JPWO2011102258A1 - (Meth) acrylate compound and curable composition containing the (meth) acrylate compound - Google Patents

Abstract

[PROBLEMS] A (meth) acrylate compound having a high refractive index, capable of giving a cured product excellent in transparency and heat resistance, and excellent in handling properties, a curable composition containing the (meth) acrylate compound, and The cured product is provided. [Solution] A (meth) acrylate compound represented by the following formula (1): (In Formula (1), R1 and R2 are each independently a hydrogen atom or a methyl group, X is an organic group having 6 to 30 carbon atoms including an aromatic ring, a is an integer of 1 to 3, b is an integer of 0-3.)

Description

  The present invention relates to a (meth) acrylate compound suitable as a raw material for producing a transparent material and an optical material, a curable composition containing the (meth) acrylate compound, and a cured product obtained by curing the curable composition. .

  In recent years, materials with excellent optical performance have been demanded along with the development of the optical industry such as optical equipment, optical communication and display. Examples include optical lenses, optical disk substrates, plastic substrates for liquid crystal display elements, color filter substrates, plastic substrates for organic EL display elements, solar cell substrates, touch panels, optical elements, optical waveguides, and LED sealing materials. There is a strong demand for optical lenses, optical elements, and optical waveguide materials.

  Generally, inorganic glass is often used as a substrate for a liquid crystal display element, a substrate for a color filter, a substrate for an organic EL display element, a solar cell substrate, a touch panel, and the like. However, in recent years, many attempts have been made to use a plastic material instead of a glass plate because of problems such as the glass plate is easily broken, cannot be bent, has a large specific gravity, and is not suitable for weight reduction.

  As an optical lens, an optical element, an optical waveguide, and an LED sealing material, in recent years, a plastic material having excellent heat resistance such as reflow resistance has been demanded. However, even if the heat resistance is excellent, a plastic material having a low refractive index increases the edge thickness or the central portion, and the light weight characteristic of plastic is impaired. Therefore, a plastic material having a higher refractive index in addition to heat resistance is desired.

  Japanese Patent Laid-Open No. 10-77321 (Patent Document 1) discloses a member obtained by curing a resin composition comprising an amorphous thermoplastic resin and bis (meth) acrylate curable with active energy rays with active energy rays. However, it can be suitably used for an optical lens, an optical disk substrate, a plastic liquid crystal substrate, and the like instead of a glass substrate. However, there is a concern that transparency may be lowered due to a difference between a refractive index of an amorphous thermoplastic resin and a refractive index of a resin obtained by curing bis (meth) acrylate with active energy rays.

  JP-A-4-325508 (Patent Document 2) describes that the refractive index and heat resistance of a plastic lens material are improved by introducing a fluorene skeleton. However, a compound containing a fluorene skeleton has a very high viscosity, is inferior in handling properties, and does not satisfy the required low viscosity.

  JP-A-2005-272773 (Patent Document 3) describes a cured product obtained by curing a curable composition containing a compound having a biphenyl skeleton, and the composition has a low viscosity and a high refractive index. It is described that a cured product can be obtained. However, there is no description regarding heat resistance, and since the compound having a biphenyl skeleton, which is a component of the composition, is a monofunctional monomer, a problem remains in heat resistance.

JP 10-77321 A JP-A-4-325508 JP 2005-272773 A

  The present invention provides a (meth) acrylate compound capable of giving a cured product having a high refractive index and excellent transparency and heat resistance, a curable composition containing the (meth) acrylate compound, and the It aims at providing the hardened | cured material obtained by hardening | curing a curable composition.

  As a result of intensive studies, the present inventors have found that a (meth) acrylate compound having a specific structure and a curable composition containing the compound can solve the above problems, and have completed the present invention.

  That is, the present invention includes the following matters.

  [1] A (meth) acrylate compound represented by the following formula (1).

(In Formula (1), R < ¹ > and R < ² > are respectively independently a hydrogen atom or a methyl group, X is a C6-C30 organic group containing an aromatic ring, a is an integer of 1-3. And b is an integer of 0 to 3.)
[2] The (meth) acrylate compound according to [1], wherein X is any one of organic groups represented by the following formulas (a) to (h).

(Note that, in the organic groups shown in (a) to (h), the portions with wavy lines represent X bonds in the compound shown in Formula (1).)
[3] The (meth) acrylate compound (1) according to [1] or [2], which is represented by the following formula (2).

(In Formula (2), R < ¹ > and R < ² > are respectively independently a hydrogen atom or a methyl group, a is an integer of 1-3, b is an integer of 0-3.)
[4] The (meth) acrylate compound according to [3], wherein in the formula (2), a naphthyl group is bonded at the α-position.

  [5] The (meth) acrylate compound according to [3] or [4], wherein a is 2 or 3 in the formula (2).

  [6] The (meth) acrylate compound according to any one of [3] to [5], wherein b is 0 or 1 in the formula (2).

[7] The (meth) acrylate compound according to any one of [3] to [6], wherein in the formula (2), R ¹ is a hydrogen atom and R ² is a methyl group.

  [8] The (meth) acrylate compound according to [1], which is represented by the following formula (6).

  [9] A curable composition comprising the (meth) acrylate compound according to any one of [1] to [8] and a polymerization initiator.

  [10] A cured product obtained by curing the curable composition according to [9].

  [11] The cured product according to [10], wherein the refractive index is 1.55 or more and 1.65 or less.

  [12] The cured product according to [10] or [11], wherein the glass transition temperature is 100 ° C. or higher and 300 ° C. or lower.

  [13] A coating material obtained by curing the curable composition according to [9].

  [14] An optical material obtained by curing the curable composition according to [9].

  [15] A lens obtained by curing the curable composition according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the (meth) acrylate compound which can give the hardened | cured material which is high refractive index and excellent in transparency and heat resistance is provided, and also the curable composition containing this (meth) acrylate compound And a cured product thereof.

  The (meth) acrylate compound of the present invention includes an optical lens, an optical disk substrate, a plastic substrate for a liquid crystal display element, a substrate for a color filter, a plastic substrate for an organic EL display element, a solar cell substrate, a touch panel, an optical element, an optical waveguide, and an LED. It is suitably used for applications such as a sealing material.

1 is a ¹ H-NMR chart of the (meth) acrylate compound (6) synthesized in Example 1. FIG.

  Hereinafter, the (meth) acrylate compound of the present invention (hereinafter also referred to as “(meth) acrylate compound (1)”), the curable composition, and the cured product will be described in detail.

[(Meth) acrylate compound (1)]
The (meth) acrylate compound (1) of the present invention is a compound having 1 to 3 ethylenically unsaturated bonds in the molecule as represented by the following formula (1). In the present specification, the (meth) acrylate of the (meth) acrylate compound means acrylate and / or methacrylate.

In the above formula (1), R ¹ and R ² are each independently a hydrogen atom or a methyl group, but R ¹ is preferably a hydrogen atom in terms of curability, and R ² has heat resistance and pencil hardness. A methyl group is preferable in terms of improvement.

  a is an integer of 1 to 3, and is preferably 2 or 3 and more preferably 3 from the viewpoints of heat resistance, pencil hardness and refractive index improvement, and availability of raw materials.

  b is an integer of 0 to 3, and is preferably 0 or 1 and more preferably 0 from the viewpoints of improvement in heat resistance and pencil hardness and availability of raw materials.

  X is an organic group having 6 to 30 carbon atoms including an aromatic ring, but preferably 7 to 24 carbon atoms and 7 to 19 carbon atoms from the viewpoint of improving the refractive index and reducing the viscosity. More preferably, it is especially preferable that it is C7-15.

  Specific examples of X include organic groups represented by the following (a) to (h). In addition, the location which attached | subjected the wavy line in the organic group represented by (a)-(h) represents the bond of X in the (meth) acrylate compound (1).

  Among the above specific examples, those having the naphthoyl skeleton of (c) are particularly preferable from the viewpoint of refractive index, viscosity, and availability of raw materials.

  The (meth) acrylate compound (1) is particularly preferably represented by the following formula (2). The compound represented by the following formula (2) is also referred to as “(meth) acrylate compound (2)”.

In the above formula (2), R ^1, R ^2, a and b are the same as those of the R ^1, R ^2, a and b of (meth) acrylate compound (1).

  The (meth) acrylate compound (2) preferably includes a naphthalene structure bonded at the α-position from the viewpoint of handling properties of the raw material, and is a compound represented by the following formula (6) (hereinafter referred to as “(meth) acrylate compound”). (6) ”is also most preferable.

  The viscosity of the (meth) acrylate compound (1) at 25 ° C. is 10 to 20,000 mPa · s, preferably 50 to 18,000 mPa · s, more preferably 100 to 15,000 mPa · s. When the viscosity is lower than 10 mPa · s, or higher than 20,000 mPa · s, handling properties may be deteriorated, workability may be poor, and use may be difficult. In addition, the apparatus and conditions used for the said viscosity measurement are B type viscometer DV-III ULTRA (made by BROOKFIELD), rotor No. as described in the Example mentioned later. 42, rotation speed is 1 to 7 rpm.

[Production method of (meth) acrylate compound (1)]
As a manufacturing method of the said (meth) acrylate compound (1), the compound (henceforth "(meth) acrylate compound (3)") represented by following formula (3), and the said formula (1) A method of reacting a compound having the same organic group as X and having a leaving ability (hereinafter also referred to as “substituent Y”) (hereinafter also referred to as “compound (4)”); A method of reacting the (meth) acrylate compound (3) with a compound having the same organic group as X in the formula (1) and having a terminal carboxylic acid (hereinafter also referred to as “compound (5)”). Etc.

  In addition, the said method shows an example of the manufacturing method of the (meth) acrylate compound (1) of this invention, It can manufacture using not only the said method but various well-known methods.

In said formula (3), R < ¹ > and R < ² > are respectively independently a hydrogen atom or a methyl group, a is an integer of 1-3, b is an integer of 0-3.

  Examples of the (meth) acrylate compound (3) include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol di (meth) acrylate, Examples include propylene oxide-modified pentaerythritol tri (meth) acrylate and propylene oxide-modified pentaerythritol di (meth) acrylate.

  In the compound (4), examples of the substituent Y include a substituent that reacts with a hydroxyl group and has a leaving ability, and examples thereof include a halogen atom and an alkoxy group. Among these, a chlorine atom, a bromine atom, a methoxy group, and an ethoxy group are particularly preferable from the viewpoints of reactivity and availability.

  Examples of the compound (4) include benzyl chloride, benzyl bromide, benzyl chloromethyl ether, benzyl chloromethyl sulfide, 4-benzyloxyphenylacetyl chloride, benzoyl chloride, benzoyl bromide, methyl 2-benzoylbenzoate, and benzoyl fluoride. , Methyl benzoylformate, ethyl benzoylformate, methyl 3-benzoylpropionate, biphenyl chloride, 4,4′-biphenyldicarbonyl chloride, dimethyl 4,4′-biphenyldicarboxylate, diethyl 4,4′-biphenyldicarboxylate, 4 -Phenylbenzoyl chloride, 4-phenylbenzyl bromide, 1-naphthoyl chloride, 2-naphthoyl chloride, 2-anthracene carboxylic acid, 9-anthracene carboxylic acid, 1,8-an Rasendicarboxylic acid dimethyl, anthraquinone-2-carbonyl chloride, 9-fluorene acetic acid, 9-fluorenecarboxylic acid, 9-fluorenone-2-carboxylic acid, chloroformate-9-fluorenylmethyl, 2,2 ', 4'- Examples include trichloroacetophenone, 2,3 ′, 4′-trichloroacetophenone, 2,4,6-trichlorobenzoyl chloride, triphenylacetic acid, triphenylmethyl chloride, triphenylmethyl bromide, methyl diphenylacetate and diphenylacetyl chloride.

  The molar ratio when the (meth) acrylate compound (3) and the compound (4) are reacted is the number of moles of hydroxyl group in the (meth) acrylate compound (3): the number of leaving groups in the compound (4). The number of moles is preferably 1: 1 to 1: 1.2.

  When the (meth) acrylate compound (3) and the compound (4) are reacted, it is preferable to use a base. By using a base, the reaction can be significantly accelerated.

  Examples of the base include triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] octane, t-butoxy potassium, water Examples include sodium oxide and ion exchange resin. These bases may be used individually by 1 type, and may be used in combination of 2 or more type. 1.0-2.0 equivalent is preferable with respect to 1 hydroxyl group in (meth) acrylate compound (3), and, as for the addition amount of a base, 1.0-1.5 equivalent is more preferable. If the addition amount is less than 1.0 equivalent, the reactivity may decrease. On the other hand, if the amount added exceeds 2.0 equivalents, side reactions may occur during the reaction.

  The reaction temperature in the reaction between the (meth) acrylate compound (3) and the compound (4) is preferably −10 to 100 ° C., more preferably 0 to 80 ° C., and particularly preferably 10 to 40 ° C.

  Examples of the solvent used in the reaction of the (meth) acrylate compound (3) and the compound (4) include cyclic ethers such as tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide; toluene and xylene, and the like. Aromatic hydrocarbons; halogenated hydrocarbons such as methylene chloride and chloroform; acetonitrile and the like. Of these, tetrahydrofuran, toluene and dichloromethane are preferred.

  By performing the reaction under the reaction conditions described above, side reactions are suppressed, and the (meth) acrylate compound (1) can be obtained with good yield and purity. Moreover, the possibility of superposition | polymerization of (meth) acrylate compound (1) is reduced by reacting at room temperature vicinity.

  The (meth) acrylate compound (1) can also be produced by reacting the (meth) acrylate compound (3) with the compound (5).

  Examples of the compound (5) include benzoic acid, 1-naphthoic acid, 2-naphthoic acid, 4-phenylbenzoic acid, 2-phenylbenzoic acid, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, and 9-anthracenecarboxylic acid. And acid and 9-fluorenecarboxylic acid. Of these, 1-naphthoic acid and 4-phenylbenzoic acid are preferred.

  The molar ratio when the (meth) acrylate compound (3) and the compound (5) are reacted is the number of moles of hydroxyl group in the (meth) acrylate compound (3): the number of moles of carboxylic acid in the compound (5). = 1: 1 to 1: 1.2 is preferable.

  When the (meth) acrylate compound (3) and the compound (5) are reacted, it is preferable to use a condensing agent. By using the condensing agent, the carboxylic acid is activated, and the reaction can be significantly accelerated.

  Examples of the condensing agent include N, N′-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1,1′-carbonyldiimidazole, 2-chloro-1-methylpyridinium iodine, methyl -3-methyl-2-fluoropyridinium tosylate, methanesulfonyloxybenzotriazole, 1-propylphosphonic acid cyclic anhydride and the like. Of these, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is preferred. The said condensing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  1.0-2.0 equivalent is preferable with respect to 1 carboxylic acid in a compound (5), and, as for the addition amount of a condensing agent, 1.0-1.5 equivalent is more preferable. If the addition amount is less than 1.0 equivalent, the reactivity may decrease. On the other hand, if the amount added exceeds 2.0 equivalents, side reactions may occur during the reaction or post-treatment may become complicated.

  When the (meth) acrylate compound (3) and the compound (5) are reacted, a tertiary amine can be added as a catalyst. The reaction can be significantly accelerated by using a tertiary amine. Examples of the tertiary amine include pyridine, N, N-dimethyl-4-aminopyridine, triethylamine, N, N-diisopropylethylamine and N, N-diethylaniline. Of these, N, N-dimethyl-4-aminopyridine is preferred.

  The reaction temperature in the reaction between the (meth) acrylate compound (3) and the compound (5) is preferably −10 to 80 ° C., more preferably 0 to 60 ° C., and further preferably 10 to 40 ° C.

  Examples of the solvent used in the reaction between the (meth) acrylate compound (3) and the compound (5) include cyclic ethers such as tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide; toluene and xylene, and the like. Aromatic hydrocarbons; halogenated hydrocarbons such as methylene chloride and chloroform; and acetonitrile. Of these, tetrahydrofuran, toluene and dichloromethane are preferred.

  By performing the reaction under the reaction conditions described above, side reactions are suppressed, and the (meth) acrylate compound (1) can be obtained with good yield and purity. Moreover, the possibility of superposition | polymerization of (meth) acrylate compound (1) is reduced by reacting at room temperature vicinity.

(Curable composition)
The curable composition of this invention contains the said (meth) acrylate compound (1) and a polymerization initiator.

  As the polymerization initiator, a photopolymerization initiator and a thermal polymerization initiator are used. In the case of using a photopolymerization initiator, the (meth) acrylate compound (1) in the curable composition causes a polymerization reaction by irradiating the curable composition with active energy rays such as ultraviolet rays or visible rays, and the cured product. Can be obtained. When a thermal polymerization initiator is used, the (meth) acrylate compound (1) undergoes a polymerization reaction by heating to obtain a cured product. Among these, a photopolymerization initiator is preferable from the viewpoint that it can be used for a substrate having low heat resistance.

  As photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-2-phenylacetophenone, xanthone, fluorene, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chloro Benzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoylpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, phenylglyoxylic acid methyl ester, thioxanthone, diethylthioxanthone, 2 Isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2, 4,6-trimethylbenzoyl) phenylphosphinate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 1- [4- (2-hydroxyethoxy) -phenyl]- Examples include 2-hydroxy-2-methylpropan-1-one. These photopolymerization initiators may be used alone or in combination of two or more.

  Examples of the thermal polymerization initiator include azo compounds and organic peroxides. As the azo compound, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyric acid) dimethyl, 4,4 ′ -Azobis (4-cyanovaleric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride and 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl)]- Propionamide} and the like. Organic peroxides include benzoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate and 1,1,3,3-tetramethylbutylperoxide. Examples thereof include oxy-2-ethylhexanoate. These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

  Although the usage-amount of a polymerization initiator is not specifically limited, It is 0.1-5 mass parts with respect to 100 mass parts of total amounts with the (meth) acrylate compound (1) and the radical reactive component mentioned later which is an arbitrary component. , Preferably it is 0.5-3 mass parts, More preferably, it is 0.5-1 mass part. When the usage-amount of a polymerization initiator exists in said range, the polymerization rate of (meth) acrylate compound (1) will become quick, and a curable composition will not receive polymerization inhibition by oxygen etc. Furthermore, high intensity | strength and heat resistance can be achieved about the cured film obtained, and coloring does not occur easily.

  The curable composition may contain other components as necessary. Examples of other components include radical reactive components such as polymerization inhibitors, urethane oligomers and reactive monomers, and solvents.

  The polymerization inhibitor is used to prevent a component from causing a polymerization reaction during storage of the curable composition. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol and 2,6-di-tert-butyl-4-methylphenol.

  The polymerization inhibitor may be contained in an amount of 0.1 parts by mass or less based on 100 parts by mass of the total amount of the (meth) acrylate compound (1) and the radical reactive component described later which is an optional component.

  The radical-reactive component is used to adjust the properties of the obtained cured product, for example, mechanical properties such as hardness, elasticity and adhesion, optical properties such as transparency, and reactivity. Examples of the radical reactive component include urethane oligomers and reactive monomers.

  The urethane oligomer is an oligomer having a urethane bond and an ethylenically unsaturated bond, and is a polymer having a relatively low molecular weight in which 2 to 20 urethane monomers obtained by reacting an isocyanate group and a hydroxyl group are bonded. It is. Examples of the urethane oligomer include those manufactured by Arakawa Chemical Industries, Ltd., trade name beam sets 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90, EM92; Name photomer 6008, 6210; manufactured by Shin-Nakamura Chemical Co., Ltd., trade names NK Oligo U-2PPA, U-4HA, U-6HA, U-15HA, UA-32P, U-324A, U-4H, U-6H , UA-160TM, UA-122P, UA-2235PE, UA-340P, UA-5201, UA-512; manufactured by Toagosei Co., Ltd., trade names Aronix M-1100, M-1200, M-1210, M-1310 , M-1600, M-1960, M-5700, Aron Oxetane OXT-101; manufactured by Kyoeisha Chemical Co., Ltd., trade name H-600, AT606, UA-306H, UF-8001; manufactured by Nippon Kayaku Co., Ltd., trade names Kayrad UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX -7101; manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade names, purple light UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000, UV-7600B, UV-7605B, UV-2010B, UV- 6630B, UV-7510B, UV-7461TE, UV-3310B, UV-6640B; manufactured by Negami Kogyo Co., Ltd., trade name Art Resin UN-1255, UN-5200, UN-7700, UN-333, UN-905, HDP -4T, HMP-2, UN-901T, UN-3320HA, UN-3320H , UN-3320HC, UN-3320HS, H-61, HDP-M20, UN-5500, UN-5507; manufactured by Daicel UC Corporation, trade names Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301, and the like. These may be used alone or in combination of two or more.

  The reactive monomer is also called a reactive diluent, and is a monomer having an ethylenically unsaturated bond. The monomer having an ethylenically unsaturated bond may be a monofunctional monomer or a polyfunctional monomer, and specifically includes an ethylenically unsaturated aromatic compound, a carboxyl group-containing unsaturated compound, a monofunctional (meth) acrylate, a difunctional monomer. Examples include (meth) acrylate, polyfunctional (meth) acrylate, epoxy poly (meth) acrylate, urethane poly (meth) acrylate, and polyester poly (meth) acrylate.

  Examples of the ethylenically unsaturated aromatic compound include diisopropenylbenzene, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, and o-chlorostyrene. , M-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, p-methoxystyrene, N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, ethylenically unsaturated pyridine And ethylenically unsaturated imidazole.

  Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.

  Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl. (Meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, Nonyl (meth) acrylate, Decyl (meth) acrylate, Isodecyl (meth) acrylate, Undecyl (meth) acrylate, Dodecyl (meth) acrylate, Lauri Alkyl (meth) acrylates such as (meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate; trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, Fluoroalkyl (meth) acrylates such as octafluoropentyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate; hydroxyalkyl such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate (Meth) acrylates; phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate Phenoxyalkyl (meth) acrylates such as; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and alkoxyalkyl (meth) ) Acrylates; polyethylene glycol (meth) such as polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate and nonylphenoxypolyethylene glycol (meth) acrylate Acrylates: Polypropylene glycol mono (meth) acrylate, methoxypolypropylene Polypropylene glycol (meth) acrylates such as lenglycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate and nonylphenoxypolypropylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclo Cycloalkyls such as pentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecanyl (meth) acrylate ( Meth) acrylates; benzyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate.

  Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, hydroxypivalic acid ester Opentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxy) Phenyl) propane, trimethylolpropane di (meth) acrylate, tricyclodecane dimethanol diacrylate and bis (2- (meth) acryloyloxyethyl) hydroxyethyl-isocyanurate.

  Examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( And (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate.

  Examples of the epoxy poly (meth) acrylate include compounds obtained by reacting (meth) acrylic acid or (meth) acrylate having a hydroxy group with a compound having two or more epoxy groups in the molecule, such as a bisphenol A type epoxy resin. It is done.

  As urethane poly (meth) acrylate, urethane di (1) -hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate and other diisocyanates are reacted with (meth) acrylates having a hydroxy group such as 2-hydroxyethyl (meth) acrylate. (Meth) acrylate, urethane hexa (meth) acrylate obtained by reacting 1,6-hexamethylene diisocyanate with pentaerythritol tri (meth) acrylate, and dicyclomethane diisocyanate and poly (repeating unit n = 6 to 15) tetramethylene glycol And polyurethane di (meth) acrylate obtained by reacting 2-hydroxyethyl (meth) acrylate with the urethanized reaction product.

  Polyester poly (meth) acrylate is a reaction of polyester (meth) acrylate, trimethylolpropane, ethylene glycol, succinic acid, and (meth) acrylic acid obtained by reacting trimethylolpropane with succinic acid and (meth) acrylic acid. Examples thereof include polyester (meth) acrylate and the like.

  The monomer having an ethylenically unsaturated bond may be used alone or in combination of two or more. The urethane oligomer and the reactive monomer may be used alone or in combination.

  The solvent is used to help disperse each component in the curable composition. Examples of the solvent include esters such as ethyl acetate, butyl acetate and isopropyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; N, N-dimethylformamide and the like. Amides; Aromatic hydrocarbons such as toluene; Halogenated hydrocarbons such as methylene chloride; Ethylene glycol, ethylene glycol methyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether , Ethylene glycol such as diethylene glycol monoethyl ether and diethylene glycol monoethyl ether acetate Propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and di And propylene glycols such as propylene glycol monomethyl ether acetate; and acetonitrile. Of these, ethyl acetate, methyl ethyl ketone, cyclohexanone, toluene, dichloromethane, diethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred.

  The viscosity of the curable composition depends on the structure of the (meth) acrylate compound (1) or the amount of the solvent in the curable composition, but is preferably 10 to 20,000 mPa · s at 25 ° C., It is more preferably 50 to 18,000 mPa · s, and most preferably 100 to 15,000 mPa · s. When the viscosity of the curable composition is higher than 20,000 mPa · s, handling properties may be poor and workability may be poor. In addition, the measurement conditions of a viscosity are described in the below-mentioned Example.

Method for producing curable composition The curable composition of the present invention comprises a (meth) acrylate compound (1) and a polymerization initiator, and if necessary, the above-mentioned other components at room temperature or under heating conditions, a mixer, a ball mill and It can mix | blend and prepare by mixing without using a solvent with mixers, such as 3 rolls, or adding the solvent etc. which were mentioned above as a diluent further, and making it melt | dissolve.

  The said solvent can be used individually or in combination of 2 or more types. Although the usage-amount of a solvent is not specifically limited, It is 50-200 mass parts with respect to a total of 100 mass parts of the component in the curable composition except a solvent, Preferably it is 50-100 mass parts.

Method for producing cured product The cured product of the present invention is cured, for example, by applying the curable composition on a substrate and forming a coating film, and then irradiating with active energy rays or heating. Obtained. Moreover, you may harden by performing both irradiation of an active energy ray, and a heating.

  Examples of the method for applying the curable composition include application by a bar coater, applicator, die coater, spin coater, spray coater, curtain coater and roll coater, application by screen printing, and application by dipping. It is done.

  The coating amount of the curable composition of the present invention on the substrate is not particularly limited, and can be appropriately adjusted according to the purpose. After coating and drying, the film thickness of the coating film obtained after curing treatment with active energy ray irradiation is an amount of 1 to 500 μm, preferably 5 to 300 μm, for evaluation of cured product properties.

  The active energy ray used for curing is not particularly limited, but an electron beam or light having a wavelength from ultraviolet to infrared is preferable. As the light source, for example, an ultrahigh pressure mercury light source or a metal halide light source can be used if the active energy ray is ultraviolet light, a metal halide light source or halogen light source can be used if it is visible light, and a halogen light source can be used if it is infrared light. Light sources such as LEDs can be used. The irradiation amount of the active energy ray is appropriately set according to the type of light source, the thickness of the coating film, and the like.

  The irradiation amount of the active energy ray is appropriately set according to the type of the light source and the film thickness of the coating film, but the reaction rate of the ethylenically unsaturated group of the (meth) acrylate compound (1) is preferably 80% or more, preferably Is set to be 90% or more. The reaction rate is calculated from the change in the absorption peak intensity of the ethylenically unsaturated group before and after the reaction by infrared absorption spectrum.

  Further, after curing by irradiating with active energy rays, curing may be further advanced by heat treatment or annealing treatment as necessary. The heating temperature at that time is 80 to 200 ° C., and the heating time is 10 to 60 minutes.

  When curing by thermal polymerization by heat treatment, the heating temperature is 80 to 200 ° C, preferably 100 to 150 ° C. When the heating temperature is lower than 80 ° C., it is necessary to lengthen the heating time, which may be not economical. On the other hand, if the heating temperature is higher than 200 ° C., energy costs are required and heating heating time and cooling time are required. The heating time is appropriately set according to the heating temperature and the film thickness of the coating film, but the reaction rate of the ethylenically unsaturated group of the (meth) acrylate compound (1) is 80% or more, preferably 90% or more. Is set to be The reaction rate is calculated from the change in the absorption peak intensity of the ethylenically unsaturated group before and after the reaction by infrared absorption spectrum.

Cured product The refractive index of the cured product of the present invention obtained by the method described above can be measured, for example, by the method described in the examples below, and is preferably 1.55 or more and 1.65 or less, more preferably 1. It is 56 or more and 1.64 or less, Especially preferably, it is 1.57 or more and 1.63 or less, Most preferably, it is 1.58 or more and 1.62 or less. When the refractive index of hardened | cured material is smaller than 1.55, the center parts, such as an optical lens, become thick, and the lightweight property which is the characteristics of a plastic may be impaired. On the other hand, when the refractive index of the cured product is larger than 1.65, the transparency may decrease due to light surface reflection and scattering loss.

  The glass transition temperature of the cured product can be measured, for example, by the method described in Examples below, and is preferably 100 ° C. or higher and 300 ° C. or lower, more preferably 120 ° C. or higher and 290 ° C. or lower, and particularly preferably 150 ° C. or higher. It is 280 degrees C or less. When the glass transition temperature is lower than 100 ° C., the heat resistance is inferior and coloring or warping may occur. On the other hand, when the glass transition temperature is higher than 300 ° C., there may be a concern about workability. In addition, the measuring method of glass transition temperature is as having described in the Example mentioned later.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to these Examples and a comparative example. Measurement methods used in Examples and Comparative Examples are shown below.

(1) Nuclear magnetic resonance ( ¹ HNMR)
This was performed in deuterated chloroform using a Bruker AMX400.

(2) Viscosity The viscosity of the curable composition was measured using a B-type viscometer DV-III ULTRA (manufactured by BROOKFIELD) with rotor No. 42, measured at 1 to 7 rpm and a measurement temperature of 25 ° C. When the viscosity is moderately low, the handling property is good.

(3) Refractive index The refractive index of the cured product was measured at a measurement temperature of 25 ° C. and a measurement wavelength of 589 nm using a multiwavelength Abbe refractometer DR-M2 (manufactured by Atago).

(4) Total light transmittance The total light transmittance of the cured product was measured using a haze meter COH400 (manufactured by Nippon Denshoku Industries Co., Ltd.).

(5) Glass transition temperature (Tg)
A cured specimen was processed into a shape of 30 mm length, 5 mm width, and 200 μm thickness, and using DMS6100 (manufactured by Seiko Denshi Kogyo Co., Ltd.), tensile mode, temperature range of 20 to 300 ° C., temperature increase rate of 2 ° C. Tan δ value was measured at a frequency of 1 Hz per minute, and the peak temperature of the tan δ value was defined as the glass transition temperature. In addition, it shows that heat resistance is so favorable that a glass transition temperature is high.

(6) Pencil hardness In accordance with JIS-K5600, the test piece is scratched using a Uni (registered trademark) manufactured by Mitsubishi Pencil Co., Ltd. so that the angle between the pencil and the cured film is 45 degrees, and the scratch is not damaged. The hardness of the pencil lead was specified and used as the pencil hardness.

[Example 1] Preparation of (meth) acrylate compound (1) 30 parts by mass of toluene (manufactured by Junsei Chemical Co., Ltd.), 26 parts by mass of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 9 parts by mass of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred. Thereafter, 17 parts by mass of 1-naphthoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added dropwise under ice cooling, followed by stirring at room temperature. After about 15 hours, it was confirmed by high performance liquid chromatography that the raw material pentaerythritol triacrylate had disappeared, and pure water was added to complete the reaction. Subsequently, extraction was performed with ethyl acetate, and washing was performed twice with saturated saline. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a compound represented by the following formula (6).

The difference between the viscosity of the following (meth) acrylate compound (6) and the viscosity of Solution 1 described later was the same value within about ± 20%. The measurement conditions are the same as for Solution 1. A ¹ H-NMR chart of the (meth) acrylate compound (6) is shown in FIG.

The ¹ H-NMR signal of the (meth) acrylate compound (6) is assigned as follows.

4.39 ppm: H ⁴ , H ⁸ , H ¹²
4.53 ppm: H ¹³
5.86 ppm: H ¹ , H ⁵ , H ⁹
6.10 ppm: H ³ , H ⁷ , H ¹¹
6.41 ppm: H ² , H ⁶ , H ^{10
7.47-7.62ppm: H 15, H 18,} H 19
7.87 ppm: H ¹⁷
8.03 ppm: H ¹⁶
8.12 ppm: H ¹⁴
8.83 ppm: H ²⁰
[Example 2] Preparation of curable composition (solution 1) In a container shielded from ultraviolet rays, 100 parts by mass of (meth) acrylate compound (6) prepared in Example 1 and ethyl (2, 4,6-trimethylbenzoyl) phenyl phosphinate (BASF Japan Co., Ltd., trade name Lucirin TPO-L) 1 part by mass is mixed, stirred and mixed at room temperature, and uniformly dissolved to obtain a curable composition (Solution 1 )

[Comparative Example 1] Preparation of comparative curable composition (solution 2) In Example 2, o-phenylphenoxyethyl acrylate (manufactured by Toagosei Co., Ltd.) was used instead of (meth) acrylate compound (6). A comparative curable composition (solution 2) was obtained in the same manner as in Example 2 except for the above.

[Comparative Example 2] Preparation of Comparative Curable Composition (Solution 3) In Example 2, instead of the (meth) acrylate compound (6), a bisarylfluorene skeleton compound (manufactured by Osaka Gas Chemical Co., Ltd., trade name OGSOL) A comparative curable composition (solution 3) was obtained in the same manner as in Example 2, except that EA-0200) was used.

[Example 3] Production of cured product The curable composition prepared in Example 2 (Solution 1) and the comparative curable compositions prepared in Comparative Examples 1 and 2 (Solutions 2 and 3) were respectively separated into glass substrates ( (50 mm × 50 mm) was applied in a film shape so that the thickness of the cured product was 200 μm. Subsequently, the coating film was cured by exposure at 4 J / cm ² with an exposure apparatus incorporating an ultrahigh pressure mercury lamp. The performance of the obtained cured film was evaluated. The results are shown in Table 1.

  From Table 1, the composition (solution 1) of Example 2 of the present invention has lower viscosity and better handling properties than Comparative Example 2 using a compound containing a bisarylfluorene skeleton. Moreover, while the refractive index of hardened | cured material is 1.55 or more, the total light transmittance is also favorable, and it can use it suitably for materials, such as an optical lens. Furthermore, since the glass transition temperature of hardened | cured material is 250 degreeC or more, heat resistance is also favorable. Further, it has a pencil hardness of 4H and can be suitably used as a coating material.

  In comparison, Comparative Example 1 using o-phenylphenoxyethyl acrylate has a good viscosity, refractive index and transparency of the cured product (solution 2), but is a monofunctional cured product. Is inferior in heat resistance and has low pencil hardness. In Comparative Example 2 using a compound containing a bisarylfluorene skeleton, the refractive index and heat resistance of the cured product are good, but the viscosity of the composition is very high and handling properties are poor.

  Since the (meth) acrylate compound and the curable composition of the present invention are excellent in handling properties, workability can be improved.

  The cured product obtained by curing the curable composition has a high refractive index and good transparency and heat resistance, so that it is used for transparent plates, optical lenses, optical disk substrates, plastic substrates for liquid crystal displays, and color filters. It is suitable as an optical material such as a substrate, a plastic substrate for organic EL display elements, a solar cell substrate, a touch panel, an optical element, an optical waveguide, and an LED sealing material. Moreover, since the said hardened | cured material is excellent also in pencil hardness, it is suitable also as coating materials, such as a liquid crystal television, a personal computer, the display of a mobile phone, and a touch panel.

Claims (15)

A (meth) acrylate compound represented by the following formula (1):

(In Formula (1), R < ¹ > and R < ² > are respectively independently a hydrogen atom or a methyl group, X is a C6-C30 organic group containing an aromatic ring, a is an integer of 1-3. And b is an integer of 0 to 3.) The (meth) acrylate compound according to claim 1, wherein X is any one of organic groups represented by the following formulas (a) to (h).

(Note that, in the organic groups represented by (a) to (h), the portions with wavy lines represent the X bond in the compound represented by the above formula (1).) The (meth) acrylate compound according to claim 1, which is represented by the following formula (2).

(In Formula (2), R < ¹ > and R < ² > are respectively independently a hydrogen atom or a methyl group, a is an integer of 1-3, b is an integer of 0-3.)   The (meth) acrylate compound according to claim 3, wherein in the formula (2), a naphthyl group is bonded at the α-position.   In the said Formula (2), a is 2 or 3, The (meth) acrylate compound of Claim 3 or 4 characterized by the above-mentioned.   In said Formula (2), b is 0 or 1, The (meth) acrylate compound in any one of Claims 3-5 characterized by the above-mentioned. In the formula (2), R ¹ is hydrogen atom, R ² is (meth) acrylate compound according to any one of claims 3-6, characterized in that a methyl group. It is represented by following formula (6), The (meth) acrylate compound of Claim 1 characterized by the above-mentioned.

  A curable composition comprising the (meth) acrylate compound according to any one of claims 1 to 8 and a polymerization initiator.   A cured product obtained by curing the curable composition according to claim 9.   The cured product according to claim 10, having a refractive index of 1.55 or more and 1.65 or less.   The cured product according to claim 10 or 11, wherein the glass transition temperature is 100 ° C or higher and 300 ° C or lower.   A coating material obtained by curing the curable composition according to claim 9.   An optical material obtained by curing the curable composition according to claim 9.   A lens obtained by curing the curable composition according to claim 9.

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