KR20150138281A - Active-energy-ray-curable composition, cured coating film thereof, and article having said cured coating film - Google Patents

Abstract

(Meth) acrylate (A) having an isocyanurate ring, a polyoxyalkylene chain having an average number of repeating units of 4 to 20, and a caprolactone structure. The present invention also provides an active energy ray curable composition. This active energy ray-curable composition can impart softness to the surface of various articles when softly felt when touched with a finger, and can form a coating film having excellent adhesion with a plastic substrate. Examples of the article include various types 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, 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 ray obtained by reacting with an (meth) acrylate having a hydroxyl group Curable urethane (meth) acrylate and a photopolymerization initiator (for example, refer to Patent Document 1). However, this active energy ray-curable top coat composition has a problem of insufficient tactile sensation such as high elasticity and low grip feeling necessary for soft-feeling property.

Therefore, there is a demand for an active energy ray curable composition that can impart excellent 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.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that (A) an isocyanurate ring, a polyoxyalkylene chain having an average number of repeating units of 4 to 20 and a caprolactone structure By using an active energy ray-curable composition comprising an active energy ray-curable composition which is capable of imparting soft feel to the surface of various articles and capable of obtaining a coating film having high adhesiveness to a substrate.

That is, the present invention relates to an active energy ray-curable composition (A) comprising an isocyanurate ring, a polyoxyalkylene chain having an average number of repeating units of 4 to 20, and a (meth) acrylate having a caprolactone structure And articles using the same.

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 contains an isocyanurate ring, a polyoxyalkylene chain having an average number of repeating units of 4 to 20, and (meth) acrylate (A) having a caprolactone structure.

In the present invention, the term "(meth) acryloyl" refers to one or both of acryloyl and methacryloyl, "(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, in its structure, an isocyanurate ring, a polyoxyalkylene chain having an average number of repeating units of 4 to 20, and a caprolactone structure.

Examples of the method for producing (meth) acrylate (A) include the following methods (1) to (7).

(A1) a polyisocyanate compound having an isocyanurate ring and an isocyanate group of a polyoxyalkylene mono (meth) acrylate (a2) and a hydroxyl group and caprolactone-modified alkylmono (meth) acrylate (a3) Is subjected to a urethanization reaction.

(2) After the urethane-forming reaction of the isocyanate group of the polyisocyanate compound (a1) and the hydroxyl group of one of the two hydroxyl groups of the polyalkylene glycol and the caprolactone-modified alkylmono (meth) acrylate (a3) , And the remaining hydroxyl group and (meth) acrylic acid are subjected to an esterification reaction.

(3) The polyisocyanate compound represented by the general formula (1) wherein the isocyanate group of the polyisocyanate compound (a1) and the hydroxyl group of the polyoxyalkylene mono (meth) acrylate (a2) A part is subjected to urethanization reaction, and the remaining hydroxyl group and (meth) acrylic acid are subjected to an esterification reaction.

(4) A method for producing a polyurethane foam, which comprises reacting a part of hydroxyl groups of a compound in which a part or all of the hydroxyl groups of one hydroxyl group and polyhydric alcohol of two polyoxyalkylene groups of the polyisocyanate compound (a1) with caprolactone are modified with urethane (Meth) acrylic acid is subjected to an esterification reaction.

(5) A method of reacting the remaining hydroxyl group with a compound (a4) having an isocyanate group and a (meth) acryloyl group after the urethanization reaction of the above (2).

(6) A method of reacting the remaining hydroxyl group with a compound (a4) having an isocyanate group and a (meth) acryloyl group after the urethanization reaction of the above (3).

(7) A method of reacting the remaining hydroxyl group with a compound (a4) having an isocyanate group and a (meth) acryloyl group after the urethanization reaction of the above (4).

The urethanization reaction and the esterification reaction carried out by the methods (1) to (7) can be carried out by a known method. For example, the urethanization reaction is preferably carried out in the presence of an urethane catalyst. Examples of the urethanization catalyst include amine compounds such as triethylamine, dibutyltin dilaurate, dioctyltin di Organic tin compounds such as octyltin dilaurate, dodecyltin dineodecanate, dibutyltin diacetate, dioctyltin diacetate and tin dioctylate, zinc octylate (zinc 2-ethylhexanoate) and the like Organic metal compounds and the like.

Further, in the above methods (2) to (7), there is a problem that polyurethane is generated by the urethanation reaction involving only the polyisocyanate compound (a1) and polyoxyalkylene. Although control is difficult, the method (1) is preferable because the (meth) acrylate (A) can be obtained more easily because there is no such a problem.

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 "BURRAMA AP-400" (oxypropylene (hereinafter abbreviated as "PO") (average number of repeating units of PO = n = 9), " Brenma AP-800 " (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 caprolactone-modified alkyl (meth) acrylate (a3) include compounds represented by the following general formula (2).

(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, the (meth) acrylate (a3) 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 (meth) acrylate (a3) include "Prakuselu FA-2D" (m = 2, n = 2 in the general formula (2)), "Prakuselu FA- (M = 2 in the general formula (2), n = 5), and "Prakuselu FA-10" (m = 2 in the general formula (2), n = 10). These (meth) acrylates (a3) may be used alone or in combination of two or more.

Examples of the compound (a4) 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 equivalent number of isocyanate groups (NCO) of the polyisocyanate compound (a1) and the number of polyoxyethylene mono (OH) of the number of hydroxyl groups (OHa2) of the acrylate (a2) and the number of equivalents (OHa3) of the hydroxyl groups contained in the caprolactone-modified alkyl (meth) acrylate (a3) OH) is preferably in the range of 0.8 to 1.1, more preferably in the range of 0.9 to 1.05, and still more preferably in the range of 0.95 to 1.02.

The active energy ray curable composition of the present invention may be one containing the above (meth) acrylate (A), but since the adhesion with the base material is improved, the ester group concentration in the solid content of the composition is preferably 1.9 to 6.5 mmol / g , And more preferably in the range of 2.2 to 6 mmol / g.

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

Is calculated in accordance with " concentration of ester group in solid component of composition (mmol / g) " = number of moles of ester group in (meth) acrylate (A) / mass of solid component (g) . The photopolymerization initiator is not included in the solid content of the composition.

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

(M mol / g) in the solid content of the composition = (number of moles of the ester group in the (meth) acrylate (A) + number of moles of the ester group in the active energy ray- Mol) " / " mass (g) of solid content of composition ". The photopolymerization initiator is not included in the solid content of the composition.

Examples of the active energy ray curable monomer (B) 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 (B) may be used singly or in combination of two or more kinds.

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 an active energy ray to form a cured coating film, it is preferable to add a photopolymerization initiator (C) 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 and? -Ray is used, it hardens rapidly without using a photopolymerization initiator (C) or a photosensitizer so that the photopolymerization initiator (C) You do not have to.

Examples of the photopolymerization initiator (C) 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 such as diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl- Nonnary compounds; 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, and camphaquinone. These photopolymerization initiators (C) 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 is preferably blended with silica particles (D) in order to give a good tactile sensation. Examples of the silica particles (D) 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.

In order to impart better tactile feel to the active energy ray-curable composition of the present invention, it is preferable to blend the silicon-based surface modifier (E). 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, as other components of the above components (A) to (E), organic solvents, antistatic agents, antifoaming agents, viscosity adjusting agents, light stabilizers, weather stabilizers, heat stabilizers, , 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 FOILER coater, a spin coater, dipping, screen printing, spraying, 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 normal 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.

(PC), acrylonitrile-butadiene-styrene copolymer (hereinafter abbreviated as ABS), polymer alloy 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 polyfunctional acrylate (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 mass%), 1.28 parts by mass of dibutylhydroxytoluene, And 0.13 parts by mass of dioctyltin dinodecanate were charged, and the mixture was heated to 60 占 폚 while stirring with passing air. Subsequently, 269.35 parts by mass of polyoxyethylene monoacrylate ("Bremen AE-400" manufactured by Nichiyu Corporation, average number of repeating units of EO = 10, hydroxyl value = 95.6), and polycaprolactone-modified hydroxyethylmono Acrylate ("Pracusheru FA-2D" manufactured by Daicel Chemical Industries, Ltd., the number of the average repeating units of caprolactone n = 2, and the hydroxyl group = 163.0) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction vessel was heated to 80 ° 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 the polyfunctional acrylate (1) Ester group concentration in solid content: 3.3 mmol / g).

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

To the 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%), 1.58 parts by mass of dibutylhydroxytoluene, And 0.16 parts by mass of dioctyltin dinneodecanate were charged and the temperature was raised to 60 占 폚 while stirring with air. Subsequently, 496.8 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), and polycaprolactone-modified hydroxyethylmono Acrylate ("PRACUSERU FA-5" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., the average number of repeating units of caprolactone n = 5 and hydroxyl group = 80.0) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C and stirred for 5 hours to carry out urethanization reaction, and diluted with ethyl acetate so as to have a nonvolatile content of 80% by mass to obtain a solution of polyfunctional acrylate (2) Ester group concentration in solid content: 2.4 mmol / g).

(Synthesis Example 3: Synthesis of polyfunctional acrylate (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%), 1.40 parts by mass of dibutylhydroxytoluene, And 0.14 parts by mass of dioctyltin dinneodecanate were charged, and the temperature was raised to 60 占 폚 while stirring with air. Subsequently, 407.02 parts by mass of polyoxyethylene monoacrylate ("Brenma AE-400" manufactured by Nichiyu Corporation, the average number of repeating units of EO = 10, the hydroxyl value = 95.6) and the polycaprolactone-modified hydroxyethylmono , And 112.3 parts by mass of acrylate ("PRACUSERU FA-2D" manufactured by Daicel Chemical Industries, Ltd., the average number of repeating units of caprolactone n = 2 and hydroxyl group = 163.0) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction vessel was heated to 80 ° 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 the polyfunctional acrylate (3) Ester group concentration in solid content: 2.4 mmol / g).

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

To 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%), 1.60 parts by mass of dibutylhydroxytoluene, And 0.16 parts by mass of dioctyltin dinneodecanate were charged and the temperature was raised to 60 占 폚 while stirring with air. Subsequently, 483.04 parts by mass of polyoxyethylene monoacrylate ("Bremen AE-400" manufactured by Nichiyu Corporation, average number of repeating units of EO = 10, hydroxyl value = 95.6), and polycaprolactone-modified hydroxyethylmono , And 138.05 parts by mass of acrylate ("Pracusheru FA-5" manufactured by Daicel Chemical Industries, Ltd., the average number of repeating units of caprolactone n = 5 and hydroxyl group = 80.0) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction vessel was heated to 80 캜 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 the polyfunctional acrylate (4) Ester group concentration in solid content: 2.5 mmol / g).

(Synthesis Example 5: Synthesis of polyfunctional acrylate (5)) [

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%), 1.76 parts by mass of dibutylhydroxytoluene, And 0.18 parts by mass of dioctyltin dinneodecanate were charged, and the mixture was heated to 60 占 폚 while stirring with air. Subsequently, 71.83 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) and polycaprolactone-modified hydroxyethylmono Acrylate ("PRAKUSERU FA-5" manufactured by Daicel Chemical Industries, Ltd., the average number of repeating units of caprolactone was n = 5, and the hydroxyl value was 80.0) was added dropwise over 1 hour. After completion of the dropwise addition, 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 the polyfunctional acrylate (5) Ester group concentration in solid content: 6.3 mmol / g).

(Synthesis Example 6: Synthesis of polyfunctional acrylate (R1)

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%), 1.44 parts by mass of dibutylhydroxytoluene, And 0.14 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 1 hour. After completion of the dropwise addition, 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 polyfunctional acrylate (R1) Ester group concentration in solid content: 1.3 mmol / g).

(Synthesis Example 7: Synthesis of polyfunctional acrylate (R2)) [

A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air inlet was charged with 111 parts by mass of isophorone diisocyanate, 1.5 parts by mass of dibutylhydroxytoluene, 0.15 parts by mass of methoquinone and 150 parts by mass of dioctyltin dinodecanate And the temperature was raised to 60 占 폚 while stirring with air. Subsequently, 715.3 parts by mass of polycaprolactone-modified hydroxyethyl monoacrylate ("PRACUSERU 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 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 polyfunctional acrylate (R2) Ester group concentration in solid content: 7.4 mmol / g).

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

112.5 parts by mass (90 parts by mass as polyfunctional acrylate (1)) of a solution (nonvolatile matter 80% by mass) of the polyfunctional acrylate (1) obtained in Synthesis Example 1 was added with a photopolymerization initiator (produced by BASF Japan Co., 10 parts by mass of silica particles (" ACEMATT 3300 ", product of Ebonikusha Co., Ltd., average particle diameter 9.5 占 퐉), 3 parts by mass of polysiloxane-modified acrylic resin (manufactured by Bikkukemi Japan K.K. 0.77 parts by mass (0.4 parts by mass as an effective component) and 50 parts by mass of a polyether-modified polydimethylsiloxane (trade name: BYK-3550, nonvolatile matter: 52 mass%; hereinafter abbreviated as " (Hereinafter referred to as " BYK-333 ", nonvolatile matter 100% by mass; hereinafter abbreviated as " surface modifier 2 ") were added and uniformly mixed to obtain an active energy ray having an ester group concentration of 2.9 mmol / To obtain a curable composition (1).

(Examples 2 to 5: preparation of active energy ray curable compositions (2) to (5)) [

(2) to (5) were prepared in the same manner as in Example 1, except that the composition shown in the following Table 1 was used.

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

The actinic energy ray curable compositions (R1) to (R2) were prepared by the same procedure as in Example 1 except that the compositions shown in the following Table 1 were used.

Table 1 shows the compositions of the active energy ray-curable compositions (1) to (5) and (R1) to (R2)

[Table 1]

(Example 6: 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 DEG C) for 10 minutes, preliminarily dried at 60 DEG C for 10 minutes in a dryer, irradiated with ultraviolet rays at a dose of 0.8 J / cm2 using a high-pressure mercury lamp with an output of 80 W / 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 by putting a 1 mm-wide cutter on the cured coating film, a cellophane tape was stuck to cover all the crosscuts, To evaluate the adhesion.

?: 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 7 to 10: Evaluation of active energy ray-curable compositions (2) to (5)

Except that the active energy ray curable composition (1) obtained in Example 1 used in Example 6 was replaced by the active energy ray curable compositions (2) to (5) obtained in Examples 2 to 5, The cured coating film for evaluation was produced in the same manner to evaluate the appearance of the coating film, the adhesion property, and the soft feel property.

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

The active energy ray curable composition (1) obtained in Example 6 was used in place of the active energy ray curable compositions (R1) to (R2) obtained in Comparative Examples 1 and 2, The cured coating film for evaluation was produced in the same manner to evaluate the appearance of the coating film, the adhesion property, and the soft feel property.

The evaluation results of Examples 6 to 10 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 5 of the present invention had a very high adhesion to a base material. In addition, it was found that the cured coating film had soft feel property with good touch (Examples 6 to 10).

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

Comparative Example 2 shows that the (meth) acrylate (A) does not have a polyoxyalkylene chain, but the softness property is insufficient (Comparative Example 4).

Claims (8)

(Meth) acrylate (A) having an isocyanurate ring, a polyoxyalkylene chain having an average number of repeating units of 4 to 20, and a caprolactone structure. The method according to claim 1,
Wherein the concentration of the ester group in the solid content is 1.9 to 6.5 mmol / g. 3. The method according to claim 1 or 2,
(Meth) acrylate (a) having an isocyanurate ring and a polyoxyalkylene mono (meth) acrylate (a2) having an average number of repeating units of 4 to 20 and a caprolactone-modified alkyl Mono (meth) acrylate (a3). 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 3 to 5,
Wherein the average number of repeating units of the caprolactone structure of the (meth) acrylate (a3) 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.