WO2011102258A1 - Composé (méth)acrylate et composition pouvant durcir contenant le composé (méth)acrylate - Google Patents

Composé (méth)acrylate et composition pouvant durcir contenant le composé (méth)acrylate Download PDF

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WO2011102258A1
WO2011102258A1 PCT/JP2011/052571 JP2011052571W WO2011102258A1 WO 2011102258 A1 WO2011102258 A1 WO 2011102258A1 JP 2011052571 W JP2011052571 W JP 2011052571W WO 2011102258 A1 WO2011102258 A1 WO 2011102258A1
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meth
acrylate
acrylate compound
curable composition
compound
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PCT/JP2011/052571
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Japanese (ja)
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慶史 浦川
山木　繁
石井　伸晃
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昭和電工株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • 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. .
  • optical lenses In recent years, materials with excellent optical performance have been demanded along with the development of 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.
  • 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.
  • 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.
  • plastic materials having excellent heat resistance such as reflow resistance have been demanded as optical lenses, optical elements, optical waveguides, and LED sealing materials.
  • heat resistance 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.
  • 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.
  • a resin composition comprising an amorphous thermoplastic resin and bis (meth) acrylate curable with active energy rays with active energy rays.
  • 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.
  • 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.
  • Patent Document 2 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.
  • a compound containing a fluorene skeleton has a very high viscosity, is inferior in handling properties, and does not satisfy the required low viscosity.
  • Patent Document 3 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.
  • heat resistance since the compound having a biphenyl skeleton, which is a component of the composition, is a monofunctional monomer, a problem remains in heat resistance.
  • 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
  • the present invention includes the following matters.
  • a (meth) acrylate compound represented by the following formula (1) [1] A (meth) acrylate compound represented by the following formula (1).
  • R 1 and R 2 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, and a is an integer of 1 to 3) And b is an integer of 0 to 3.
  • X is any one of organic groups represented by the following formulas (a) to (h).
  • R 1 and R 2 are each independently a hydrogen atom or a methyl group, a is an integer of 1 to 3, and b is an integer of 0 to 3.
  • [4] The (meth) acrylate compound according to [3], wherein in the formula (2), a naphthyl group is bonded at the ⁇ -position.
  • a curable composition comprising the (meth) acrylate compound according to any one of [1] to [8] and a polymerization initiator.
  • the (meth) acrylate compound which can give the hardened
  • 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.
  • FIG. 1 shows a 1 H-NMR chart of the (meth) acrylate compound (6) synthesized in Example 1.
  • (meth) acrylate compound (1) the (meth) acrylate compound of the present invention
  • the curable composition the curable composition
  • the cured product will be described in detail.
  • 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).
  • the (meth) acrylate of the (meth) acrylate compound means acrylate and / or methacrylate.
  • 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, preferably 2 or 3, 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, but 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, and 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 particularly preferably 7 to 15 carbon atoms.
  • X include organic groups represented by the following (a) to (h).
  • the portions with wavy lines represent the X bond in the (meth) acrylate compound (1).
  • 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)”.
  • 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 ⁇ -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.
  • the apparatus and conditions used for the above-mentioned viscosity measurement are as described in the examples described later.
  • B-type viscometer DV-III ULTRA manufactured by BROOKFIELD
  • rotor No. 42 the rotational speed is 1 to 7 rpm.
  • 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 a various well-known method.
  • R 1 and R 2 are each independently a hydrogen atom or a methyl group, a is an integer of 1 to 3, and b is an integer of 0 to 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the amount of the base added is preferably 1.0 to 2.0 equivalents, more preferably 1.0 to 1.5 equivalents, per one hydroxyl group in the (meth) acrylate compound (3). 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 Aromatic hydrocarbons; halogenated hydrocarbons such as methylene chloride and chloroform; acetonitrile and the like. Of these, tetrahydrofuran, toluene and dichloromethane are preferred.
  • 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, 9-anthracenecarboxylic acid. And acid and 9-fluorenecarboxylic acid. Of these, 1-naphthoic acid and 4-phenylbenzoic acid are preferred.
  • the (meth) acrylate compound (3) and the compound (5) are reacted, it is preferable to use a condensing agent.
  • the condensing agent By using the condensing agent, the carboxylic acid is activated, and the reaction can be significantly accelerated.
  • the condensing agent examples 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.
  • the amount of the condensing agent added is preferably 1.0 to 2.0 equivalents, more preferably 1.0 to 1.5 equivalents, relative to one carboxylic acid in the compound (5). 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.
  • a tertiary amine can be added as a catalyst when reacting the (meth) acrylate compound (3) and the compound (5).
  • the reaction can be significantly accelerated by using a tertiary amine.
  • 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 of the (meth) acrylate compound (3) with the compound (5) include cyclic ethers such as tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide; toluene and xylene Aromatic hydrocarbons; halogenated hydrocarbons such as methylene chloride and chloroform; and acetonitrile. Of these, tetrahydrofuran, toluene and dichloromethane are preferred.
  • the curable composition of this invention contains the said (meth) acrylate compound (1) and a polymerization initiator.
  • the polymerization initiator As the polymerization initiator, a photopolymerization initiator and a thermal polymerization initiator are used.
  • 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.
  • active energy rays such as ultraviolet rays or visible rays
  • the (meth) acrylate compound (1) undergoes a polymerization reaction by heating to obtain a cured product.
  • a photopolymerization initiator is preferable from the viewpoint that it can be used for a substrate having low heat resistance.
  • Photopolymerization initiators include 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, -Isopropylthioxan
  • thermal polymerization initiator examples include azo compounds and organic peroxides.
  • 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. And oxy-2-ethylhexanoate.
  • thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the polymerization initiator used is not particularly limited, but is 0.1 to 5 parts by mass with respect to 100 parts by mass as a total of the (meth) acrylate compound (1) and the radical reactive component described later which is an optional component.
  • the amount is preferably 0.5 to 3 parts by mass, more preferably 0.5 to 1 part by mass.
  • the curable composition may contain other components as necessary.
  • 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 with respect to 100 parts by mass as a total of the (meth) acrylate compound (1) and a 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.
  • a 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.
  • urethane oligomer examples 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.
  • 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, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, and o-chlorostyrene.
  • carboxyl group-containing unsaturated compound examples 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, laur Alkyl (meth) acrylates such as ru (meth) acrylate, stearyl (meth) acrylate and isostearyl (meth) acrylate; trifluoroethyl (meth) acrylate, tetrafluoropropyl (
  • di (meth) acrylate examples 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 Neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate,
  • 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.
  • urethane poly (meth) acrylate As urethane poly (meth) acrylate, urethane di (1) -hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate are reacted with diisocyanate such as 2-hydroxyethyl (meth) acrylate and other (meth) acrylates having a hydroxy group.
  • (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 urethanization 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.
  • polyester (meth) acrylate and the like examples thereof include polyester (meth) acrylate and the like.
  • the monomers 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.
  • Solvent is used to help disperse each component in the curable composition.
  • 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.
  • 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.
  • 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., More preferably, it is 50 to 18,000 mPa ⁇ s, and most preferably 100 to 15,000 mPa ⁇ s.
  • the viscosity of the curable composition is higher than 20,000 mPa ⁇ s, handling properties may be poor and workability may be poor.
  • the measurement conditions of a viscosity are described in the below-mentioned Example.
  • 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
  • the above solvents can be used alone or in combination of two or more.
  • the amount of the solvent to be used is not particularly limited, but is 50 to 200 parts by mass, preferably 50 to 100 parts by mass with respect to 100 parts by mass in total of the components in the curable composition excluding the solvent.
  • 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.
  • the thickness of the coating film obtained after coating and drying and then curing by irradiation with active energy rays is 1 to 500 ⁇ m, preferably 5 to 300 ⁇ m, for evaluating the properties of the cured product.
  • 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.
  • 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 the light source, the film 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.
  • 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.
  • the heating temperature is 80 to 200 ° C, preferably 100 to 150 ° C.
  • the heating temperature is lower than 80 ° C., it is necessary to lengthen the heating time, which may be not economical.
  • 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.
  • the refractive index of the cured product of the present invention obtained by the above-described method 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.
  • 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.
  • 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.
  • the glass transition temperature is lower than 100 ° C., the heat resistance is inferior and coloring or warping may occur.
  • the glass transition temperature is higher than 300 ° C., there may be a concern about workability.
  • the measuring method of glass transition temperature is as having described in the Example mentioned later.
  • Viscosity The viscosity of the curable composition was measured using a B-type viscometer DV-III ULTRA (manufactured by BROOKFIELD) with a rotor No. The measurement was performed at 42, at a rotational speed of 1 to 7 rpm, and at a measurement temperature of 25 ° C. When the viscosity is moderately low, the handling property is good.
  • the refractive index of the cured product was measured using a multiwavelength Abbe refractometer DR-M2 (manufactured by Atago) at a measurement temperature of 25 ° C. and a measurement wavelength of 589 nm.
  • 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.).
  • Glass transition temperature (Tg) A cured specimen was processed into a shape of 30 mm in length, 5 mm in width, and 200 ⁇ m in thickness, and using DMS6100 (manufactured by Seiko Denshi Kogyo Co., Ltd.) in a tensile mode, a temperature range of 20 to 300 ° C., and a heating rate of 2 ° C. Tan ⁇ value was measured at a frequency of 1 Hz per minute, and the peak temperature of the tan ⁇ 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.
  • 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.
  • 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.
  • the 1 H-NMR signal of the (meth) acrylate compound (6) is assigned as follows.
  • Comparative Example 1 Preparation of comparative curable composition (solution 2)
  • o-phenylphenoxyethyl acrylate manufactured by Toagosei Co., Ltd.
  • (meth) acrylate compound (6) 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 Curable Composition (Solution 3)
  • a bisarylfluorene skeleton compound manufactured by Osaka Gas Chemical Co., Ltd., trade name: OGSOL
  • a comparative curable composition 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 separated into separate glass substrates ( (50 mm ⁇ 50 mm) was applied in a film shape so that the thickness of the cured product was 200 ⁇ m. 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.
  • the composition (solution 1) of Example 2 of the present invention has a lower viscosity and better handling properties than Comparative Example 2 using a compound containing a bisarylfluorene skeleton.
  • 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.
  • 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.
  • Comparative Example 1 using o-phenylphenoxyethyl acrylate is good in viscosity, refractive index and transparency of the composition (solution 2), but cured because it is monofunctional. Is inferior in heat resistance and has low pencil hardness.
  • 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.
  • 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

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Abstract

L'invention porte sur un composé (méth)acrylate qui peut donner des produits durcis ayant des indices de réfraction élevés et d'excellentes caractéristiques en termes de transparence, de résistance à la chaleur et de maniabilité ; sur une composition pouvant durcir qui comprend le composé (méth)acrylate, et sur des produits durcis de celle-ci. L'invention porte notamment sur un composé (méth)acrylate, caractérisé en ce qu'il est représenté par la formule générale (1) [dans laquelle R1 et R2 représentent chacun indépendamment de l'autre un atome d'hydrogène ou le groupe méthyle ; X est un groupe organique en C6-30 qui contient un noyau aromatique ; a est un entier de 1 à 3, et b est un entier de 0 à 3].
PCT/JP2011/052571 2010-02-19 2011-02-08 Composé (méth)acrylate et composition pouvant durcir contenant le composé (méth)acrylate WO2011102258A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5693776A (en) * 1979-12-28 1981-07-29 Dainippon Ink & Chem Inc Ultraviolet curing type printing ink composition
JPS5714613A (en) * 1980-06-30 1982-01-25 Dainippon Ink & Chem Inc Photosetting composition
JPH11282157A (ja) * 1997-10-31 1999-10-15 Nippon Zeon Co Ltd ポリイミド系感光性樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5693776A (en) * 1979-12-28 1981-07-29 Dainippon Ink & Chem Inc Ultraviolet curing type printing ink composition
JPS5714613A (en) * 1980-06-30 1982-01-25 Dainippon Ink & Chem Inc Photosetting composition
JPH11282157A (ja) * 1997-10-31 1999-10-15 Nippon Zeon Co Ltd ポリイミド系感光性樹脂組成物

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