TWI719154B - Active energy ray hardening composition - Google Patents

Abstract

The present invention provides an active energy ray-curable composition, the cured film obtained is excellent in hardness, scratch resistance, and moldability. The active energy ray-curable composition of the present invention contains an urethane (meth)acrylate which is a reaction product of the following (A), (B) and (C): (A) (Meth) acrylic acid adducts of aliphatic polyhydric alcohol compounds with a hydroxyl value of 160 mgKOH/g or more and 220 mgKOH/g or more; (B) bis(2-(meth)acryloyloxyethyl) Hydroxyethyl isocyanurate; (C) organic isocyanate compound.

Description

Active energy ray hardening composition

The present invention relates to an active energy ray curable composition which contains a urethane (meth)acrylate and can obtain a cured film excellent in hardness, scratch resistance, and moldability.

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, and the protective film is obtained by using a coating composition. In particular, plastic substrates are light in weight, excellent in impact resistance and formability, but have low surface hardness and are easily damaged. Therefore, if they are used as they are, there is a problem that the appearance will be damaged over time. Therefore, plastic surfaces are seeking to increase surface hardness.

As a method to solve this problem, a method of coating the plastic surface with a coating composition (hard coating treatment) has been used. As a coating composition, silicone resin composition, acrylic resin composition, Thermosetting resin compositions such as melamine-based resin compositions have a problem that it takes a long time to cure and cannot be applied to plastic film substrates that are less heat-resistant.

In recent years, active energy ray-curing resin compositions have been used as hard coat treatment agents for plastic film substrates because they have rapid curing properties and can be cured 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 (meth) It is formed by reacting a poly)acrylate and a polyisocyanate, and this radiation-curable polyfunctional (meth)acrylate has at least two (meth)acryloyl groups and a hydroxyl group in the molecule (Patent Document 1).

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

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

[Problem 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, which is a combination of pentaerythritol triacrylate and isophorone diisocyanate Addition (refer to paragraph [0026]). The polyfunctional urethane acrylate has a large curing shrinkage. Therefore, in order to obtain the required scratch resistance film thickness, the curl after curing will be too large and the film will The problem of formability such as warpage.

In addition, in Patent Document 2, as a specific example of an active energy ray curable composition, a combination of urethane acrylate (see paragraph [0091]) and polypropylene glycol diacrylate (see paragraph [0052]) is described. A mixture in which the urethane acrylate is obtained by adding an acrylate of pentaerythritol with a hydroxyl value of 173 mgKOH/g and isophorone diisocyanate. This mixture has the problem of insufficient scratch resistance.

The present invention was completed in view of the above-mentioned problems, and its object is to provide an active energy ray curable composition capable of obtaining a cured film having an excellent balance between hardness, scratch resistance, and moldability. [Technical means to solve the problem]

The active energy ray curable composition of the present invention contains an amine ester (meth)acrylate which is a reaction product of the following (A), (B) and (C): ( A) (meth)acrylic acid adducts of aliphatic polyhydric alcohol compounds with a hydroxy value of 160 mgKOH/g or more and 220 mgKOH/g or more; (B) bis(2-(meth)acryloyloxyethyl) Group) hydroxyethyl isocyanurate; (C) organic isocyanate compound.

(A) The (meth)acrylic acid adduct of an aliphatic polyhydric alcohol compound having a hydroxy value of 160 mgKOH/g or more and 220 mgKOH/g or more. The aliphatic polyol compound is preferably trivalent or more and The aliphatic polyol with a valence of less than 6 is 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 multifunctional (meth)acrylate having 3 or more (meth)acryloyl groups in one molecule.

The ratio of the aforementioned (A) component to (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 the total value a+b of the molar number of the hydroxyl group of the component (A) and the molar number of the hydroxyl group of the component (B) calculated from the hydroxyl value and the aforementioned ( C) The molar ratio (a+b)/c of the molar number c of the isocyanate group of the component is 0.5 or more and less than 1. [effect]

According to the active energy ray-curable composition of the present invention, a cured film with high hardness, high scratch 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 contains an amine ester (meth)acrylate which is a reaction product of the following (A), (B) and (C): ( A) (meth)acrylic acid adducts of aliphatic polyhydric alcohol compounds with a hydroxy value of 160 mgKOH/g or more and 220 mgKOH/g or more; (B) bis(2-(meth)acryloyloxyethyl) Group) hydroxyethyl isocyanurate; (C) organic isocyanate compound. Furthermore, the so-called (meth)acrylic acid refers to acrylic acid and/or methacrylic acid, and the so-called bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate refers to bis(2 -Acrylicoxyethyl)hydroxyethyl isocyanurate and/or bis(2-methacryloxyethyl)hydroxyethyl isocyanurate. In this manual, "(methyl)..." all have the same meaning.

(A) The (meth)acrylic acid adduct of a trivalent or higher aliphatic polyol compound with a hydroxyl value of 160 mgKOH/g or more and 220 mgKOH/g or less (hereinafter may also be referred to as (meth)acrylic acid adduct) ) Can be obtained by adding (meth)acrylic acid to a predetermined trivalent or higher aliphatic polyol (hereinafter sometimes referred to as aliphatic polyol) through an esterification reaction.

The aliphatic polyol is not particularly limited as long as it is a trivalent or higher alcohol compound, but is preferably a trivalent or higher to 6-valent aliphatic polyol, and more preferably a tetravalent aliphatic polyol. When the valence of the aliphatic polyol is 3 or more, the hardness of the hardened product obtained from the composition can be easily increased, and when the valence of the aliphatic polyol is 6 or less, the occurrence of hardened materials can be easily reduced Curl also improves formability.

As the above-mentioned aliphatic polyol, specifically, for example, trimethylolpropane, alkylene oxide adduct of trimethylolpropane, pentaerythritol, alkylene oxide adduct of pentaerythritol, bis(trimethylolpropane) Alkyl propane), bis(trimethylolpropane) alkylene oxide adduct, dipentaerythritol, dipentaerythritol alkylene oxide adduct, tripentaerythritol, tripentaerythritol alkylene oxide adduct, glycerin, glycerin Sugar derivatives such as alkylene oxide adducts, sucrose, and alkylene oxide adducts of sucrose, and alkylene oxide adducts of sugar derivatives, etc. 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 increasing the hardness of the cured product obtained from the composition, the alkylene oxide adduct of trimethylolpropane and trimethylolpropane, pentaerythritol, and alkylene oxide of pentaerythritol are preferred. Adducts, dipentaerythritol, alkylene oxide adducts of dipentaerythritol, tripentaerythritol, and alkylene oxide adducts of tripentaerythritol, more preferably pentaerythritol and dipentaerythritol. Especially preferred is pentaerythritol.

In addition, the aforementioned aliphatic polyols may be used singly or in combination of two or more, and it is preferable to use one singly.

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

When manufacturing the said (meth)acrylic acid adduct, in addition to (meth)acrylic acid, (meth)acrylic acid halide, (meth)acrylic anhydride, (meth)acrylic acid ester compound, etc. 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, 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, it is easy to obtain a cured film excellent in hardness, scratch resistance, and moldability.

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

The aforementioned (meth)acrylic acid adduct may include a (meth)acrylic acid adduct having no hydroxyl group, preferably a (meth)acrylic acid adduct having 1 hydroxyl group, and more preferably a (meth)acrylic acid adduct having 2 (Meth) acrylic acid adducts of a hydroxyl group.

The above-mentioned (meth)acrylic acid adduct can be produced by a conventional esterification reaction, and it is preferable to use a catalyst or stabilizer. The catalyst preferably includes, for example, an acid catalyst. In addition, examples of the stabilizer include conventional polymerization inhibitors such as hydroquinone monomethyl ether. In addition, it is also preferable to use oxygen as a stabilizer, especially a polymerization inhibitor. For example, by esterifying the aliphatic polyol with (meth)acrylic acid in an oxygen-containing environment, it is possible to prevent the polymerization of excess (meth)acrylic acid or (meth)acrylate. In addition, the method for producing the above-mentioned (meth)acrylic acid adduct preferably includes a method such as purification by liquid-liquid extraction (liquid separation). According to the above-mentioned production method, the above-mentioned (meth)acrylic acid adduct having a hydroxyl value of 160 mgKOH/g or more and 220 mgKOH/g or less can be easily produced.

The above-mentioned bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate can be produced by the following method: tris(2-hydroxyethyl)isocyanurate and (methyl) ) Acrylic acid undergoes dehydration esterification reaction. At this time, the reaction product is obtained in the form of a mixture of 1 to 3 substitutions of (meth)acrylic acid. Generally speaking, the 1 substitution will be removed during the refining process, and the 2 substitution is the bis(2- The form of a mixture of (meth)acryloxyethyl)hydroxyethyl isocyanurate and the 3-substituent, that is, tris(2-(meth)acryloxyethyl)isocyanurate Circulate on the market. Examples of commercially available products of such a mixture include "ARONIX M-215" manufactured by Toagosei Co., Ltd.

The mixing ratio of bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate and tris(2-(meth)acryloyloxyethyl)isocyanurate is double (2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate/tris(2-(meth)acryloyloxyethyl)isocyanurate is not particularly limited, and is based on mass ratio In total, 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) component, namely bis(2-(meth)acryloxyethyl)hydroxyethyl isocyanurate can be used: bis(2-(meth)acryloxyethyl)hydroxyethyl A mixture of isocyanurate and tris(2-(meth)acryloxyethyl) isocyanurate. When a mixture is used, the reaction product may contain both 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 type 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 araliphatic polyisocyanates.

Examples of aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene 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, etc.

Examples of alicyclic polyisocyanates include isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate , Methylcyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, etc.

Examples of aromatic polyisocyanates include toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate ( MDI), 4,4'-diphenylmethyl diisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate, 1,3-benzene diisocyanate, 1,4-benzene diisocyanate, etc.

As the araliphatic polyisocyanate, for example, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α,α,α,α-tetramethylxylene diisocyanate, etc. may be mentioned.

In addition, for example, modified products such as dimers or trimers of these organic isocyanate compounds, or biureated isocyanates can also be cited.

These organic isocyanate compounds can also be used alone or in combination of two or more kinds. In view of the fact that the cured product obtained from the composition will have higher hardness and low curling properties, the organic isocyanate compound is preferably one selected from the group consisting of the above-mentioned aliphatic polyisocyanate and alicyclic polyisocyanate Or more than 2 kinds. Among them, more preferred are hexamethylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate.

The mass ratio of the (A) component to the (B) component 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 a+b of the molar number of the hydroxyl groups of the component (A) and the component (B) calculated from the hydroxyl value is the molar ratio of the molar number c of the isocyanate group of the component (C), which 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 3 or more (meth)acryloyl groups in one molecule (hereinafter sometimes only referred to as polyfunctional ( Meth)acrylate). By containing the above-mentioned polyfunctional (meth)acrylate, the hardness of the cured film obtained from the composition can be further increased.

The content of the polyfunctional (meth)acrylate (the total amount when two or more types are used in combination) is not particularly limited, and is 0 to 90 parts by mass based on 100 parts by mass of the total amount of the amine ester (meth)acrylate. Preferably, it is preferably 0 to 80 parts by mass, more preferably 0 to 70 parts by mass.

The polyfunctional (meth)acrylate is not particularly limited, and specific examples include: acrylate of trimethylolpropane, acrylate of alkylene oxide adduct of trimethylolpropane, acrylate of pentaerythritol, The acrylate of the alkylene oxide adduct of pentaerythritol, the acrylate of bis(trimethylolpropane), the acrylate of the alkylene oxide adduct of bis(trimethylolpropane), the acrylate of dipentaerythritol, two The acrylate of the alkylene oxide adduct of pentaerythritol, the acrylate of tripentaerythritol, the acrylate of the alkylene oxide adduct of tripentaerythritol, the acrylate of 2-propenoxyethyl isocyanurate, the acrylate of glycerin, The acrylate of the alkylene oxide adduct of glycerin, the acrylate of sucrose, the acrylate of the alkylene oxide adduct of sucrose, and the like, and the acrylate of the alkylene oxide adduct of sugar derivatives. These can also be used individually, and can also use 2 or more types together.

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 increasing the hardness of the cured product obtained from the composition, acrylate of pentaerythritol, acrylate of pentaerythritol alkylene oxide adduct, acrylate of dipentaerythritol, and acrylate of dipentaerythritol are preferred. Acrylate of alkylene oxide adduct, acrylate of tripentaerythritol, acrylate of alkylene oxide adduct of tripentaerythritol, 2-propylene oxyethyl 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 in the following manner, for example, in the presence of a polymerization inhibitor such as hydroquinone monomethyl ether. Heat at ~80°C until the free isocyanate disappears, while stirring predetermined amounts of (A), (B), and (C). At this time, in order to promote the reaction, a tin-based catalyst such as dibutyltin dilaurate can also 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 needed. Examples of monomers include: acrylate of pentaerythritol, acrylate of alkylene oxide adduct of pentaerythritol, acrylate of dipentaerythritol, acrylate of alkylene oxide adduct of dipentaerythritol, acrylate of tripentaerythritol, Acrylate of tripentaerythritol alkylene oxide adduct, 2-propenyloxyethyl isocyanurate, etc. These may be used individually by 1 type, and may use 2 or more types together.

In the active energy ray curable composition, the content of the urethane (meth)acrylate is not particularly limited, and is preferably 50% by mass or 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 for active energy rays as needed. The polymerization initiator of active energy rays herein refers to both a polymerization initiator including a photopolymerization initiator and active energy rays such as ultraviolet rays.

The photopolymerization initiator is not particularly limited. For example, aromatic ketones such as benzophenone; aromatic compounds such as anthracene and α-chloromethylnaphthalene; diphenyl sulfide, thiocarbamate, etc. can be used. Sulfur compounds.

The polymerization initiator for active energy rays such as ultraviolet rays other than visible light is not particularly limited, and examples include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethyl ketone. Oxy-1,2-diphenylethan-1-one, xanthone (xanthone), ketone, benzaldehyde, fennel, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone , 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzophenone 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)-1-propanone, 2-benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)butanone-1, 4-( 2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,6-dimethoxy) Benzyl)-2,4,4-trimethylpentylphosphine oxide, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)acetone )Wait.

Commercially available products as polymerization initiators for active energy rays include, for example, Ciba Specialty Chemicals' product name: 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; Japanization Product name manufactured by the pharmaceutical company: KAYACURE DETX, etc.

In addition, a radical polymerization initiator and an active energy ray initiator can also be used together as needed. Examples of radical polymerization initiators include benzyl peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, di(tertiary butyl) ) Organic peroxides such as peroxide, tertiary butyl peroxybenzoate, diisopropyl peroxycarbonate, and tertiary butyl peroxyisopropyl carbonate; 2,2'-azobisisobutyronitrile (AIBN) and other azo compounds.

The content of these polymerization initiators may vary depending on the type, etc. The index is preferably: 1 to 100 parts by mass of the total amount of urethane (meth)acrylate and 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, and when the content is 8 parts by mass or less, the active energy ray will 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 active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, and gamma rays. Examples of energy ray sources include high-pressure mercury lamps, carbon arc lamps, and xenon lamps. ,Metal halide lamp.

In the active energy ray-curable composition of the present invention, in addition to the above-mentioned organic solvents, monomers, and various initiators, it is also possible to add paints, coating agents, etc., as needed, within a range that does not impair the effects of the present invention. Various additives usually contained. Examples of additives include: light stabilizers, ultraviolet absorbers, catalysts, leveling agents, defoamers, polymerization accelerators, antioxidants, flame retardants, infrared absorbers, antistatic agents, sliding剂 etc.

The active energy ray-curable composition of the present invention is used in the form of paint, coating agent, or the like. Examples of objects to be painted (coated objects) include: mobile phones, watches, optical discs, audio equipment, office automation (OA) equipment and other electronic equipment; touch panels, cathode ray tubes, etc. anti-reflection Electronic parts such as plates; 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 , Locomotive fuel tanks, aluminum wheel frames, rearview mirrors and other auto parts that have been plated/evaporated or sputtered; carport roofs, daylighting roofs; polyvinyl chloride, acrylic resin, 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 corrective glasses lenses; stairs, floors , Tables, chairs, cabinets, other furniture and other woodworking products; cloth, paper, etc.

The coating method is not particularly limited as long as it conforms to 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 brushing or coating is not particularly limited, but is preferably about 1 to 100 μm. Since the thickness of the coating film is 1 μm or more, it has sufficient coating function. When the thickness of the coating film is 100 μm or less, the thickness of the coating film will not be too thick, and the physical properties of the coating target can be easily exhibited. [Example]

Next, examples will be described together with comparative examples. However, the present invention is not limited by these embodiments. In addition, in the following, unless otherwise specified, the content and the like are based on quality.

[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 Guangrong Chemical Industry Co., Ltd.), and p-toluenesulfonate were added. 43.9 parts of acid, 2.1 parts of hydroquinone monomethyl ether, and 552 parts of toluene were mixed, and the reaction was allowed to proceed under reduced pressure in a manner that while blowing air while maintaining the reaction temperature at about 100°C until all of the pentaerythritol was contained 58% of the hydroxyl group is esterified. The reaction proceeded while removing the condensation water, and the generated condensation water was 179 parts. After the reaction, 353 parts of toluene were additionally added. With respect to the acid content of the reaction liquid after the toluene was additionally added, a 1.1-fold mol amount of a 20% by mass aqueous sodium hydroxide solution 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 under stirring to perform a water washing treatment. The organic layer was separated and heated under reduced pressure to distill off 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 Guangrong Chemical Industry Co., Ltd.), and p-toluenesulfonate were added. 43.9 parts of acid, 2.1 parts of hydroquinone monomethyl ether, and 552 parts of toluene were mixed, and the reaction was allowed to proceed under reduced pressure in a manner that while blowing air while maintaining the reaction temperature at about 100°C until all of the pentaerythritol was contained 58% of the hydroxyl group is esterified. The reaction proceeded while removing the condensation water, and the generated condensation water was 179 parts. After the reaction, 353 parts of toluene were additionally added. With respect to the acid content of the reaction solution after adding toluene, a 20% by mass aqueous sodium hydroxide solution corresponding to 1.4 times mol 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 under stirring to perform a water washing treatment. The organic layer was separated and heated under reduced pressure to distill off toluene. The obtained acrylate was 837 parts, and the hydroxyl value was 163 mgKOH/g.

[Synthesis Example 3] 　　 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 Guangrong Chemical Industry Co., Ltd.), and p-toluenesulfonate were added. 43.9 parts of acid, 2.1 parts of hydroquinone monomethyl ether, and 552 parts of toluene were mixed, and the reaction was allowed to proceed under reduced pressure in a manner that while blowing air while maintaining the reaction temperature at about 100°C until all of the pentaerythritol was contained 80% of the hydroxyl groups are esterified. The reaction proceeded while removing the condensation water, and the generated condensation water was 256 parts. After the reaction, 353 parts of toluene were additionally added. With respect to the acid content of the reaction solution after adding toluene, a 20% by mass aqueous sodium hydroxide solution corresponding to 1.4 times mol 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 under stirring to perform a water washing treatment. The organic layer was separated and heated under reduced pressure to distill off toluene. The obtained acrylate was 1082 parts, and the hydroxyl value was 120 mgKOH/g.

In addition, in each of the above synthesis examples, the hydroxyl value was obtained 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 adding a small amount of water and further reacting for 10 minutes, it was cooled to room temperature. Add phenolphthalein as an indicator, and titrate with 1 mol/L potassium hydroxide (KOH) ethanol solution to obtain the hydroxyl value.

Using the acrylate of pentaerythritol obtained in the above-mentioned synthesis example, the urethane acrylate was produced in the following manner. When manufacturing the following urethane acrylates, when the viscosity is high, use a butyl acetate solution to reduce the viscosity.

[Synthesis Example 4] 　 168 g (1 mol) of hexamethylene diisocyanate (manufactured by Asahi Kasei Chemical Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and the hydroxyl value obtained in the above synthesis example 1 were fed into the flask 190 mgKOH/g of pentaerythritol acrylate 532 g (1.8 mol) and (2-acryloxyethyl) hydroxyethyl isocyanurate/2-acryloxyethyl isocyanurate mixture ( Mass ratio = 56/44 mixture, "ARONIX M-215" manufactured by Toagosei Co., Ltd.) 187 g (0.4 mol), and react at 70 to 80°C until the amount of free isocyanate becomes 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 the hydroxyl value of 190 obtained in the above synthesis example 1 were fed into the flask. mgKOH/g pentaerythritol acrylate 532 g (1.8 mol) and (2-acryloxyethyl) hydroxyethyl isocyanurate/2-acryloxyethyl isocyanurate mixture (mass Ratio=56/44 mixture, "ARONIX M-215" manufactured by Toagosei 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 an amine Ester acrylate B (UB).

[Synthesis Example 6] 　　 Into a flask, 206 g (1 mol) of norbornene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and the hydroxyl value obtained in the above synthesis example 2 were 163 mgKOH/g pentaerythritol acrylate 532 g (1.8 mol) and (2-acryloxyethyl) hydroxyethyl isocyanurate/2-acryloxyethyl isocyanurate mixture (mass Ratio=56/44 mixture, "ARONIX M-215" manufactured by Toagosei 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 an amine Ester Acrylate 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 hydroxyl value of 190 obtained in the above synthesis example 1 were fed into the flask. mgKOH/g of pentaerythritol acrylate 325 g (1.1 mol) and (2-acryloxyethyl) hydroxyethyl isocyanurate/2-acryloxyethyl isocyanurate mixture (mass Ratio=56/44 mixture, "ARONIX M-215" manufactured by Toagosei Co., Ltd.) 514 g (1.1 mol), and react at 70 to 80°C until the amount of free isocyanate becomes 0.1% or less to obtain an amine Ester Acrylate D (UD).

[Comparative Synthesis Example 1] 　 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 were charged into the flask 1028 g (2.2 mol) of pentaerythritol acrylate of 120 mgKOH/g 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] 　　 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 the above synthesis example 3 were fed into the flask 120 mgKOH/g pentaerythritol acrylate 514 g (1.1 mol) and (2-acryloxyethyl) hydroxyethyl isocyanurate/2-acryloxyethyl isocyanurate mixture ( Mass ratio = 56/44 mixture, "ARONIX M-215" manufactured by Toagosei 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. Urethane acrylate F (UF).

[Table 1]

The numerical value of each component described in Table 1 indicates the content, and the unit is "mol".

(Preparation and evaluation of curable composition) Compared with the urethane acrylate (UA to F) obtained in the above synthesis example prepared in the ratio shown in Table 2 and the polyfunctional (meth)acrylate compound or others The total amount of the (meth)acrylate is 100 parts by mass, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) are prepared and dissolved. Then, coat it on a polyethylene terephthalate substrate (PET made by Toyobo Co., Ltd., model: COMOSHINE A4300) so that the film thickness becomes about 7 μm, and use a high-pressure mercury lamp 80 W/cm to accumulate The illuminance is 600 mJ/cm ² irradiated in a nitrogen environment to make it harden.

With respect to each of the obtained cured products, the pencil hardness, scratch resistance, and curling properties were investigated by the following methods. The results are shown in Table 2 below.

[Pencil hardness] 　　 According to JIS K5400, after applying a load of 750 g and scratching using a pencil scratch tester, the hardness of the hardest pencil without scratches was defined as the pencil hardness of the hardened product.

[Scratch resistance] 　　 According to JIS K5701-1:2000, the film (hardened product) obtained in the above was used a friction tester (Daheira Chemical Industry Co., Ltd.) to make the steel wool #0000 go back and forth 100 times with a load of 1 kg. Times. A haze meter ("NDH4000" manufactured by Nippon Denshoku Industry 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 scratch resistance.

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

[Table 2]

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

From Table 2, Examples 1 to 4 using the curable composition containing the amine ester (meth)acrylate of the present invention are compared with the acrylic adduct using pentaerythritol with a hydroxyl value smaller than 160 mgKOH/g. Comparing Comparative Example 1 using (2-acryloyloxyethyl)hydroxyethyl isocyanurate, it can be confirmed that according to the present invention, it is possible to maintain or improve the formability while improving the scratch resistance, and the hardness can be obtained. , A cured film with excellent scratch resistance and moldability. In addition, Examples 1 to 4 are compared with Comparative Example 2 using acrylic acid adducts of pentaerythritol with a hydroxyl value smaller than 160 mgKOH/g and (2-propylene oxyethyl) hydroxyethyl isocyanurate After comparison, it can be confirmed that the cured film obtained by the present invention can improve the scratch resistance while maintaining the formability, and has an excellent balance between hardness, scratch resistance, and formability.

Moreover, in addition to Examples 1 to 4, experiments have also been conducted on a hardening type composition and it has been confirmed that the same pencil hardness, scratch resistance, and moldability as in the examples can be obtained. The hardening type composition contains urethane (methyl ) Acrylate, the amine ester (meth)acrylate is a (meth)acrylic acid adduct using the following: a trivalent or more aliphatic polyol compound with a hydroxyl value of 160 mgKOH/g or more and 220 mgKOH/g or less; Bis(2-(meth)acryloxyethyl)hydroxyethyl isocyanurate; and, organic isocyanate compound.

[Impossible/Impossible Case] 　　 The urethane (meth)acrylate contained in the present invention is the reaction product of the following (A), (B) and (C): (A) hydroxyl value 160 mgKOH/g or more (Meth) acrylic acid adducts of aliphatic polyhydric alcohol compounds with three or more valences and 220 mgKOH/g or less; (B) bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanuric acid Esters; (C) organic isocyanate compounds. Because of 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 reacting a plurality of different monomers, if the mixing ratio and reaction conditions are different, the characteristics of the obtained reaction product will also be quite different. In other words, the specific amine ester (meth)acrylate contained in the present invention cannot be directly identified by structure or characteristics. [Industrial availability]

Since the active energy ray-curable composition of the present invention can obtain a cured product excellent in hardness, scratch resistance, and moldability, it is suitable as a paint or coating agent in fields requiring scratch resistance. Specifically, it can be coated for use in the following: electronic equipment such as mobile phones, watches, optical discs, audio equipment, and OA equipment; electronic parts such as touch panels; household appliances such as refrigerators, vacuum cleaners, microwave ovens, and thin TVs; measuring plates , Dashboard and other interior decorations of automobiles; auto 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 with ordinary knowledge in the technical field to which the present invention belongs. Easy to know matters. This case is based on the Japanese Patent Application 2016-058852 filed on March 23, 2016, and the content is incorporated in this specification for reference.

no

no

Domestic hosting information (please note in the order of hosting organization, date, and number) None

Foreign hosting information (please note in the order of hosting country, institution, date, and number) None

(Please change the page to record separately) None

Claims (7)

An active energy ray hardening composition characterized by containing an amine ester (meth)acrylate which is a reaction product of the following (A), (B) and (C): (A) (Meth) acrylic acid adducts of aliphatic polyhydric alcohol compounds with a hydroxyl value of 190 mgKOH/g or more and 220 mgKOH/g or more; (B) Bis(2-(meth)acryloyloxyethyl) ) Hydroxyethyl isocyanurate; (C) Organic isocyanate compound. The active energy ray curable composition according to claim 1, wherein (A) a (meth)acrylic acid adduct of a trivalent or higher aliphatic polyol compound having a hydroxyl value of 190 mgKOH/g or more and 220 mgKOH/g or less , The aliphatic polyol compound is an aliphatic polyol with a valence of 3 or more and 6 or less. The active energy ray curable composition according to claim 2, wherein the aforementioned (A) a (meth)acrylic acid adduct of a trivalent or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 190 mgKOH/g or more and 220 mgKOH/g or less , Its 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 hexamethylene diisocyanate, isophorone diisocyanate, and norbornene One or two or more selected from the group consisting of ethylene diisocyanate. The active energy ray curable composition according to any one of claims 1 to 3, which further contains (D) a multifunctional (meth)acrylic acid having 3 or more (meth)acryloyl 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 aforementioned (A) component to (B) component, that is, (A)/(B), is calculated by 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) are calculated from the hydroxyl value. (A+b)/c, which is the molar ratio of the total value a+b of the number of ears and the molar number c of the isocyanate group of the component (C), is 0.5 or more and less than 1.