 parts by mass of dioctyltin dinneodecanate were charged, and the temperature was raised to 60 占 폚 while stirring with air. Subsequently, 715.3 parts by mass of polycaprolactone-modified hydroxyethyl monoacrylate ("PRACUSELU FA-5" manufactured by Daishu K.K.), the number of average repeating units of caprolactone (n = 5, hydroxyl value = 80.0) And added. After completion of the dropwise addition, the inside of the reaction vessel was heated to 80 DEG C and stirred for 5 hours to carry out the urethanization reaction, and diluted with ethyl acetate so as to have a nonvolatile content of 80% by mass to obtain a solution of (meth) acrylate (B-3) (Ester group concentration in solid content: 6.8 mmol / g).

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

(67.5 parts by mass as (meth) acrylate (A-1)) of the solution of the (meth) acrylate (A-1) obtained in Synthesis Example 1 (nonvolatile matter 80% (22.5 parts by mass as a (meth) acrylate (B-1)) (28% by mass of a nonvolatile component of 80% by mass) was added a photopolymerization initiator (BASF Japan, 10 parts by mass of silica particles (" ACEMATT 3300 ", product of Ebonit Co., Ltd., average particle diameter 9.5 占 퐉), 3 parts by mass of polysiloxane-modified acrylic resin (Big Chemie Japan 0.77 parts by mass (0.4 parts by mass as an effective component) and polyether-modified polydimethylsiloxane (produced by BYK-3550, nonvolatile matter: 52 mass%; hereinafter abbreviated as " (BYK-333 manufactured by Japan Kogyo Co., Ltd., nonvolatile content of 100 mass%; hereinafter abbreviated as "surface control agent (2)") It was uniformly mixed, and an ester group concentration of the solid content to obtain the active energy ray curable composition (1) of the 2.2m㏖ / g.

(Examples 2 to 7: preparation of active energy ray curable compositions (2) to (7)) [

Except that the solution of the (meth) acrylate (A-1) used in Example 1 and the solution of the (meth) acrylate (B-1) were changed to the compositions shown in the following Table 1 , Active energy ray curable compositions (2) to (7) were prepared.

(Comparative Examples 1 and 2: preparation of active energy ray-curable compositions (R1) to (R2)

Except that the solution of the (meth) acrylate (A-1) and the solution of the (meth) acrylate (B-1) used in Example 1 were changed to the compositions shown in the following Table 2 , Active energy ray-curable compositions (R1) to (R2) were prepared.

The compositions of the active energy ray-curable compositions (1) to (7) and (R1) to (R2) obtained above are shown in Table 1.

[Table 1]

The "(meth) acrylate (B-4)" in the above Table 1 is a mixture of a polylactone-modified DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.: polycaprolactone-modified dipentaerythritol hexaacrylate, (Number of repeating units: 2, ester group concentration in the solid content: 9.2 mmol / g), and "(meth) acrylate (B-5)" was a copolymer of FAX-5 (manufactured by Daicel Chemical Industries, Ltd .: polycaprolactone The average number of repeating units of caprolactone is 5, the hydroxyl value is 80.0, and the ester group concentration in the solid content is 8.6 mmol / g).

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

The active energy ray curable composition (1) obtained above was applied to a surface of a resin plate (thickness: 1 mm) of ABS by using a thinner (diacetone alcohol / methyl isobutyl ketone / ethyl acetate / butyl acetate = 30/30/20/20 (mass%)), and spray-applied. Thereafter, the resultant was allowed to stand at room temperature (25 ° C) for 10 minutes, preliminarily dried at 60 ° C for 10 minutes in a dryer, irradiated with ultraviolet rays at a dose of 0.8 J / cm 2 using a high pressure mercury lamp with an output of 80 W / cm, A cured coating film for evaluation was prepared.

[Adhesion Test and Evaluation]

The cured coating film for evaluation obtained above was measured according to the crosscut test method of JIS K-5400. The number of crosscuts was set to 100 in a 1 mm-wide sheath with a cutter on the cured coating film. A cellophane tape was attached so as to cover all the crosscuts. From the number of crosscuts remaining attached, The adhesion was evaluated by the standards.

?: 90 to 100

○: 80 to 89

?: 50 to 79

X: 49 or less

[Evaluation of softness]

The surface of the cured coating film for evaluation obtained above was touched with a finger, and the soft feel was evaluated from the obtained tactile sensation by the following criteria.

5: Resilient and silky tactile

4: Slightly less elastic but smooth touch

3: There is no elasticity and a little grip.

2: No elasticity and a feeling of grip

1: Touching touch

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

Except that the active energy ray curable composition (1) obtained in Example 1 used in Example 8 was replaced with the active energy ray curable compositions (2) to (7) obtained in Examples 2 to 7, respectively, To prepare a cured coating film for evaluation, and the appearance of the coating film, the adhesion property and the soft feel property were evaluated.

(Comparative Examples 3 to 4: Evaluation of active energy ray curable compositions (R1) to (R2)

Except that the active energy ray curable compositions (R1) to (R2) obtained in Comparative Examples 1 and 2 were used instead of the active energy ray curable composition (1) obtained in Example 1 used in Example 8, To prepare a cured coating film for evaluation, and the appearance of the coating film, the adhesion property and the soft feel property were evaluated.

The evaluation results of Examples 8 to 14 and Comparative Examples 3 to 4 are shown in Table 2.

[Table 2]

It was found that the active energy ray curable compositions of Examples 1 to 7 of the present invention had very high adhesion to a substrate. In addition, it was found that the cured coating film had soft feel property with good touch (Examples 8 to 14).

On the other hand, Comparative Example 1 shows that the composition does not contain a (meth) acrylate having a polycaprolactone structure, but has poor adhesion to a substrate (Comparative Example 3).

Comparative Example 2 was an example of not containing (meth) acrylate having an isocyanurate ring and a polyoxyalkylene chain in its structure, but it was found that the soft solubility was insufficient (Comparative Example 4).

Claims (8)

A polyoxyalkylene chain having an average number of repeating units of 4 to 20 is bonded through a urethane bond and a structure having an isocyanurate ring, and a (meth) acryloyl group is bonded to the terminal of the polyoxyalkylene chain on the opposite side of the urethane bond Wherein the active energy ray-curable composition contains a (meth) acrylate (A) having a diene group and a (meth) acrylate (B) having a caprolactone structure. The method according to claim 1,
Wherein the concentration of the ester group in the solid content is 1.2 to 6.5 mmol / g. 3. The method according to claim 1 or 2,
(Meth) acrylate (A) is obtained by reacting a polyisocyanate (a1) having an isocyanurate ring with a polyoxyalkylene mono (meth) acrylate (a2) having an average number of repeating units of 4 to 20 ≪ / RTI > active energy ray curable composition. The method of claim 3,
Wherein the polyoxyalkylene mono (meth) acrylate (a2) is polyoxypropylene mono (meth) acrylate and / or polyoxyethylene mono (meth) acrylate. The method according to claim 3 or 4,
Wherein the polyisocyanate (a1) comprises a trimer of hexamethylene diisocyanate. 6. The method according to any one of claims 1 to 5,
Wherein the average number of repeating units of the caprolactone structure of the (meth) acrylate (B) is 2 to 10. A cured coating film obtained by irradiating the active energy ray curable composition according to any one of claims 1 to 6 with an active energy ray. An article characterized by having the cured coating film according to claim 7.