TW201802132A - Active energy ray curable composition - Google Patents

Abstract

To provide an active energy ray curable composition providing a cured film excellent in hardness, scratch property and moldability. An active energy ray curable composition contains urethane (meth)acrylate which is a reaction product of (A) a (meth)acrylic acid addition of tri- or higher valent aliphatic polyvalent alcohol compound having hydroxyl group value of 160 mgKOH/g to 220 mgKOH/g, (B) (2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate and (C) an organic isocyanate compound.

Description

Active energy ray hardening composition

The present invention relates to an active energy ray-curable composition containing an amine ester (meth) acrylate and capable of obtaining a cured film excellent in hardness, scratch resistance, and formability.

For various substrates such as metal, plastic, and wood, a method of forming a protective film has been used for the purpose of protecting the surface of the substrate. The protective film is obtained by using a coating composition. In particular, the plastic substrate is light in weight and excellent in impact resistance and formability, but has a low surface hardness and is easy to be damaged. Therefore, if it is used directly, the appearance may be damaged over time. Therefore, plastic surfaces are seeking to improve surface hardness.

As a method for solving this problem, a method of coating a plastic surface with a coating composition (hard coating treatment) has been used. As the coating composition, a silicone resin composition, an acrylic resin composition, A thermosetting resin composition such as a melamine-based resin composition has a problem that it takes a long time to cure and cannot be applied to a less heat-resistant plastic film substrate.

In recent years, active energy ray-curable resin compositions have been used as a hard coating treatment agent for plastic film substrates because of their rapid hardening properties and their ability to harden even at low energy and low temperatures.

As such an active energy ray-curable resin composition, a radiation-curable resin composition has been proposed, which contains a polyfunctional urethane acrylate, which is a radiation-curable polyfunctional (formaldehyde) (Meth) acrylate is reacted with polyisocyanate, and this radiation-curable polyfunctional (meth) acrylate has at least two (meth) acryl groups and hydroxyl groups in the molecule (Patent Document 1).

In addition, an active energy ray-curable composition has also been proposed, which contains: a reaction product of an amine ester (meth) acrylate and a compound having an ethylenically unsaturated group; and the amine ester (meth) acrylate The reaction product is obtained by reacting a (meth) acrylic acid adduct having a hydroxyl value of 140 mgKOH / g or more with a polyisocyanate compound (Patent Document 2). [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Publication No. 2001-113648 Patent Document 2: Japanese Patent Publication No. 2015-021089

[Problems to be Solved by the Invention] However, in Patent Document 1, as a specific example of a radiation-curable resin composition, a polyfunctional amine ester acrylate is described in which pentaerythritol triacrylate and isophorone diisocyanate are used. Addition (refer to paragraph [0026]), the polyfunctional amine acrylate has a large shrinkage due to hardening. Therefore, in order to obtain a film thickness required for abrasion resistance, curling after hardening may be excessive and the film may be excessively large. The problem of moldability such as warpage.

Further, in Patent Document 2, as a specific example of the active energy ray-curable composition, an amine ester acrylate (see paragraph [0091]) and polypropylene glycol diacrylate (see paragraph [0052]) are described. This amine ester acrylate is obtained by adding an acrylate of pentaerythritol having a hydroxyl value of 173 mgKOH / g and isophorone diisocyanate, and this mixture has a problem of insufficient scratch resistance.

The present invention has been made in view of the problems described above, and an object thereof is to provide an active energy ray-curable composition capable of obtaining a cured film having an excellent balance among hardness, scratch resistance, and formability. [Technical means to solve the problem]

The active energy ray-curable composition of the present invention includes an amine ester (meth) acrylate, which is a reaction product of the following (A), (B), and (C): ( (A) (meth) acrylic acid adduct of a ternary or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less; (B) bis (2- (meth) acrylic acid oxyethyl) Group) hydroxyethyl isocyanurate; (C) organic isocyanate compound.

(A) The (meth) acrylic acid adduct of a ternary or higher aliphatic polyol compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less, and the aliphatic polyol compound thereof is preferably ternary or higher and Below 6 yuan aliphatic polyhydric alcohol, more preferably pentaerythritol.

The (C) organic isocyanate compound is preferably one or two or more selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate.

The active energy ray-curable composition preferably further contains (D) a polyfunctional (meth) acrylate having three or more (meth) acrylfluorenyl groups in one molecule.

The ratio of the (A) component to the (B) component, that is, (A) / (B) is 95/5 to 50/50 in terms of mass ratio.

In the active energy ray-curable composition, it is preferable that a total value a + b of the Mohr number of the hydroxyl group of the component (A) and the Mohr number of the hydroxyl group of the component (B) calculated from the hydroxyl value, and the ( C) The molar ratio of the molar number c of the isocyanate group of the component, that is, (a + b) / c, is 0.5 or more and less than 1. [efficacy]

According to the active energy ray-curable composition of the present invention, a cured film having high hardness, high abrasion resistance, and excellent moldability can be obtained.

Hereinafter, embodiments of the present invention will be described in detail. The active energy ray-curable composition of the present invention includes an amine ester (meth) acrylate, which is a reaction product of the following (A), (B), and (C): ( (A) (meth) acrylic acid adduct of a ternary or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less; (B) bis (2- (meth) acrylic acid oxyethyl) Group) hydroxyethyl isocyanurate; (C) organic isocyanate compound. In addition, (meth) acrylic acid refers to acrylic acid and / or methacrylic acid, and bis (2- (meth) acryloxyethyl) hydroxyethyl isocyanurate refers to bis (2) -Acryloxyethyl) hydroxyethyl isocyanurate and / or bis (2-methacryloxyethyl) hydroxyethyl isocyanurate. In this specification, "(methyl) ..." all have the same meaning.

(A) A (meth) acrylic acid adduct of a ternary or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less (hereinafter sometimes referred to as (meth) acrylic acid adduct) ) Can be obtained by adding (meth) acrylic acid to a predetermined ternary or higher aliphatic polyol (hereinafter sometimes referred to as an aliphatic polyol) by an esterification reaction.

The above-mentioned aliphatic polyol is not particularly limited as long as it is an alcohol compound having 3 or more members, and is preferably an aliphatic polyol having 3 or more members and 6 members or less, and more preferably a 4-membered aliphatic polyol. When the valence of the aliphatic polyol is 3 yuan or more, the hardness of the hardened material obtained from the composition can be easily increased. When the valence of the aliphatic polyol is 6 yuan or less, the occurrence of hardened materials can be easily reduced. Curl means improved formability.

Specific examples of the aliphatic polyol include trimethylolpropane, an alkylene oxide adduct of trimethylolpropane, pentaerythritol, an alkylene oxide adduct of pentaerythritol, and bis (trimethylol). Propane), bis (trimethylolpropane) alkylene oxide adduct, dipentaerythritol, dipentaerythritol alkylene oxide adduct, tripentaerythritol, tripentaerythritol alkylene oxide adduct, glycerin, glycerol Sugar derivatives such as alkylene oxide adducts, sucrose, and alkylene oxide adducts of sucrose; and alkylene oxide adducts of sugar derivatives. Examples of the alkylene oxide adduct include ethylene oxide, propylene oxide, and butylene oxide, and one or two or more of these can be used.

Among these, from the viewpoint of improving the hardness of the hardened product obtained from the composition, trimethylolpropane, an alkylene oxide adduct of trimethylolpropane, pentaerythritol, and an alkylene oxide of pentaerythritol are preferred. Adducts, dipentaerythritol, alkylene oxide adducts of dipentaerythritol, tripentaerythritol, and tripentaerythritol alkylene oxide adducts, more preferably pentaerythritol and dipentaerythritol. Particularly preferred is pentaerythritol.

Moreover, the said aliphatic polyhydric alcohol can be used individually by 1 type or in combination of 2 or more types, It is preferable to use 1 type individually.

The (meth) acrylic acid is acrylic acid and / or methacrylic acid, and preferably only acrylic acid is used.

When producing the (meth) acrylic acid adduct, in addition to (meth) acrylic acid, (meth) acrylic halide, (meth) acrylic anhydride, (meth) acrylate compound, and the like can also be used.

The hydroxyl value of the (meth) acrylic acid adduct is preferably 160 mgKOH / g or more, more preferably 170 mgKOH / g or more; preferably 220 mgKOH / g or less, and more preferably 200 mgKOH / g or less. When a compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less is used, a cured film excellent in hardness, scratch resistance, and formability is easily obtained.

Here, the hydroxyl value in this specification refers to the number of milligrams (mg) of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated, and is based on JIS. K 0070-1992.

The (meth) acrylic acid adduct may include a (meth) acrylic acid adduct having no hydroxyl group, preferably includes a (meth) acrylic acid adduct having one hydroxyl group, and more preferably includes a (meth) acrylic acid adduct having 2 (Meth) acrylic acid adduct of each hydroxyl group.

The (meth) acrylic acid adduct can be produced by a conventional esterification reaction, and a catalyst or a stabilizer is preferably used. The catalyst is preferably, for example, an acid catalyst. In addition, the stabilizer may be a conventional polymerization inhibitor such as hydroquinone monomethyl ether. In addition, it is also preferable to use oxygen as a stabilizer, especially a polymerization inhibitor. For example, by performing an esterification reaction of the above-mentioned aliphatic polyol and (meth) acrylic acid in an oxygen-containing environment, it is possible to prevent excess (meth) acrylic acid or (meth) acrylic acid ester from polymerizing. Moreover, it is preferable that the manufacturing method of the said (meth) acrylic-acid adduct includes the following methods, for example, refinement | purification by liquid-liquid extraction (liquid separation). According to the manufacturing method described above, the (meth) acrylic acid adduct having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less can be easily manufactured.

The above bis (2- (meth) acryloxyethyl) hydroxyethyl isocyanurate can be produced by: tris (2-hydroxyethyl) isocyanurate and (methyl ) Acrylic acid undergoes dehydration esterification. At this time, the reaction product is obtained as a mixture of 1 to 3 substitutions of (meth) acrylic acid. Generally, the 1 substitution is removed during the refining process, and the 2 substitution, that is, bis (2- The form of a mixture of (meth) acryloxyethyl) hydroxyethyl isocyanurate and 3 substituents, that is, tris (2- (meth) acryloxyethyl) isocyanurate is in Circulation on the market. A commercially available product of such a mixture is, for example, "ARONIX M-215" manufactured by Toa Synthesis Co., Ltd.

The mixing ratio of bis (2- (meth) acryloxyethyl) hydroxyethyl isocyanurate and tris (2- (meth) acryloxyethyl) isocyanurate is bis (2- (Meth) acryloxyethyl) hydroxyethyl isocyanurate / tris (2- (meth) acryloxyethyl) isocyanurate is not particularly limited, and the mass ratio is It is preferably 100/0 to 30/70, more preferably 100/0 to 35/65, and still more preferably 100/0 to 40/60.

(B) The component is bis (2- (meth) acryloxyethyl) hydroxyethyl isocyanurate. Bis (2- (meth) acryloxyethyl) hydroxyethyl can be used. Mixtures of isocyanurate and tris (2- (meth) acryloxyethyl) isocyanurate. When using a mixture, the reaction product may contain both an amine ester (meth) acrylate and unreacted tris (2- (meth) acryloxyethyl) isocyanurate, but it can be used directly This reaction product is used as the hardening composition of the present invention.

Various compounds can be used as the (C) organic isocyanate compound, and are not particularly limited. Specific examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecyl methylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2, 4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,4-cyclohexane diisocyanate. , Methylcyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like.

Examples of the aromatic polyisocyanate include toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate ( MDI), 4,4'-diphenylmethyl diisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate, 1,3-benzenediisocyanate, 1,4-benzenediisocyanate, and the like.

Examples of the aromatic aliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylene diisocyanate, and the like.

In addition, for example, a dimer or trimer of such an organic isocyanate compound, or a modified body such as a diuretized isocyanate.

These organic isocyanate compounds can be used alone or in combination of two or more. From the viewpoint that the hardened material obtained from the composition will have high hardness and low curlability, the organic isocyanate compound is preferably one selected from the group consisting of the above-mentioned aliphatic polyisocyanate and alicyclic polyisocyanate. Or 2 or more. Among these, hexamethylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate are more preferable.

The mass ratio of the component (A) to the component (B) of the present invention, that is, (A) / (B) is not particularly limited, but is preferably 95/5 to 50/50.

In addition, the total value of the mole numbers of the hydroxyl groups (A) component (B) and (B) component calculated from the hydroxyl value a + b and the mole ratio c of the isocyanate group of the component (C) is (a + b) ) / c is not particularly limited, but is preferably 0.5 or more and less than 1.

The active energy ray-curable composition of the present invention can further contain (D) a polyfunctional (meth) acrylate having three or more (meth) acrylfluorenyl groups in one molecule (hereinafter sometimes referred to simply as multifunctional (meth) (Meth) acrylate). By containing the said polyfunctional (meth) acrylate, the hardness of the hardened film obtained from a composition can be improved more.

The content of the above-mentioned polyfunctional (meth) acrylate (the total amount when two or more kinds are used in combination) is not particularly limited, and it is 0 to 90 parts by mass in a total amount of 100 parts by mass with the amine ester (meth) acrylate. Preferably, 0 to 80 parts by mass is more preferred, and 0 to 70 parts by mass is more preferred.

The polyfunctional (meth) acrylate is not particularly limited, and specific examples thereof include an acrylate of trimethylolpropane, an acrylate of an alkylene oxide adduct of trimethylolpropane, an acrylate of pentaerythritol, Acrylates of alkylene oxide adducts of pentaerythritol, acrylates of bis (trimethylolpropane), acrylates of bis (trimethylolpropane) alkylene oxide adducts, acrylates of dipentaerythritol, Acrylates of alkylene oxide adducts of pentaerythritol, acrylates of tripentaerythritol, acrylates of alkylene oxide adducts of pentaerythritol, 2-propenyloxyethyl isocyanurate, acrylates of glycerol, Sugar derivatives such as acrylates of alkylene oxide adducts of glycerol, acrylates of sucrose, and acrylates of sucrose alkylene oxide adducts, and acrylates of alkylene oxide adducts of sugar derivatives. These can be used alone or in combination of two or more.

Examples of the alkylene oxide adduct include ethylene oxide, propylene oxide, and butylene oxide, and one or two or more of these can be used.

Among these, from the viewpoint of improving the hardness of the hardened material obtained from the composition, acrylates of pentaerythritol, acrylates of alkylene oxide adducts of pentaerythritol, acrylates of dipentaerythritol, and dipentaerythritol are preferred. Acrylates of alkylene oxide adducts, acrylates of tripentaerythritol, acrylates of alkylene oxide adducts of tripentaerythritol, 2-propenyloxyethyl isocyanurate, more preferably acrylic acid of dipentaerythritol Ester, 2-propenyloxyethyl isocyanurate.

The amine ester (meth) acrylate of the present invention can be synthesized by a conventional method, and is not particularly limited. It can be synthesized by, for example, the presence of a polymerization inhibitor such as hydroquinone monomethyl ether in one side of about 70 It heats at -80 degreeC until the free isocyanate disappears, stirring a predetermined amount of (A), (B), (C). In this case, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate may be added.

The active energy ray-curable composition of the present invention can contain organic solvents such as ethyl acetate and methyl ethyl ketone and / or monomers as required. Examples of the monomers include acrylates of pentaerythritol, acrylates of alkylene oxide adducts of pentaerythritol, acrylates of dipentaerythritol, acrylates of alkylene oxide adducts of dipentaerythritol, acrylates of tripentaerythritol, Acrylates of alkylene oxide adducts of tripentaerythritol, 2-propenyloxyethyl isocyanurate, and the like. These may be used alone or in combination of two or more.

In the active-energy-ray-curable composition, the content of the amine ester (meth) acrylate is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more.

The curable composition of the present invention can contain a polymerization initiator of an active energy ray as required. The polymerization initiator of the active energy ray herein refers to both a polymerization initiator including a photopolymerization initiator and an active energy ray such as ultraviolet rays.

The photopolymerization initiator is not particularly limited, and examples thereof include aromatic ketones such as benzophenone; aromatic compounds such as anthracene and α-chloromethylnaphthalene; diphenyl sulfide and thiourethane. Sulfur compounds.

Although it does not specifically limit as a polymerization initiator of active energy ray other than visible light, such as acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2, 2-dimethyl Oxy-1,2-diphenylethyl-1-one, xanthone, fluorenone, benzaldehyde, pyrene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone , 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzoin Methyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2 -(N-morpholinyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- (N-morpholinyl) phenyl) butanone-1, 4- ( 2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2,6-dimethoxy Benzamidine) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) Ketone) and so on.

Commercially available products as active energy ray polymerization initiators include, for example: Ciba Specialty Chemicals, trade names: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, 1000, 1300, 1700, 1800, 1850, DAROCUR 1116, 1173; BASF company product name: Lucirin TPO; UCB company product name: UVECRYL P36; Fratelli-Lamberti company product name: Ezacure KIP150, KIP100F, KT37, KT55, KTO46, TZT, KIP75LT; Japanese Trade name of pharmaceutical company: KAYACURE DETX, etc.

In addition, a radical polymerization initiator and an active energy ray initiator can be used in combination as needed. Examples of the radical polymerization initiator include: benzamyl peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, di (tertiary butyl) ) Peroxides, tert-butyl peroxybenzoate, diisopropyl peroxycarbonate, tert-butylperoxycarbonate isopropyl carbonate and other organic peroxides; 2,2'-azobisisobutyronitrile (AIBN) and other azo compounds.

The content of these polymerization initiators varies depending on the type and the like, and the index is preferably: 1 to 100 parts by mass based on 100 parts by mass of the total amount of the amine ester (meth) acrylate and the polyfunctional (meth) acrylate. 8 parts by mass. When the content is 1 part by mass or more, sufficient active energy ray sensitivity can be obtained. When the content is 8 parts by mass or less, the active energy ray can be fully transmitted to the deep part of the coating film, and sufficient hardening of the deep part of the coating film can be obtained. Sex.

Furthermore, in the present invention, examples of the active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, and gamma rays, and energy source sources include, for example, high-pressure mercury lamps, carbon arc lamps, and xenon lamps. ,Metal halide lamp.

In addition to the organic solvents, monomers, and various initiators, the active energy ray-curable composition of the present invention can be added to coatings, coating agents, and the like as needed within a range that does not impair the effects of the present invention. Various additives usually contained. Examples of the additives include light stabilizers, ultraviolet absorbers, catalysts, leveling agents, defoamers, polymerization accelerators, antioxidants, flame retardants, infrared absorbers, antistatic agents, and sliding agents. Agent.

The active energy ray-curable composition of the present invention is used in the form of a paint, a coating agent, or the like. Examples of target objects (to-be-coated) that are painted or coated include electronic devices such as mobile phones, watches, optical discs, audio equipment, office automation (OA) equipment, and anti-reflection devices such as touch panels and cathode-ray tubes. Electronic components such as boards; household appliances such as refrigerators, vacuum cleaners, microwave ovens; interior decorations of automobiles such as measuring panels and dashboards; pre-coated metal steel plates; automobile bodies, bumpers, spoilers, door handles, steering wheels, headlights , Fuel tanks for locomotives, aluminum wheel frames, rearview mirrors and other auto parts that have been plated / evaporated or sputtered; carport roofs, daylighting roofs; polyvinyl chloride, acrylic resins, polyethylene terephthalate , Polycarbonate, acrylonitrile-butadiene-styrene (ABS) resin and other plastic molded products; protective layers for optical disc recording media, protective layers for various optical lenses such as sunglasses and correction glasses lenses; stairs, floors , Tables, chairs, cabinets, other furniture and other woodwork products; cloth, paper, etc.

The painting method is not particularly limited as long as it is a conventional method, and examples thereof include an air spray method, an electrostatic coating method, a roll coating method, a flow coating method, and a spin coating method.

The thickness of the film obtained by painting or coating is not particularly limited, but is preferably about 1 to 100 μm. When the thickness of the coating is 1 μm or more, the film has sufficient functions of the coating. When the thickness of the coating is 100 μm or less, the thickness of the coating is not excessively thick, and the physical properties of the coating target are easily exhibited. [Example]

Next, examples will be described together with comparative examples. However, the present invention is not limited by these examples. In addition, in the following, unless otherwise stated, content etc. are set as a mass basis.

[Synthesis Example 1] In a four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 1,151 parts (16.0 mol) of acrylic acid, 604 parts (4.44 mol) of pentaerythritol (manufactured by Guang Rong Chemical Industry Co., Ltd.), and p-toluenesulfonic acid were prepared. 43.9 parts of acid, 2.1 parts of hydroquinone monomethyl ether, and 552 parts of toluene were mixed, and the reaction temperature was maintained at about 100 ° C while blowing air while reacting under reduced pressure until all of the pentaerythritol was reacted. 58% of the hydroxyl groups have been esterified. The reaction proceeded while removing the condensation water, and the condensation water produced was 179 parts. After completion of the reaction, 353 parts of toluene was additionally added. With respect to the acid content of the reaction liquid after the toluene was additionally added, a 20 mass% sodium hydroxide aqueous solution corresponding to 1.1 times the molar amount was added under stirring to perform a neutralization treatment, and excess acrylic acid and p-toluenesulfonic acid were removed. The organic layer was separated, and 10 parts of water was added to 100 parts of the organic layer with stirring to perform a water washing treatment. The organic layer was separated and heated under reduced pressure to remove toluene. The obtained acrylate was 837 parts and the hydroxyl value was 190 mgKOH / g.

[Synthesis Example 2] In a four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 1,151 parts (16.0 mol) of acrylic acid, 604 parts (4.44 mol) of pentaerythritol (manufactured by Guang Rong Chemical Industry Co., Ltd.), and p-toluenesulfonic acid were prepared. 43.9 parts of acid, 2.1 parts of hydroquinone monomethyl ether, and 552 parts of toluene were mixed, and the reaction temperature was maintained at about 100 ° C while blowing air while reacting under reduced pressure until all of the pentaerythritol was reacted. 58% of the hydroxyl groups have been esterified. The reaction proceeded while removing the condensation water, and the condensation water produced was 179 parts. After completion of the reaction, 353 parts of toluene was additionally added. With respect to the acid content of the reaction solution after the toluene was additionally added, a 20 mass% sodium hydroxide aqueous solution corresponding to 1.4 times the molar amount was added under stirring to perform a neutralization treatment, and excess acrylic acid and p-toluenesulfonic acid were removed. The organic layer was separated, and 10 parts of water was added to 100 parts of the organic layer with stirring to perform a water washing treatment. The organic layer was separated and heated under reduced pressure to remove toluene. The obtained acrylate was 837 parts, and the hydroxyl value was 163 mgKOH / g.

[Synthesis Example 3] 1. In a four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 1,151 parts (16.0 mol) of acrylic acid, 604 parts (4.44 mol) of pentaerythritol (manufactured by Guang Rong Chemical Industry Co., Ltd.), and p-toluenesulfonic acid were prepared. 43.9 parts of acid, 2.1 parts of hydroquinone monomethyl ether, and 552 parts of toluene were mixed, and the reaction temperature was maintained at about 100 ° C while blowing air while reacting under reduced pressure until all of the pentaerythritol was reacted. Until 80% of the hydroxyl groups are esterified. The reaction proceeded while removing the condensation water, and the resulting condensation water was 256 parts. After completion of the reaction, 353 parts of toluene was additionally added. With respect to the acid content of the reaction solution after the toluene was additionally added, a 20 mass% sodium hydroxide aqueous solution corresponding to 1.4 times the molar amount was added under stirring to perform a neutralization treatment, and excess acrylic acid and p-toluenesulfonic acid were removed. The organic layer was separated, and 10 parts of water was added to 100 parts of the organic layer with stirring to perform a water washing treatment. The organic layer was separated and heated under reduced pressure to remove toluene. The obtained acrylate was 1,082 parts, and the hydroxyl value was 120 mgKOH / g.

In each of the above Synthesis Examples, the hydroxyl value was determined by the following method. The sample was dissolved in acetic anhydride / pyridine (15 g / 85 g) and allowed to react at 90 ° C for 1.5 hours. After a small amount of water was added and the reaction was further allowed to proceed for 10 minutes, it was cooled to room temperature. Phenolphthalein was added as an indicator, and the hydroxyl value was determined by titration with a 1 mol / L potassium hydroxide (KOH) ethanol solution.

The pentaerythritol acrylate obtained by the said synthesis example was used, and the urethane acrylate was manufactured by the following method. When producing the following amine ester acrylate, when the viscosity is high, a butyl acetate solution is suitably used to reduce the viscosity.

[Synthesis Example 4] Into a flask, 168 g (1 mol) of hexamethylene diisocyanate (manufactured by Asahi Kasei Chemical Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and a hydroxyl value obtained in Synthesis Example 1 were fed. 190 mgKOH / g pentaerythritol 532 g (1.8 mol) and (2-propenyloxyethyl) hydroxyethyl isocyanurate / 2-propenyloxyethyl isocyanurate mixture ( Mass ratio = 56/44 mixture, "ARONIX M-215" manufactured by Toa Synthesis Co., Ltd.) 187 g (0.4 mol), and the reaction was performed at 70 to 80 ° C until the amount of free isocyanate became 0.1% or less, Urethane acrylate A (UA).

[Synthesis Example 5] 222 g (1 mol) of isophorone diisocyanate (manufactured by Evonik Japan Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and a hydroxyl value of 190 obtained in the above Synthesis Example 1 were fed into a flask. mgKOH / g Pentaerythritol 532 g (1.8 mol) and (2-propenyloxyethyl) hydroxyethyl isocyanurate / 2-propenyloxyethyl isocyanurate mixture (mass Ratio = 56/44 mixture, "ARONIX M-215" manufactured by Toa Synthesis Co., Ltd.) 187 g (0.4 mol), and reacted at 70 to 80 ° C until the amount of free isocyanate becomes 0.1% or less to obtain amine Ester acrylate B (UB).

[Synthesis Example 6] 烧瓶 Into a flask, 206 g (1 mol) of norbornene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and a hydroxyl value of 163 obtained in the above Synthesis Example 2 were fed. mgKOH / g Pentaerythritol 532 g (1.8 mol) and (2-propenyloxyethyl) hydroxyethyl isocyanurate / 2-propenyloxyethyl isocyanurate mixture (mass Ratio = 56/44 mixture, "ARONIX M-215" manufactured by Toa Synthesis Co., Ltd.) 187 g (0.4 mol), and reacted at 70 to 80 ° C until the amount of free isocyanate becomes 0.1% or less to obtain amine Esters C (UC).

[Synthesis Example 7] 222 g (1 mol) of isophorone diisocyanate (manufactured by Evonik Japan Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and a hydroxyl value of 190 obtained in Synthesis Example 1 were fed into a flask. mgKOH / g Pentaerythritol 325 g (1.1 mol) and (2-propenyloxyethyl) hydroxyethyl isocyanurate / 2-propenyloxyethyl isocyanurate mixture (mass Ratio = 56/44 mixture, "ARONIX M-215" manufactured by Toa Synthesis Co., Ltd.) 514 g (1.1 mol), and reacted at 70 to 80 ° C until the amount of free isocyanate becomes 0.1% or less to obtain amine Ester Acrylate D (UD).

[Comparative Synthesis Example 1] 烧瓶 Feed 222 g (1 mol) of isophorone diisocyanate (manufactured by Evonik Japan Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and the hydroxyl value obtained in Synthesis Example 3 into a flask. 1028 g (2.2 mol) of 120 mgKOH / g of pentaerythritol acrylate was reacted at 70 to 80 ° C. until the amount of free isocyanate became 0.1% or less to obtain urethane acrylate E (UE).

[Comparative Synthesis Example 2] 烧瓶 Feed a flask with 222 g (1 mol) of isophorone diisocyanate (manufactured by Evonik Japan Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and the hydroxyl value obtained in Synthesis Example 3 above. 120 mgKOH / g pentaerythritol 514 g (1.1 mol) and (2-propenyloxyethyl) hydroxyethyl isocyanurate / 2-propenyloxyethyl isocyanurate mixture ( Mass ratio = 56/44 mixture, "ARONIX M-215" manufactured by Toa Synthesis Co., Ltd.) 514 g (1.1 mol), and reacted at 70 to 80 ° C until the amount of free isocyanate becomes 0.1% or less, to obtain Urethane acrylate F (UF).

[Table 1]

The numerical value of each component shown in Table 1 shows content, and its unit is "mol".

(Preparation and evaluation of hardening composition) The amine ester acrylate (UA to F) and the polyfunctional (meth) acrylate compound or other obtained in the synthesis example prepared at the ratio shown in Table 2 or others The total amount of (meth) acrylic acid ester was 100 parts by mass, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) was prepared and dissolved. Then, it was coated on a polyethylene terephthalate substrate (PET, manufactured by Toyobo Co., Ltd .: COMOSHINE A4300) so that the film thickness was about 7 μm, and a high-pressure mercury lamp of 80 W / cm was used for accumulation. Irradiation at 600 mJ / cm ² in a nitrogen environment to harden.

About each obtained hardened | cured material, pencil hardness, abrasion resistance, and curlability were investigated by the following method. The results are shown in Table 2 below.

[Pencil Hardness] According to JIS K5400, a pencil scratch tester was used to apply a load of 750 g to scratch, and the hardness of the hardest pencil without scratches was set to the hardness of the hardened pencil.

[Abrasion resistance] The film (hardened product) obtained in the above was subjected to a steel wire # 0000 back and forth with a load of 1 kg using a friction tester (Dai Hira Chemical Industry Co., Ltd.) in accordance with JIS K5701-1: 2000. Times. A haze meter ("NDH4000" manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze value of the test film before and after the test, and the difference between the two values was used to evaluate the scratch resistance. The lower the value, the better the abrasion resistance.

[Curlability] 切割 Cut the test film into a size of 10 cm × 10 cm, place it on a horizontal surface, and fix one corner, and then measure the degree of floating (mm) of the three corners from the horizontal plane. The lower the value, the better the curlability (formability).

[Table 2]

The unit of the content of each component described in Table 2 is part by mass.

From Table 2, Examples 1 to 4 using the hardened composition containing the amine ester (meth) acrylate of the present invention and acrylic acid adducts using pentaerythritol having a hydroxyl value of less than 160 mgKOH / g were used. After comparing with Comparative Example 1 using (2-propenyloxyethyl) hydroxyethyl isocyanurate, it was confirmed that according to the present invention, the abrasion resistance can be improved while the moldability can be maintained or improved, and the hardness can be obtained. Hardened film with excellent scratch resistance and formability. In addition, Examples 1 to 4 were compared with Comparative Example 2 using an acrylic acid adduct of pentaerythritol having a hydroxyl value smaller than 160 mgKOH / g and (2-propenyloxyethyl) hydroxyethyl isocyanurate. After comparison, it was confirmed that the cured film obtained by the present invention can improve scratch resistance while maintaining moldability, and has an excellent balance between hardness, scratch resistance, and moldability.

In addition to Examples 1 to 4, experiments have been performed on a hardening composition, and it has been confirmed that the same pencil hardness, scratch resistance, and moldability as those of the example can be obtained. The hardening composition contains an amine ester (methyl ) An acrylate, the amine ester (meth) acrylate is a (meth) acrylic acid adduct of a ternary or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less; Bis (2- (meth) acryloxyethyl) hydroxyethyl isocyanurate; and an organic isocyanate compound.

[Impossible / unrealistic situation] The amine ester (meth) acrylate contained in the present invention is a reaction product of the following (A), (B), and (C): (A) a hydroxyl value of 160 mgKOH / g or more (Meth) acrylic acid adducts of aliphatic polyhydric alcohols of more than 3 yuan with a molecular weight of 220 mgKOH / g or less; (B) bis (2- (meth) acryloxyethyl) hydroxyethyl isocyanurate Esters; (C) organic isocyanate compounds. Due to its complex structure, it is difficult to express it in a general formula. Moreover, if a specific structure is not identified, the specific characteristics of the substance determined by the structure cannot be easily identified. In addition, when different types of monomers are reacted, if the mixing ratios and reaction conditions are different, the characteristics of the reaction products obtained will also be quite different. In other words, the specific amine ester (meth) acrylate contained in the present invention cannot be directly identified by the structure or characteristics. [Industrial availability]

The active energy ray-curable composition of the present invention is suitable as a coating or a coating agent in a field requiring abrasion resistance because a hardened material having excellent hardness, abrasion resistance, and formability can be obtained. Specifically, it can be applied to the following: electronic devices such as mobile phones, watches, optical discs, audio equipment, and OA devices; electronic parts such as touch panels; household appliances such as refrigerators, vacuum cleaners, microwave ovens, and thin TVs; measuring disks , Dashboard and other automotive interior decorations; automotive parts, etc.

The present invention has been described in detail and with reference to specific embodiments, but various changes or modifications can be made without departing from the spirit and scope of the present invention. This fact is obvious to those having ordinary knowledge in the technical field to which the present invention belongs. Easy to know matters. This case is based on Japanese Patent Application No. 2016-058852 filed on March 23, 2016, and the contents are incorporated herein by reference.

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Claims (7)

An active energy ray-curable composition, comprising an amine ester (meth) acrylate, which is a reaction product of the following (A), (B), and (C): (A) (meth) acrylic acid adduct of a ternary or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less; (Ethyl) hydroxyethyl isocyanurate; (C) organic isocyanate compounds. The active energy ray-curable composition according to claim 1, wherein the (A) (meth) acrylic acid of a ternary or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less The product is an aliphatic polyhydric alcohol compound having 3 to 6 members. The active energy ray-curable composition according to claim 2, wherein the (A) (meth) acrylic acid of a ternary or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 160 mgKOH / g or more and 220 mgKOH / g or less An aliphatic polyol compound is pentaerythritol. The active energy ray-curable composition according to any one of claims 1 to 3, wherein the (C) organic isocyanate compound is selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and norbornene di One or more selected from the group consisting of isocyanates. The active energy ray-curable composition according to any one of claims 1 to 3, further comprising (D) a polyfunctional (meth) acrylic acid having three or more (meth) acrylfluorenyl groups in one molecule. ester. The active-energy-ray-curable composition according to any one of claims 1 to 3, wherein the ratio of the component (A) to the component (B), that is, (A) / (B), is in a mass ratio, It is 95/5 ～ 50/50. The active energy ray-curable composition according to any one of claims 1 to 3, wherein the molar number of the hydroxyl group of the component (A) calculated from the hydroxyl value and the molar number of the hydroxyl group of the component (B) The molar ratio of the total number of ears a + b to the mole number c of the isocyanate group of the (C) component, that is, (a + b) / c, is 0.5 or more and less than 1.