TW202100599A - Active energy ray-curable composition - Google Patents

Abstract

The present invention provides a technology that enables the achievement of a cured film which has high hardness, excellent scratch resistance and excellent formability, and which is able to be imparted with high antistatic properties. An active energy ray-curable composition according to the present invention contains a urethane (meth)acrylate that is obtained by reacting (A) a (meth)acrylic acid addition product which is obtained by adding a (meth)acrylic acid to an aliphatic polyhydric alcohol compound having a functionality of 3 or more, and which has a hydroxyl value of from 160 mgKOH/g to 220 mgKOH/g (inclusive) with (B) one or more organic isocyanates which are selected from the group consisting of xylylene diisocyanates and toluene diisocyanates; and the molar ratio of the number of moles (a) of the hydroxyl groups in the (meth)acrylic acid addition product to the number of moles (b) of the isocyanate groups in the organic isocyanates (B), namely (a)/(b) is from 1.00 to 1.60 (inclusive).

Description

Active energy ray hardening composition

The present invention relates to an active energy ray curable composition containing (meth)acrylate urethane.

In recent years, as a film for protecting the surface of liquid crystal displays, electroluminescent displays, touch panels, tablet personal computers (PC), etc., it is known to use active energy rays that cure quickly and can form films at low temperatures. The cured film of the cured composition (for example, Patent Documents 1 to 3).

Patent Document 1 describes a composition containing a polyfunctional acrylic urethane to which pentaerythritol triacrylate and isophorone diisocyanate are added.

Patent Document 2 describes a composition containing urethane acrylate, which is obtained by adding an acrylate of pentaerythritol with a hydroxyl value of 173 mgKOH/g and isophorone diisocyanate.

Patent Document 3 describes a composition containing dipentaerythritol hexaacrylate, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, and an antistatic polymer. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-113648 [Patent Document 2] Japanese Patent Laid-Open No. 2015-021089 [Patent Document 3] Japanese Patent Laid-Open No. 2010-001398

[The problem to be solved by the invention]

However, the composition described in Patent Document 1 has a large curing shrinkage, and therefore has the following problem: in the case of forming a film with the required scratch resistance, the warpage of the film becomes large, and the moldability is insufficient. , Antistatic performance is also insufficient.

In addition, the composition described in Patent Document 2 has a problem of insufficient scratch resistance and insufficient antistatic performance. Furthermore, the composition described in Patent Document 3 has antistatic performance, but has a problem of insufficient hardness.

Therefore, it is desired to obtain an active energy ray composition that can provide a cured film with high hardness, excellent scratch resistance and moldability, and capable of imparting high antistatic performance. [Means to solve the problem]

The present invention was completed to solve the above-mentioned problems, and it can be realized in the following manner.

(1) According to one aspect of the present invention, there is provided an active energy ray curable composition. This active energy ray curable composition contains (meth)acrylate urethane formed by reacting (A) (meth)acrylic acid adduct and (B) organic isocyanate, The (A) (meth)acrylic acid adduct is obtained by adding (meth)acrylic acid to an aliphatic polyol compound with a trivalent or higher valence, and the hydroxyl value is 160 mgKOH/g or higher, 220 mgKOH/g the following; The (B) organic isocyanate is one or more organic isocyanates selected from the group consisting of xylylene diisocyanate and toluene diisocyanate, The molar ratio (a/b) of the molar number a of the hydroxyl group in the (meth)acrylic acid adduct to the molar number b of the isocyanate group in the (B) organic isocyanate is 1.00 or more and 1.60 or less .

According to the active energy ray-curable composition of this aspect, it is possible to obtain a cured film having high hardness, excellent scratch resistance and moldability, and high antistatic performance.

(2) The active energy ray-curable composition described above, wherein the aliphatic polyol compound having a valence of three or more may be an aliphatic polyol compound having a valence of three or more and less than six valence.

According to the active energy ray-curable composition of this aspect, the hardness of the cured film can be further increased, and the formability can be improved by suppressing warpage in the cured film.

(3) The active energy ray curable composition as described above, wherein the aliphatic polyhydric alcohol compound having a valence of three or more may be pentaerythritol.

According to the active energy ray-curable composition of this aspect, the hardness of the cured film can be increased, and the formation of warpage in the cured film can be suppressed to improve moldability.

(4) In the active energy ray-curable composition as described above, it may further contain (C) a multifunctional (meth)acrylate having three or more (meth)acryloyl groups in one molecule.

According to the active energy ray curable composition of this form, the scratch resistance of the cured film can be further improved.

(5) The active energy ray-curable composition as described above may further contain an antistatic polymer.

According to the active energy ray-curable composition of this aspect, a cured film having antistatic properties can be obtained.

The active energy ray curable composition as an embodiment of the present invention contains (meth)acrylate urethane formed by reacting (A) (meth)acrylic acid adduct and (B) organic isocyanate, so The (A) (meth)acrylic acid adduct is obtained by adding (meth)acrylic acid to an aliphatic polyhydric alcohol compound with trivalent or more, and the hydroxyl value is 160 mgKOH/g or more, 220 mgKOH/g or less ; The (B) organic isocyanate is one or more organic isocyanates selected from the group consisting of xylylene diisocyanate and toluene diisocyanate. In addition, in the active energy ray-curable composition of the present embodiment, (A) the molar number a of the hydroxyl group in the (meth)acrylic adduct and (B) the molar number b of the isocyanate group in the organic isocyanate The molar ratio (a/b) is 1.00 or more and 1.60 or less. Here, "(meth)acrylic acid" means methacrylic acid or acrylic acid.

In this specification, "active energy ray curable composition" refers to a composition hardened by active energy rays. The active energy rays are not particularly limited, and examples thereof include visible light, ultraviolet rays, electron beams, infrared rays, X-rays, α rays, β rays, and γ rays. Examples of the energy line source include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, electrodeless lamps, and light-emitting diodes (Light Emitting Diode, LED) lamps.

According to the active energy ray-curable composition of this embodiment, a cured film having high hardness, excellent scratch resistance and moldability, and high antistatic performance can be obtained. The estimation mechanism of these effects will be explained below.

In the active energy ray-curable composition of the present embodiment, (A) the molar number a of the hydroxyl group in the (meth)acrylic acid adduct and (B) the molar number b of the isocyanate group in the organic isocyanate The ratio (a/b) is 1.00 or more. In this way, the isocyanate group in (B) organic isocyanate reacts with the hydroxyl group in (A) (meth)acrylate, and it is considered that the isocyanate group in (B) organic isocyanate can be suppressed from being present in the (meth)acrylate amine group In the formate. As a result, it is considered that while suppressing the occurrence of white turbidity of the active energy ray-curable composition, the scratch resistance of the cured film after the active energy ray-curable composition is cured, and the hardness is also improved. From the viewpoint of scratch resistance and hardness, the molar ratio (a/b) is preferably 1.05 or more, more preferably 1.10 or more, and still more preferably 1.20 or more.

The molar ratio (a/b) of the active energy ray curable composition of this embodiment is 1.60 or less. In this way, although the reason is not clear, the antistatic performance can be improved when an antistatic polymer is blended in the active energy ray curable composition. From the viewpoint of improving the antistatic performance, the molar ratio (a/b) is preferably 1.55 or less, more preferably 1.50 or less, and still more preferably 1.45 or less.

By setting the hydroxyl value in the (A) (meth)acrylic acid adduct of the present embodiment to 160 mgKOH/g or more, the scratch resistance can be improved. From the viewpoint of improving scratch resistance, the hydroxyl value in the (A) (meth)acrylic acid adduct is preferably 170 mgKOH/g or more.

In addition, by setting the hydroxyl value in the (A) (meth)acrylic acid adduct to 220 mgKOH/g or less, the occurrence of warpage in the cured film can be suppressed, and thus the moldability can be improved. From the viewpoint of improving moldability, the hydroxyl value in the (A) (meth)acrylic acid adduct is preferably 200 mgKOH/g or less.

Here, in this specification, the "hydroxyl value" refers to milligrams of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when a sample of 1 g (meth)acrylic acid adduct is acetylated ( mg) number, measured in accordance with Japanese Industrial Standards (JIS) K 0070-1992.

＜(A)(Meth)acrylic acid adducts＞ The (A) (meth)acrylic acid adduct of this embodiment is a (meth)acrylic acid adduct of an aliphatic polyhydric alcohol compound having a trivalent or higher valence, and has a hydroxyl value of 160 mgKOH/g or higher and 220 mgKOH/g The following (meth)acrylic acid adducts. The (A) (meth)acrylic acid adduct of the present embodiment can be obtained by adding (meth)acrylic acid to an aliphatic polyol compound having a valence of three or more by esterification reaction.

There are no particular limitations on the aliphatic polyol compound having a valence of three or more, but an aliphatic polyol compound having a valence of three or more and less than six is preferable, and a tetravalent aliphatic polyol compound is more preferable. By being trivalent or more, the hardness of the cured film obtained by curing the active energy ray-curable composition can be increased, and by being quadrivalent or more, the hardness of the cured film can be further increased. On the other hand, by being hexavalent or less, the occurrence of warpage in the cured film can be suppressed, and thus the moldability can be improved.

There are no particular limitations on the aliphatic polyhydric alcohol compound having a valence of three or more. Examples include trimethylolpropane and alkylene oxide adducts of trimethylolpropane, pentaerythritol, and alkylene oxide adducts of pentaerythritol, and ditrimethylolpropane. Alkylene oxide adduct of methylol propane, ditrimethylolpropane, dipentaerythritol, alkylene oxide adduct of dipentaerythritol, tripentaerythritol, alkylene oxide adduct of tripentaerythritol, glycerin, glycerin ring Alkylene oxide adducts, sugar derivatives such as sucrose and sucrose alkylene oxides, and alkylene oxide adducts of sugar derivatives, etc. Moreover, as an alkylene oxide of an alkylene oxide adduct, ethylene oxide, a propylene oxide, butylene oxide, etc. are mentioned, for example. The aliphatic polyhydric alcohol compound having trivalent or more may be used alone or in combination of two or more, but it is preferable to use one kind alone.

Among them, from the viewpoint of increasing the hardness of the cured film, the aliphatic polyhydric alcohol compound having a valence of three or more is more preferably trimethylolpropane, trimethylolpropane alkylene oxide adduct, pentaerythritol, and pentaerythritol epoxy Alkyl adducts, dipentaerythritol, alkylene oxide adducts of dipentaerythritol, tripentaerythritol, and alkylene oxide adducts of tripentaerythritol, more preferably pentaerythritol and dipentaerythritol.

The (meth)acrylic acid added in the (meth)acrylic acid adduct of the present embodiment uses at least one of acrylic acid and methacrylic acid, but it is preferable to use only acrylic acid.

In the production of (meth)acrylic acid adducts, in addition to (meth)acrylic acid, (meth)acrylic acid halide, (meth)acrylic anhydride, (meth)acrylic acid ester compounds, and the like can be used.

The (meth)acrylic acid adduct may contain a (meth)acrylic acid adduct that does not have a hydroxyl group, but preferably contains a (meth)acrylic acid adduct that has one hydroxyl group, and more preferably contains two hydroxyl groups.的(meth)acrylic acid adducts.

The (meth)acrylic acid adduct can be produced by a known esterification reaction. The esterification reaction preferably uses a catalyst or stabilizer. As the catalyst, for example, an acid catalyst is preferably mentioned. In addition, as the stabilizer, for example, known polymerization inhibitors such as hydroquinone monomethyl ether can be preferably cited. In addition, as a stabilizer, particularly a polymerization inhibitor, oxygen is also preferably used. For example, in an oxygen-containing atmosphere, by carrying out the esterification reaction of an aliphatic polyhydric alcohol compound with a trivalent or higher value with (meth)acrylic acid, it is possible to prevent unwanted polymerization of (meth)acrylic acid or (meth)acrylate . In addition, as a method of producing the (meth)acrylic acid adduct, for example, it is preferable to include a method of purification by performing liquid-liquid extraction (liquid separation). According to this production method, a (meth)acrylic acid adduct having a hydroxyl value of 160 mgKOH/g or more and 220 mgKOH/g or less can be easily produced.

＜(B) Organic isocyanate＞ The (B) organic isocyanate of the present embodiment includes one or more selected from the group consisting of xylylene diisocyanate and toluene diisocyanate. In this way, high hardness can be achieved and formability can be improved. In addition, these organic isocyanates are also preferable in terms of obtaining a high refractive index and being able to suppress yellowing of the cured film. As the organic isocyanate, modifiers such as dimers or trimers of these organic isocyanates, and biuretated isocyanates can be used.

The molar ratio (a/b) of the molar number a of the hydroxyl group in the (meth)acrylic acid adduct in the present embodiment and the molar number b of the isocyanate group in the (B) organic isocyanate is 1.00 or more, 1.5 or less. When the molar ratio (a/b) is less than 1.00, the compatibility with the antistatic polymer becomes poor, causing the coating to become cloudy. On the other hand, when the molar ratio (a/b) is more than 1.5, although the compatibility with the antistatic polymer is good, the surface specific resistance value of the cured coating film becomes high, and sufficient antistatic performance cannot be obtained.

＜(C) Multifunctional (meth)acrylate＞ The active energy ray-curable composition of this embodiment may further contain (C) a multifunctional (meth)acrylate having 3 or more (meth)acryloyl groups in one molecule (hereinafter, also simply referred to as "multifunctional ( Meth)acrylate"). By doing so, the hardness of the cured film can be made higher, which is preferable.

The content of the polyfunctional (meth)acrylate is not particularly limited, and it is preferably 0 parts by mass to 90 parts by mass, more preferably 0 parts by mass to 80 parts by mass relative to 100 parts by mass of (meth)acrylate urethane Parts, more preferably 0 parts by mass to 70 parts by mass. Here, when two or more polyfunctional (meth)acrylates are used in combination, the above-mentioned content is calculated as the total amount.

The polyfunctional (meth)acrylate is not particularly limited, and examples include trimethylolpropane acrylate, trimethylolpropane alkylene oxide adduct, pentaerythritol acrylate, and pentaerythritol The acrylate of the alkylene oxide adduct, the acrylate of ditrimethylolpropane, the acrylate of the alkylene oxide adduct of ditrimethylolpropane, the acrylate of dipentaerythritol, the alkylene oxide of dipentaerythritol Acrylate of the product, acrylate of tripentaerythritol, acrylate of alkylene oxide adduct of tripentaerythritol, acrylate of glycerin, acrylate of alkylene oxide adduct of glycerol, acrylate of sucrose, sucrose ring Sugar derivatives such as oxanes and acrylates of alkylene oxide adducts of sugar derivatives. These may be used individually by 1 type, and may use 2 or more types together.

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

From the viewpoint of increasing the hardness of the cured film, the polyfunctional (meth)acrylate is more preferably an acrylate of pentaerythritol, an acrylate of an alkylene oxide adduct of pentaerythritol, an acrylate of dipentaerythritol, and an epoxy of dipentaerythritol The acrylate of the alkane adduct, the acrylate of tripentaerythritol, the acrylate of the alkylene oxide adduct of tripentaerythritol, and the acrylate of dipentaerythritol are more preferable.

＜(Meth)acrylate urethane＞ The (meth)acrylate urethane of this embodiment can be synthesized by a known method, and the synthesis method is not particularly limited. For example, in the presence of a polymerization inhibitor such as hydroquinone monomethyl ether, a predetermined amount of (A) (meth)acrylic acid adduct and (B) organic isocyanate are heated at about 70°C to 80°C. By stirring until the free isocyanate disappears, (meth)acrylate urethane can be synthesized. At this time, 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 embodiment may contain organic solvents such as ethyl acetate and methyl ethyl ketone and/or monomers as needed. The monomers are not particularly limited, and examples include acrylates of pentaerythritol, acrylates of alkylene oxide adducts of pentaerythritol, acrylates of dipentaerythritol, acrylates of alkylene oxide adducts of dipentaerythritol, and tripentaerythritol. Acrylate of pentaerythritol, acrylate of alkylene oxide adduct of tripentaerythritol, etc. These may be used individually by 1 type, and may use 2 or more types together.

The content of the (meth)acrylate urethane in the active energy ray curable composition is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.

＜Antistatic polymer＞ As the antistatic polymer used in this embodiment, a polymer of (meth)acrylate and a cationic quaternary ammonium salt monomer can be used. The manufacturing method of the antistatic polymer used in this embodiment is not specifically limited. For example, by copolymerizing (meth)acrylate and cationic quaternary ammonium salt monomer in the presence of a radical initiator, the antistatic polymer used in this embodiment can be obtained.

The (meth)acrylate is not particularly limited. Examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, ( Butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, laurel (meth)acrylate Esters, stearyl (meth)acrylate, isostearyl (meth)acrylate, etc. These may be used individually by 1 type, and may use 2 or more types together.

The cationic quaternary ammonium salt monomer is not particularly limited, and examples thereof include: dimethylaminoethyl (meth)acrylate methyl chloride quaternary salt, dimethylaminoethyl (meth)acrylate methyl sulfate Ester quaternary salt, dimethylaminopropyl (meth)acrylate quaternary methyl chloride salt, dimethylaminopropyl (meth)acrylate methyl sulfate quaternary salt, etc. These may be used individually by 1 type, and may use 2 or more types together.

The antistatic polymer of this embodiment can be synthesized by a known method and is not particularly limited. For example, a predetermined amount of (meth)acrylate and cationic can be combined in the presence of a polymerization initiator such as azobisbutyronitrile. The quaternary ammonium salt monomer is heated at about 65°C while stirring until the monomer component disappears, thereby synthesizing an antistatic polymer. At this time, as solvent dilution, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, etc. can be used.

＜Polymerization initiator＞ The active energy ray curable composition of the present embodiment may further contain a polymerization initiator based on active energy rays as necessary. Here, the polymerization initiator based on active energy rays includes both a photopolymerization initiator and a polymerization initiator based on active energy rays 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-chloromethyl naphthalene, diphenyl sulfide, thiurethane, etc. Sulfur compounds, etc.

The polymerization initiator using active energy rays such as ultraviolet rays is not particularly limited, and examples thereof include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethyl Oxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chloro Benzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethyl Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,4-(2-hydroxyethoxy)phenyl-(2 -Hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4 , 4-Trimethylpentylphosphine oxide, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)acetone), etc.

The commercially available product of a polymerization initiator that utilizes active energy rays such as ultraviolet rays is not particularly limited. For example, the product names manufactured by CIBA SPECIALTY CHEMICALS: IRGACURE 184, IRGACURE369, IRGACURE651, IRGACURE500, IRGACURE819, IRGACURE907, IRGACURE784, IRGACURE2959, IRGACURE1000, IRGACURE1300, IRGACURE1700, IRGACURE1800, IRGACURE1850, DAROCUR 1116, DAROCUR1173; manufactured by BASF (BASF) Xilin The trade name of UBECRYL (UBECRYL) P36; the trade name of Fratelli Lamberti (Fratelli Lamberti) is the trade name of ESACURE KIP150, ESACURE KIP100F, ESACURE KT37, ESACURE KT55, ESACURE KTO46, ESACURE TZT , ESACURE KIP75LT; trade name Kayacure DETX manufactured by Nippon Kayaku Company.

In addition, if necessary, a radical polymerization initiator may be used in combination with the active energy ray initiator. The radical polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, and diisopropylbenzene peroxide. Organic peroxides such as tertiary butyl peroxide, tertiary butyl peroxybenzoate, diisopropyl peroxycarbonate, tertiary butyl peroxyisopropyl monocarbonate, 2,2'-azobis Isobutyronitrile (2,2'-azobisisobutyronitrile, AIBN) and other azo compounds.

The content of these polymerization initiators varies according to their kind, etc., and is preferably 1 per 100 parts by mass of the total amount of (meth)acrylate urethane and polyfunctional (meth)acrylate as a standard. Parts by mass ~ 8 parts by mass. When the content is 1 part by mass or more, the active energy ray sensitivity is sufficient, and when the content is 8 parts by mass or less, the active energy ray sufficiently reaches the deep part of the coating film, and the curability of the deep part of the coating film is sufficient.

＜Other additives＞ In the active energy ray curable composition of the present embodiment, in addition to the organic solvents, monomers, and various initiators, as long as the effects of the present invention are not impaired, it may be added as necessary, usually contained in paints and coatings. Various additives in cloth agents. Examples of additives are not particularly limited. Examples include light stabilizers, ultraviolet absorbers, catalysts, leveling agents, defoamers, polymerization accelerators, antioxidants, flame retardants, infrared absorbers, and antistatic agents. Agent, slip agent, etc.

<Use> The use of the active energy ray-curable composition of the present embodiment is not particularly limited, and examples thereof include coatings for optical films and coating agents. The object to be coated or coated (substrate) is not particularly limited, and examples include: mobile phones, watches, compact discs (compact discs), audio equipment, office automation (Office Automation, OA) equipment and other electrical-electronics Equipment; electronic parts such as touch panels and anti-reflective panels of cathode ray tubes; household appliances such as refrigerators, vacuum cleaners, microwave ovens, etc.; automobile interior accessories such as meter panels and dashboards; pre-coated metal steel plates; automobile bodies , Bumpers, spoilers, door handles, steering wheels, headlights, motorcycle gasoline tanks, aluminum wheels with plating-evaporation or sputtering, rearview mirrors and other automobile parts; garages (carport) Roofs, lighting roofs; plastic molded products such as polyvinyl chloride, acrylic resin, polyethylene terephthalate, polycarbonate, acrylonitrile-butadiene-styrene copolymer (Acrylonitrile Butadiene Styrene, ABS) resin, etc. , Protective layers for optical disc recording media, protective layers for various optical lenses such as sunglasses or corrective glasses.

The coating method or coating method is not particularly limited, and examples thereof include an air spray method, an electrostatic coating method, a roll coater method, a flow coater method, and a spin coating method.

The thickness of the coating film obtained by coating or coating is not particularly limited, but for example, it is preferably about 1 μm to 100 μm. By setting the thickness of the coating film to be 1 μm or more, it sufficiently functions as a coating film, and by setting the thickness to be 100 μm or less, the thickness of the coating film is not too thick, and the physical properties of the coating object can be easily exhibited. [Example]

Next, embodiments will be described in conjunction with comparative examples. However, the present invention is not limited to these Examples. In addition, below, content etc. are based on mass unless otherwise indicated.

＜Synthesis example of (meth)acrylic acid adduct＞ [Acrylic (A-A)] In a four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 1,151 parts by mass (16.0 mol) of acrylic acid, 604 parts by mass (4.44 mol) of pentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), and 43.9 parts by mass of p-toluenesulfonic acid were added Parts by mass, 2.1 parts by mass of hydroquinone monomethyl ether, and 552 parts by mass of toluene were mixed. Thereafter, under reduced pressure, while blowing in air, the reaction was allowed to react until 68% of all hydroxyl groups in the pentaerythritol were esterified while maintaining the reaction temperature at about 100°C. The reaction proceeded while removing the condensation water, and the generated condensation water was 179 parts by mass. After the reaction, 353 parts by mass of toluene was added. With respect to the acid component of the reaction liquid to which toluene was added, a 20% by mass aqueous sodium hydroxide solution corresponding to 1.1 times mol was added while stirring to perform a neutralization treatment, thereby removing excess acrylic acid and p-toluenesulfonic acid. Then, the organic layer was separated, and 10 parts by mass of water was added to 100 parts by mass of the organic layer while stirring, thereby performing a water washing treatment. Then, the organic layer was separated again and heated under reduced pressure, whereby toluene was distilled off. The obtained acrylate (A-A) was 837 parts by mass, and the hydroxyl value was 250 mgKOH/g.

[Acrylic (A-B)] In a four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 1,151 parts by mass (16.0 mol) of acrylic acid, 604 parts by mass (4.44 mol) of pentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), and 43.9 parts by mass of p-toluenesulfonic acid were added Parts by mass, 2.1 parts by mass of hydroquinone monomethyl ether, and 552 parts by mass of toluene were mixed. Thereafter, while blowing in air, the reaction was allowed to react until 75% of all hydroxyl groups in the pentaerythritol were esterified while maintaining the reaction temperature at about 100°C under reduced pressure. The reaction proceeded while removing the condensation water, and the generated condensation water was 179 parts by mass. After the reaction, 353 parts by mass of toluene was added. With respect to the acid component of the reaction liquid to which toluene was added, a 20% by mass aqueous sodium hydroxide solution corresponding to 1.1 times mol was added while stirring to perform a neutralization treatment, thereby removing excess acrylic acid and p-toluenesulfonic acid. Then, the organic layer was separated, and 10 parts by mass of water was added to 100 parts by mass of the organic layer while stirring, thereby performing a water washing treatment. Then, the organic layer was separated again and heated under reduced pressure, whereby toluene was distilled off. The obtained acrylate (A-B) was 837 parts by mass, and the hydroxyl value was 190 mgKOH/g.

[Acrylic (A-C)] In a four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 1,151 parts by mass (16.0 mol) of acrylic acid, 604 parts by mass (4.44 mol) of pentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), and 43.9 parts by mass of p-toluenesulfonic acid were added Parts by mass, 2.1 parts by mass of hydroquinone monomethyl ether, and 552 parts by mass of toluene were mixed. Thereafter, under reduced pressure, while blowing in air, the reaction was allowed to react until 78% of all hydroxyl groups in the pentaerythritol were esterified while maintaining the reaction temperature at about 100°C. The reaction proceeded while removing the condensation water, and the generated condensation water was 179 parts by mass. After the reaction, 353 parts by mass of toluene was added. With respect to the acid component of the reaction liquid to which toluene was added, a 20% by mass aqueous sodium hydroxide solution corresponding to 1.4 times mol was added while stirring to perform a neutralization treatment, thereby removing excess acrylic acid and p-toluenesulfonic acid. Then, the organic layer was separated, and 10 parts by mass of water was added to 100 parts by mass of the organic layer while stirring, thereby performing a water washing treatment. Then, the organic layer was separated again and heated under reduced pressure, whereby toluene was distilled off. The obtained acrylate (A-C) was 837 parts by mass, and the hydroxyl value was 163 mgKOH/g.

[Acrylic (A-D)] In a four-necked flask equipped with a thermometer, a stirrer, and a water-cooled condenser, 1,151 parts by mass (16.0 mol) of acrylic acid, 604 parts by mass (4.44 mol) of pentaerythritol (manufactured by Koei Chemical Industry Co., Ltd.), and 43.9 parts by mass of p-toluenesulfonic acid were added Parts by mass, 2.1 parts by mass of hydroquinone monomethyl ether, and 552 parts by mass of toluene were mixed. Thereafter, under reduced pressure, while blowing in air, the reaction was allowed to react until 83% of all hydroxyl groups in the pentaerythritol were esterified while maintaining the reaction temperature at about 100°C. The reaction proceeded while removing condensation water, and the generated condensation water was 256 parts by mass. After the reaction, 353 parts by mass of toluene was added. With respect to the acid component of the reaction liquid to which toluene was added, a 20% by mass aqueous sodium hydroxide solution corresponding to 1.4 times mol was added while stirring to perform a neutralization treatment, thereby removing excess acrylic acid and p-toluenesulfonic acid. Then, the organic layer was separated, and 10 parts by mass of water was added to 100 parts by mass of the organic layer while stirring, thereby performing a water washing treatment. Then, the organic layer was separated again and heated under reduced pressure, whereby toluene was distilled off. The obtained acrylate (A-D) was 1082 parts by mass, and the hydroxyl value was 120 mgKOH/g.

In addition, the hydroxyl value is obtained by the following method. Specifically, the acrylate obtained in each synthesis example described above was dissolved in acetic anhydride/pyridine (15 parts by mass/85 parts by mass). Then, after reacting at 90°C for 1.5 hours, a small amount of water was added to react for another 10 minutes, and then cooled to room temperature. Then, add phenolphthalein as an indicator and titrate with a 1 mol/L potassium hydroxide (KOH) ethanol solution to obtain the hydroxyl value.

＜Synthesis example of (meth)acrylate urethane＞ Using the acrylate of pentaerythritol obtained by the above-mentioned synthesis example, urethane acrylate was produced as follows. When the viscosity is high when producing the following acrylic urethane, the viscosity is reduced appropriately with a butyl acetate solution.

In addition, as a method for measuring the refractive index described later, a refractive index measuring device (product name: prism coupler) manufactured by Metricon Corporation was used to measure the obtained film (coating layer). ) Method of refractive index at a wavelength of 589 nm. The higher the refractive index, the better. Specifically, the refractive index is preferably 1.520 or more, more preferably 1.530 or more, and still more preferably 1.540 or more.

[Acrylic Urethane (U-A)] To the flask were added toluene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) 174 g (1 mol), hydroquinone monomethyl ether 0.44 g, and 621 g of pentaerythritol acrylate (AB) with a hydroxyl value of 190 mgKOH/g. After 2.1 mol), the reaction is carried out at 70°C to 80°C until the amount of free isocyanate becomes 0.1% or less, thereby obtaining acrylic urethane (UA). A cured film of the obtained urethane acrylate (U-A) was produced, and the refractive index of the cured film was measured to be 1.549.

[Acrylic Urethane (U-B)] Add xylylene diisocyanate [manufactured by Mitsui Chemicals Co., Ltd.] 188 g (1 mol), hydroquinone monomethyl ether 0.44 g, and the above-mentioned acrylate (AB) of pentaerythritol with a hydroxyl value of 190 mgKOH/g. After 829 g (2.8 mol), the reaction was carried out at 70° C. to 80° C. until the amount of free isocyanate became 0.1% or less, thereby obtaining acrylic urethane (UB). A cured film of the obtained acrylic urethane (U-B) was produced, and the refractive index of the cured film was measured to be 1.542.

[Acrylic Urethane (U-C)] Add toluene diisocyanate [manufactured by Mitsui Chemicals Co., Ltd.] 174 g (1 mol), hydroquinone monomethyl ether 0.44 g, and the above-mentioned hydroxyl value of 163 mgKOH/g pentaerythritol acrylate (AC) 964 g After (2.8 mol), the reaction is carried out at 70°C to 80°C until the amount of free isocyanate becomes 0.1% or less, thereby obtaining acrylic urethane (UC). A cured film of the obtained urethane acrylate (U-C) was produced, and the refractive index of the cured film was measured to be 1.546.

[Acrylic Urethane (U-D)] Into the flask were added xylylene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) 188 g (1 mol), hydroquinone monomethyl ether 0.44 g, and the above-mentioned acrylate (AC) of pentaerythritol with a hydroxyl value of 163 mgKOH/g After 964 g (2.8 mol), the reaction was performed at 70°C to 80°C until the amount of free isocyanate became 0.1% or less, thereby obtaining acrylic urethane (UD). A cured film of the obtained acrylic urethane (U-D) was produced, and the refractive index of the cured film was measured to be 1.541.

[Acrylic Urethane (U-E) (Comparative Example)] Add 222 g (1 mol) of isophorone diisocyanate (manufactured by Evonik Japan), 0.44 g of hydroquinone monomethyl ether, and pentaerythritol with the above hydroxyl value of 120 mgKOH/g into the flask After 982 g (2.1 mol) of acrylate (AD) of cyanoacrylate (AD), the reaction was carried out at 70°C to 80°C until the amount of free isocyanate became 0.1% or less, thereby obtaining acrylic urethane (UE). A cured film of the obtained acrylic urethane (U-E) was produced, and the refractive index of the cured film was measured to be 1.525.

[Acrylic Urethane (U-F) (Comparative Example)] Add 222 g (1 mol) of isophorone diisocyanate (manufactured by Evonik Japan), 0.44 g of hydroquinone monomethyl ether, and pentaerythritol with the above hydroxyl value of 190 mgKOH/g into the flask After 621 g (2.1 mol) of the acrylate (AB) of phosphate, the reaction was carried out at 70°C to 80°C until the amount of free isocyanate became 0.1% or less, thereby obtaining acrylic urethane (UF). A cured film of the obtained urethane acrylate (U-F) was produced, and the refractive index of the cured film was measured to be 1.525.

[Acrylic Urethane (U-G) (Comparative Example)] To the flask were added toluene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) 174 g (1 mol), hydroquinone monomethyl ether 0.44 g, and 471 g of pentaerythritol acrylate (AA) with the above hydroxyl value of 250 mgKOH/g After (2.1 mol), the reaction is carried out at 70°C to 80°C until the amount of free isocyanate becomes 0.1% or less, thereby obtaining acrylic urethane (UG). A cured film of the obtained acrylic urethane (U-G) was produced, and the refractive index of the cured film was measured to be 1.554.

[Acrylic Urethane (U-H) (Comparative Example)] Add 174 g (1 mol) of toluene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and 982 g of pentaerythritol acrylate (AD) with the above hydroxyl value of 120 mgKOH/g in the flask After (2.1 mol), the reaction is carried out at 70°C to 80°C until the amount of free isocyanate becomes 0.1% or less, thereby obtaining acrylic urethane (UH). A cured film of the obtained urethane acrylate (U-H) was produced, and the refractive index of the cured film was measured to be 1.544.

[Acrylic Urethane (U-I) (Comparative Example)] Into the flask, 174 g (1 mol) of toluene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.), 0.44 g of hydroquinone monomethyl ether, and 532 g of pentaerythritol acrylate (AB) with a hydroxyl value of 190 mgKOH/g were added After (1.8 mol), the reaction is carried out at 70°C to 80°C until the amount of free isocyanate becomes 0.1% or less, thereby obtaining acrylic urethane (UI). A cured film of the obtained urethane acrylate (U-I) was produced, and the refractive index of the cured film was measured to be 1.557.

[Acrylic Urethane (U-J) (Comparative Example)] Add toluene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) 174 g (1 mol), hydroquinone monomethyl ether 0.44 g, and pentaerythritol acrylate (AB) with a hydroxyl value of 190 mgKOH/g, 1063 g. After (3.6 mol), the reaction is carried out at 70°C to 80°C until the amount of free isocyanate becomes 0.1% or less, thereby obtaining acrylic urethane (UJ). A cured film of the obtained acrylic urethane (U-J) was produced, and the refractive index of the cured film was measured to be 1.527.

＜Antistatic polymer＞ [Antistatic Polymer (P-A)] Add 60 g of lauryl methacrylate, 30 g of dimethylaminoethyl methacrylate quaternary salt of methyl chloride, 147 g of isopropanol, and 63 g of methyl ethyl ketone into the flask, and then use nitrogen for 30 minutes Degas. Then, 0.9 g of azoisobutyronitrile was added and reacted at 65° C. until the residual monomer amount became 1.0% or less, thereby obtaining an antistatic polymer (P-A).

[Antistatic Polymer (P-B)] After adding 60 g of butyl methacrylate, 30 g of dimethylaminoethyl methacrylate quaternary salt of methyl chloride, 147 g of isopropanol, and 63 g of methyl ethyl ketone into the flask, it was heated with nitrogen for 30 minutes Degas. Then, 0.9 g of azoisobutyronitrile was added and reacted at 65° C. until the residual monomer amount reached 1.0% or less, thereby obtaining an antistatic polymer (P-B).

[Table 1] UA UB UC UD UE UF UG UH UI UJ (A) AA (hydroxyl value: 250 mgKOH/g) 2.1 AB (hydroxyl value: 190 mgKOH/g) 2.1 2.8 2.1 1.8 3.6 AC (hydroxyl value: 163 mgKOH/g) 2.8 2.8 AD (hydroxyl value: 120 mgKOH/g) 2.1 2.1 (B) Toluene diisocyanate 1 1 1 1 1 1 Xylylene diisocyanate 1 1 Isophorone diisocyanate 1 1 a/b 1.05 1.4 1.4 1.4 1.05 1.05 1.05 1.05 0.9 1.8

The numerical value of each component described in Table 1 indicates the content, and the unit is "mole". In addition, Table 1 shows a list of the composition of the (meth)acrylate urethanes (UA to UJ) contained in the active energy ray curable compositions of the Examples and Comparative Examples described in Table 2 described later .

<Preparation of active energy ray hardening composition> With respect to 100 parts by mass of the total amount of (meth)acrylate urethane (UA to UJ) and polyfunctional (meth)acrylate prepared in the ratio shown in Table 2 described later, antistatic polymer 3.5 was prepared Parts by mass, 3 parts by mass of photopolymerization initiator (IRGACURE 184 manufactured by CIBA SPECIALTY CHEMICALS (stock)), and 100 parts by mass of methyl ethyl ketone. Make a coating liquid.

On a polyethylene terephthalate substrate (PET made by Toyobo Co., Ltd., model: COSMOSHINE A4300), the coating is applied in such a way that the film thickness is about 7 μm in a dry state. The liquid was irradiated under a nitrogen atmosphere with a high-pressure mercury lamp of 80 W/cm and a cumulative illuminance of 600 mJ/cm ² to harden it to obtain a film.

For each obtained film, various evaluations were performed according to the following methods. The results are shown in Table 2 below.

＜Evaluation method＞ 〔Whether the coating liquid is cloudy〕 The appearance of the above-mentioned coating liquid was visually judged. When the coating liquid is transparent, it is ○, and when it is cloudy, it is ×. In addition, for those who are cloudy, no subsequent evaluation will be performed.

〔Pencil Hardness〕 According to JIS K5400, use a pencil scratch tester to apply a load of 750g to scratch, which is the hardest pencil hardness without scratches.

〔Scratch resistance〕 For the film obtained above (hereinafter also referred to as "test film"), in accordance with JIS K5701-1 as a standard, using a friction tester (manufactured by Ohira Rika Kogyo Co., Ltd.), the steel wool #0000 was round-tripped 100 with a load of 1 kg Times. The haze value of the test film before and after the test was measured using a haze meter ("NDH4000" manufactured by Nippon Denshoku Industries Co., Ltd.), and the difference between the two values was used for evaluation. The smaller the value, the better the scratch resistance.

〔Formability〕 After cutting the test film into a size of 10 cm×10 cm, place it on a horizontal surface and fix one corner. Then, the float (mm) of the three corners with respect to the horizontal plane was measured, and the average value was calculated. The smaller the value, the less warpage and the better the moldability.

[Surface resistance value] Using a surface resistance measuring device (trade name: R8340A, manufactured by Advantest), the surface resistance value (Ω/□) of the test film was measured in an atmosphere of 20°C and 65% RH. The smaller the measured surface resistance value, the better the antistatic performance.

[Table 2] Deployment Example Comparative example 1 2 3 4 5 1 2 3 4 5 6 (Meth) acrylic urethane UA 80 UB 80 100 UC 80 UD 80 UE 80 UF 100 UG 80 UH 80 UI 80 UJ 80 a/b 1.05 1.4 1.4 1.4 1.4 1.05 1.05 1.05 1.05 0.9 1.8 Hydroxyl value 190 190 163 163 190 120 190 250 120 190 190 Organic isocyanate TDI XDI TDI XDI XDI IPDI IPDI TDI TDI TDI TDI Multifunctional (meth)acrylate Dipentaerythritol hexaacrylate 20 20 20 20 20 20 20 20 20 20 Antistatic polymer PA 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 PB 3.5 Evaluation results Whether the mixed paint is cloudy ○ ○ ○ ○ ○ ○ × ○ ○ × ○ Pencil hardness 2H 2H 2H 2H 2H 2H - H 2H - 2H Scratch resistance 1 1 1 1 2 1 - 2 2 - 1 Formability 3 3 4 4 2 8 - 1 8 - 4 Surface intrinsic resistance value 5.8×10 ⁹ 3.0×10 ⁹ 3.2×10 ⁹ 6.2×10 ⁹ 2.0×10 ⁹ 7.2×10 ⁹ - 8.6×10 ⁹ 8.2×10 ⁹ - 6.0×10 ¹¹

The content unit of each component described in Table 2 is parts by mass. In addition, in order to make it easier to understand the content, Table 2 describes conditions related to (meth)acrylate urethane. Specifically, Table 2 describes the molar ratio of (i) the molar number a of the hydroxyl group in the (meth)acrylic acid adduct and (B) the molar number b of the isocyanate group in the organic isocyanate (a/ b), (ii) hydroxyl value of (meth)acrylic acid adduct, (iii) type of organic isocyanate. In Table 2, "TDI" means "toluene diisocyanate", "XDI" means "xylylene diisocyanate", and "IPDI" means "isophorone diisocyanate".

According to Table 2, the following can be known. That is, it can be seen that Examples 1 to 5 using a (meth)acrylic acid adduct having a hydroxyl value of 160 mgKOH/g or more and Comparative Example 1 using a (meth)acrylic acid adduct having a hydroxyl value of less than 160 mgKOH/g Compared with Comparative Example 4, the moldability is superior.

In addition, it can be seen that Examples 1 to 5 using a (meth)acrylic acid adduct having a hydroxyl value of 220 mgKOH/g or less are compared with Comparative Example 3 using a (meth)acrylic acid adduct having a hydroxyl value of more than 220 mgKOH/g. Compared with, the hardness is excellent.

In addition, it can be seen that Examples 1 to 5 using xylylene diisocyanate or toluene diisocyanate as the organic isocyanate are compared with Comparative Example 1 and Comparative Example 2 using isophorone diisocyanate as the organic isocyanate. Excellent compatibility and excellent antistatic performance.

It can be seen that Examples 1 to 5 having a molar ratio (a/b) of 1.00 or more have superior compatibility with the antistatic polymer compared to Comparative Example 5 having a molar ratio (a/b) of less than 1.00.

In addition, it can be seen that Examples 1 to 5 having a molar ratio (a/b) of 1.60 or less have superior antistatic performance compared to Comparative Example 6 having a molar ratio (a/b) of more than 1.60. It can be seen that especially Example 2 and Example 5 have excellent antistatic performance.

Furthermore, in addition to Examples 1 to 5, the (meth)acrylic acid adducts using trivalent or higher aliphatic polyol compounds having a hydroxyl value of 160 mgKOH/g or higher and 220 mgKOH/g or lower were also used. The test was conducted with a (meth)acrylate urethane hardening composition of xylylene diisocyanate or toluene diisocyanate, and it was confirmed that the same high refractive index, pencil hardness, scratch resistance, moldability, and Electrostatic performance.

<Impossible-Unrealistic situation> The (meth)acrylic urethane contained in the active energy ray curable composition of this embodiment is (A) (meth)acrylic acid (meth)acrylic acid added to an aliphatic polyol compound having a valence of three or more. (Meth)acrylic acid adduct with hydroxyl value of 160 mgKOH/g or more and 220 mgKOH/g or less, and (B) selected from the group consisting of xylylene diisocyanate and toluene diisocyanate The reaction product of one or more organic isocyanates in the group has a complicated structure and is therefore difficult to express by a general formula. Moreover, if the structure is not determined, the properties of the substance determined by the structure are not easy to determine. In addition, when multiple different monomers are reacted, if their blending ratios and reaction conditions are different, the characteristics of the obtained reaction products are also very different. That is, the (meth)acrylate urethane contained in the active energy ray curable composition of the present embodiment cannot be directly determined by its structure or characteristics. [Industrial availability]

The active energy ray-curable composition of the present embodiment can obtain a cured film excellent in hardness, scratch resistance, and moldability, and is therefore suitable as a paint or coating agent in fields requiring scratch resistance. Specifically, the present invention can be applied to, for example, a plastic film that protects the screen surface of image display devices such as liquid crystal displays, electroluminescent displays, touch panels, and tablet PCs.

The present invention is not limited to the above-described embodiment, and can be implemented in various configurations within a range that does not deviate from the gist. For example, in order to solve part or all of the above-mentioned problems, or to achieve part or all of the above-mentioned effects, the technical features in the embodiments and the embodiments corresponding to the technical features in each mode described in the summary of the invention can be appropriately replaced and combined. . In addition, if the technical features are not described as necessary technical features in this specification, they can be deleted as appropriate.

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Claims (5)

An active energy ray curable composition containing (meth)acrylate urethane formed by reacting (A) (meth)acrylic acid adduct and (B) organic isocyanate, The (A) (meth)acrylic acid adduct is obtained by adding (meth)acrylic acid to an aliphatic polyol compound with a trivalent or higher valence, and the hydroxyl value is 160 mgKOH/g or higher, 220 mgKOH/g the following; The (B) organic isocyanate is one or more organic isocyanates selected from the group consisting of xylylene diisocyanate and toluene diisocyanate, The molar ratio (a/b) of the molar number a of the hydroxyl group in the (meth)acrylic acid adduct to the molar number b of the isocyanate group in the (B) organic isocyanate is 1.00 or more and 1.60 or less . The active energy ray-curable composition according to claim 1, wherein the aliphatic polyol compound having a valence of three or more is an aliphatic polyol compound having a valence of three or more and less than six valence. The active energy ray curable composition according to claim 1 or claim 2, wherein the aliphatic polyhydric alcohol compound having a valence of three or more is pentaerythritol. The active energy ray curable composition according to claim 1 or claim 2, which further contains (C) a multifunctional (meth)acrylate having three or more (meth)acryloyl groups in one molecule. The active energy ray curable composition according to claim 1 or claim 2, which further contains an antistatic polymer.