WO2019116798A1 - Composé (méth)acrylate ayant un squelette fluorène - Google Patents

Composé (méth)acrylate ayant un squelette fluorène Download PDF

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WO2019116798A1
WO2019116798A1 PCT/JP2018/041645 JP2018041645W WO2019116798A1 WO 2019116798 A1 WO2019116798 A1 WO 2019116798A1 JP 2018041645 W JP2018041645 W JP 2018041645W WO 2019116798 A1 WO2019116798 A1 WO 2019116798A1
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meth
acrylate
same
different
acrylate compound
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PCT/JP2018/041645
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Japanese (ja)
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英信 中山
崇史 佐伯
芳範 河村
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田岡化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • 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

Definitions

  • the present invention relates to a novel difunctional (meth) acrylate compound having a fluorene skeleton, a method for producing the same, a curable composition containing the (meth) acrylate compound, and a cured product obtained by curing the curable composition. .
  • optical materials such as prism sheets, overcoating agents, hard coating agents, antireflection films, or camera lenses, eyeglass lenses, optical fibers, optical waveguides, and holograms used for liquid crystal display devices have light weight, safety, design Plastics (resin) is widely used as a substitute material for inorganic glass from the viewpoint of conductivity, and among these resins, (meth) acrylate resin obtained by polymerizing (hardening) a (meth) acrylate compound is active energy ray It is a kind of resin widely used as the above-mentioned material because it is characterized by its relatively low temperature and its ability to be cured easily.
  • the resin has a lower refractive index than inorganic glass, and when used as a substitute for inorganic glass, there is a problem that the thickness tends to be large compared to inorganic glass. From the viewpoint, further increase in refractive index is required.
  • difunctional (meth) acrylate compounds derived from a bisphenol compound having a fluorene skeleton are known as compounds having a high refractive index [e.g. 04-325508 gazette (patent documents 1)].
  • a difunctional (meth) acrylate compound derived from a bisphenol compound having a fluorene skeleton has a high refractive index
  • a single cured product of the difunctional (meth) acrylate compound has poor adhesion to a substrate Therefore, it is necessary to blend a monofunctional (meth) acrylate compound for the purpose of improving the adhesion to the target substrate.
  • the difunctional (meth) acrylate compound derived from the bisphenol compound having a fluorene skeleton has poor compatibility with the monofunctional (meth) acrylate compound described above, the difunctional (meth) acrylate compound is high. It has often been difficult to prepare curable compositions containing concentrations.
  • An object of the present invention is to provide a compound having excellent compatibility with a monofunctional (meth) acrylate compound and having a refractive index equal to or higher than that of a difunctional (meth) acrylate compound derived from a conventionally known bisphenol compound having a fluorene skeleton It is an object of the present invention to provide a difunctional (meth) acrylate compound having the following formula, a curable composition containing the compound, and a cured product obtained by curing the curable composition.
  • the present inventors found that the difunctional (meth) acrylate compound represented by the following general formula (1) is compatible with a monofunctional (meth) acrylate compound. It was found to be excellent.
  • the present invention includes the following inventions.
  • R 1 to R 4 are the same or different and each represents an alkyl group, an aryl group or a halogen atom, and R 5 and R 6 are each the same or different and may have a branch and have 2 to 4 carbon atoms represents an alkylene group
  • R 7 and R 8 the same or different and each represents an integer of .
  • k 1 ⁇ k 4 are the same or different and each is 0 to 4 represent a hydrogen atom or a methyl group
  • n 1 and n 2 are respectively
  • the same or different represents an integer of 1 or more
  • p 1 and p 2 are the same or different and each represents an integer of 1 or more, and when k 1 to k 4 is 2 or more, the corresponding R 1 to R 4 are respectively It may be the same or different.
  • R 1 to R 4 are the same or different and each represents an alkyl group, an aryl group or a halogen atom, and R 5 and R 6 are each the same or different and may have a branch and have 2 to 4 carbon atoms
  • each of k 1 to k 4 is the same or different and represents an integer of 0 to 4
  • n 1 and n 2 are respectively the same or different and each represents an integer of 1 or more
  • p 1 and p 2 are respectively the same.
  • R 1 to R 4 may be the same or different.
  • R 1 to R 4 are the same or different and each represents an alkyl group, an aryl group or a halogen atom, and R 5 and R 6 are each the same or different and may have a branch and have 2 to 4 carbon atoms
  • each of k 1 to k 4 is the same or different and represents an integer of 0 to 4
  • n 1 and n 2 are respectively the same or different and each represents an integer of 1 or more
  • p 1 and p 2 are respectively the same.
  • a difunctional (meth) acrylate compound derived from a bisphenol compound having a conventionally known fluorene skeleton which is excellent in compatibility with monofunctional (meth) acrylate compounds and has a high refractive index It is possible to provide a difunctional (meth) acrylate compound which exhibits a refractive index equal to or higher than that of the above, and also has characteristics such as excellent transparency and low Abbe number.
  • a curable composition containing the (meth) acrylate compound of the present invention at a high concentration can be prepared.
  • a curable composition having the properties of the (meth) acrylate compound of the present invention such as refractive index, high transparency and low Abbe, and properties such as low viscosity and adhesion possessed by a monofunctional acrylate compound and a cured product thereof Is possible.
  • (meth) acrylate compound of the present invention compatibilizing the (meth) acrylate compound of the present invention with 2-phenoxyethyl acrylate, which is a kind of monofunctional acrylate compound, (meth) acrylate cured having high refractive index and high adhesion to a substrate such as polycarbonate. It is possible to obtain a cured product having a higher refractive index than that of the cured product while having adhesion by compatiblizing with 2- (2-phenylphenoxyethyl) acrylate. It becomes possible.
  • the (meth) acrylate compound of the present invention is a (meth) acrylate compound having a structure represented by the above general formula (1).
  • “(meth) acrylate” represents at least one selected from acrylate and methacrylate.
  • the “(meth) acryloyl group” represents at least one selected from an acryloyl group and a methacryloyl group.
  • the alkyl group in the substituents (R 1 to R 4 ) is an alkyl group which may have a branch, such as a methyl group, an ethyl group, a propyl group or an isopropyl group, a cyclopentyl group, Examples thereof include cyclic alkyl groups such as a cyclohexyl group.
  • the aryl group in the substituent (R 1 to R 4 ) include an aromatic group which may have a substituent such as a phenyl group or a tolyl group.
  • halogen atom in the substituent (R 1 to R 4 ) examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • substituents an alkyl group having 1 to 4 carbon atoms which may have a branch is preferable from the viewpoint of the productivity of the bisalcohol compound represented by the above general formula (2) which is a raw material.
  • K 1 to k 4 representing the number of substituents (R 1 to R 4 ) are the same or different and each is an integer of 0 or 1 to 4 and are bis alcohol represented by the above general formula (2) as a raw material It is preferable that it is 0 or 1 from a viewpoint of the producibility of a compound, and it is more preferable that it is 0 (it does not have a substituent). When at least one of k 1 to k 4 is 2 or more, the corresponding substituents may be the same or different.
  • N 1 and n 2 each representing the number of methylene groups connecting a phenyl group having a (meth) acryloyl group and another phenyl group are the same or different and each represents an integer of 1 or more, preferably an integer of 1 to 4 It is more preferably 1 or 2 and still more preferably 1 from the viewpoint of the productivity of the bisalcohol compound represented by the above general formula (2), which is a raw material.
  • R 5 and R 6 are each the same or different and each represent an alkylene group having 2 to 4 carbon atoms which may have a branch.
  • Examples of the optionally branched alkylene group having 2 to 4 carbon atoms represented by R 5 and R 6 include, for example, ethylene group, n-propylene group, (methyl) ethylene group, n-butylene group, s- ( Examples include methyl) propylene group and t- (dimethyl) ethylene group.
  • ethylene group or (methyl) ethylene group is preferable.
  • p 1 and p 2 representing the number of oxyalkylenes are the same or different and each represents an integer of 1 or more, preferably 1 or 2, and particularly preferably 1.
  • R 7 and R 8 are the same or different and each independently represent a hydrogen atom or a methyl group.
  • the (meth) acrylate compound of the present invention is excellent in compatibility with monofunctional (meth) acrylate compounds, it is excellent in handleability, and a curable composition containing the (meth) acrylate compound of the present invention in a high concentration Can be prepared. For this reason, the curable composition which can fully exhibit the characteristic of the (meth) acrylate compound of this invention, or the hardened
  • the refractive index of the (meth) acrylate compound of the present invention measured under the conditions described later is usually 1.59 or more, particularly 1.60 or more, and further 1.61 or more.
  • the Abbe number is 29 or less, particularly 27 or less, and since it is possible to cancel the chromatic aberration by combining with a material with a high Abbe number in particular, various optical materials in which the chromatic aberration becomes a problem and the high refractive index is preferable It can be suitably used as
  • the (meth) acrylate compound represented by the above general formula (1) of the present invention has the following general formula (3):
  • the bis alcohol compound represented by the above general formula (2) is obtained by reacting the bisphenol compound represented by and the alkylene oxide or the alkylene carbonate, and the bis alcohol compound and the (meth) acrylate are reacted. It can be manufactured.
  • the alkylene oxide is a gas at normal temperature or a liquid having a low boiling point, so it is special in its handling Alkylene carbonate is preferably used because it requires equipment and it is difficult to improve the purity of the obtained bisalcohol compound represented by the above general formula (2).
  • the reaction of the bisphenol compound represented by the general formula (3) and the alkylene carbonate will be described in detail.
  • the amount of the alkylene carbonate used is usually 2 to 10 moles, preferably 2 to 4 moles, per mole of the bisphenol compound represented by the general formula (3). A sufficient reaction rate can be obtained by using 2 moles or more, and by making the amount used 10 moles or less, it is possible to obtain the bisalcohol compound represented by the above general formula (2) more economically. .
  • the alkylene carbonate may be used alone or in combination of two or more as needed.
  • carbonates, hydrogencarbonates, hydroxides, organic bases etc. are illustrated, for example, More specifically, as carbonates, potassium carbonate, sodium carbonate, carbonated Lithium, cesium carbonate and the like, and as hydrogen carbonates, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate and cesium hydrogen carbonate etc., and as hydroxides, sodium hydroxide, potassium hydroxide, lithium hydroxide etc.
  • organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride and the like.
  • organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride and the like.
  • potassium carbonate, sodium carbonate and triphenylphosphine are preferably used from the viewpoint of good handleability.
  • the amount of the basic compound to be used is generally 0.01 to 1.0 mol, preferably 0.03 to 0.2 mol, per 1 mol of the bisphenol compound represented by the general formula (3). use. These basic compounds may be used alone or in combination of two or more, as required.
  • organic solvent When carrying out the above reaction, an organic solvent may be used in combination, if necessary.
  • the organic solvents usable in combination may be those which are inert to the bisphenol compound and the alkylene carbonate represented by the above general formula (3), and such organic solvents include ketones and aromatic hydrocarbons.
  • Halogenated aromatic hydrocarbons such as toluene, xylene, mesitylene etc.
  • the amount of these organic solvents to be used in combination is usually 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 1 part by weight of the bisphenol compound represented by the general formula (3). .
  • the reaction between the bisphenol compound represented by the above general formula (3) and the alkylene carbonate can be performed by using the bisphenol compound and the alkylene carbonate represented by the above general formula (3), and optionally a basic compound and / or a combination thereof
  • An organic solvent is added to the reaction vessel, which is usually performed at 30 to 150 ° C., preferably 100 to 130 ° C.
  • the bisalcohol compound represented by the above general formula (2) can be taken out from the obtained reaction solution by a conventional method such as neutralization, water washing, concentration, crystallization, filtration and the like, as necessary.
  • the obtained bisalcohol compound represented by the above general formula (2) can also be purified by a standard method such as recrystallization, distillation, adsorption, column chromatography and the like.
  • the bisalcohol compound represented by the above general formula (2) of the present invention is used as a raw material of the (meth) acrylate compound represented by the above general formula (1), and further thermoplastics such as polycarbonate, polyester and polyester polycarbonate It is also possible to obtain an epoxy resin by using a monomer for resin or epoxidation according to a conventional method. In particular, since the refractive index is high, it can be suitably used as a monomer for resin that constitutes an optical member represented by an optical lens or an optical film.
  • Examples of (meth) acrylic acids used in (meth) acrylate formation reaction include (meth) acrylic acid, (meth) acrylic acid lower alkyl ester (eg, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) C. 4 ) alkyl (meth) acrylates such as butyl acrylate, etc., (meth) acrylic acid halides (eg, (meth) acrylic acid chloride etc.), (meth) acrylic anhydride and the like.
  • the (meth) acrylic acids may be used alone or in combination of two or more as required.
  • the amount of (meth) acrylic acids used is usually 2 to 20 mol, preferably 2.2 to 10 mol, more preferably 2.5 to 20 mol, per 1 mol of the bisalcohol compound represented by the above general formula (2). 5 moles.
  • An acid or a base can be suitably used in (meth) acrylation reaction.
  • an acid which can be used for (meth) acrylation reaction various acids, such as an inorganic acid and an organic acid, are mentioned, for example.
  • inorganic acids include sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, heteropoly acids, zeolites, and clay minerals.
  • organic acids include methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, and ion exchange resins. Etc. are illustrated. These acids may be used alone or, if necessary, in combination of two or more.
  • an inorganic base and an organic base are mentioned, for example.
  • a metal carbonate such as an alkali metal or alkaline earth metal carbonate such as sodium carbonate, an alkali metal or alkaline earth metal bicarbonate such as sodium hydrogencarbonate
  • a carboxylic acid metal salt acetic acid
  • alkali metal or alkaline earth metal acetates such as calcium acetate
  • metal hydroxides such as alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide
  • organic base examples include amines [for example, tertiary amines (trialkylamines such as triethylamine, triisopropylamine, tributylamine, etc., aromatic tertiary amines such as N, N-dimethylaniline, complex such as pyridine, etc. Cyclic tertiary amines) and the like are exemplified. These bases may be used alone or, if necessary, in combination of two or more.
  • amines for example, tertiary amines (trialkylamines such as triethylamine, triisopropylamine, tributylamine, etc., aromatic tertiary amines such as N, N-dimethylaniline, complex such as pyridine, etc. Cyclic tertiary amines) and the like are exemplified. These bases may be used alone or, if necessary, in combination of two or more.
  • the amount of the acid or base to be used is generally 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 10 mol, per 1 mol of the bisalcohol compound represented by the above general formula (2). 3 moles.
  • the (meth) acrylate formation reaction may be carried out in the presence of a polymerization inhibitor (thermal polymerization inhibitor), if necessary.
  • a polymerization inhibitor thermal polymerization inhibitor
  • the polymerization inhibitor include hydroquinones (for example, hydroquinone; hydroquinone monoalkyl ethers such as hydroquinone monomethyl ether (methquinone) and the like), catechols (for example, alkyl catechol such as t-butyl catechol and the like), amines (for example, Diphenylamine and the like), 2,2-diphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperazine-1-oxyl and the like.
  • the polymerization inhibitor may be used alone or in combination of two or more if necessary.
  • the amount thereof used is usually 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, more preferably 0.5 to 100 parts by weight of (meth) acrylic acid. 5 parts by weight.
  • the (meth) acrylate reaction may be carried out without using a solvent, or an organic solvent may be used in combination.
  • organic solvent which can be used in combination include hydrocarbons, halogenated hydrocarbons, ethers, ketones, nitriles and the like.
  • hydrocarbons include aliphatic hydrocarbons such as hexane, heptane and octane, and aromatic hydrocarbons such as benzene, toluene and xylene.
  • halogenated hydrocarbons include chlorides.
  • Aliphatic halogenated hydrocarbons such as methylene, chloroform and carbon tetrachloride, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and the like, and as ethers, for example, dialkyl ethers such as diethyl ether, tetrahydrofuran, dioxane And cyclic ethers such as anisole, etc., and ketones such as dialkyl ketones such as acetone and methyl ethyl ketone etc., and nitriles such as acetonitrile, propionitrile, benzonitrile etc. These organic solvents may be used alone or, if necessary, in combination of two or more. When the acid or base is a liquid, the acid or base may be used as a solvent.
  • the amount thereof used is usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, per 1 part by weight of the bisalcohol compound represented by the general formula (2).
  • the (meth) acrylate formation reaction is usually carried out at 80 to 140 ° C., preferably 100 to 130 ° C. Further, when carrying out the (meth) acrylate formation reaction, it may be carried out while removing by-produced water and alcohols. The reaction can also be carried out under pressure or under reduced pressure.
  • the reaction liquid After completion of the (meth) acrylate formation reaction, the reaction liquid is used as it is for the preparation of a curable composition described later without removing the (meth) acrylate compound represented by the above general formula (1) from the obtained reaction liquid It is also good. Moreover, after taking out the (meth) acrylate compound represented by the said General formula (1) by usual methods, such as neutralization, water washing, concentration, crystallization, filtration as needed, the said General formula (1) taken out The (meth) acrylate compound represented by these may be used for preparation of a curable composition.
  • the (meth) acrylate compound represented by the above general formula (1) once taken out is purified by a regular method such as recrystallization, distillation, adsorption, column chromatography and the like, and then purified with the above general formula (1)
  • the (meth) acrylate compounds represented may be used for the preparation of the curable composition.
  • ⁇ Curable composition containing (meth) acrylate compound of the present invention in addition to the (meth) acrylate compound represented by the above general formula (1), other polyfunctional (meth) acrylate compounds, a polymerization initiator, It may contain a diluent or the like. Since the (meth) acrylate compound represented by the above general formula (1) has a low melt viscosity, only the (meth) acrylate compound represented by the above general formula (1) is used as a curable composition and cured. It is also possible to obtain a cured product.
  • polyfunctional (meth) acrylate compound which may be contained in the curable composition of the present invention, for example, difunctional (meth) acrylate ⁇ alkylene glycol di (meth) acrylate [ethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, C 2-10 alkylene glycol di (meth) acrylate such as 1,4-butanediol di (meth) acrylate, etc.], polyalkylene glycol di (meth) acrylate [di or tetra ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, di- to tetrapropylene glycol di (meth) acrylate, poly C 2-4 alkylene glycol di (meth) such as polytetramethylene glycol di (meth) acrylate Accession Rate, etc.], and di (meth) acrylate of bisphenol A (or C 2-3 alkylene oxide adduct) ⁇
  • the amount of the other polyfunctional (meth) acrylate compound to be used in combination is usually 1 to 300 parts by weight, preferably 100 parts by weight of the (meth) acrylate compound represented by the general formula (1).
  • the amount is 2 to 200 parts by weight, more preferably 5 to 100 parts by weight.
  • Examples of the polymerization initiator that may be contained in the curable composition of the present invention include a thermal polymerization initiator and a photopolymerization initiator, and the thermal polymerization initiator and the photopolymerization initiator can be used in combination as needed.
  • thermal polymerization initiator for example, dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide etc.), diacyl peroxides [dialkanoyl peroxide (lauroyl peroxide etc.), diaroyl peroxide ( Benzoyl peroxide etc., etc., peroxy esters (eg t-butyl peracetate), ketone peroxides, peroxycarbonates, peroxyketals etc .; azo nitrile compounds [2, 2 '- Azo bis (isobutyronitrile) etc.], azo amide compounds, azo compounds such as azo amidine compounds, etc. may be mentioned.
  • thermal polymerization initiators may be used alone or, if necessary, in combination of two or more.
  • benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin alkyl ethers such as benzoin isopropyl ether, etc.), acetophenones (acetophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy) -2-Methyl-1-phenylpropan-1-one etc.), aminoacetophenones ⁇ 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone etc ⁇ , anthraquinones (anthraquinone) , 2-methylanthraquinone, etc., thioxanthones (2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone etc.), ketals (acetophenone dimethyl ketal), Such emission Jill
  • Photopolymerization initiators may also be used in combination with photosensitizers.
  • photosensitizers that can be used in combination include tertiary amines ⁇ eg, trialkylamines, trialkanolamines (such as triethanolamine), ethyl N, N-dimethylaminobenzoate [p- (dimethylamino) Dialkylaminobenzoic acid alkyl esters such as ethyl benzoate etc., amyl N, N-dimethylaminobenzoic acid [amyl p- (dimethylamino) benzoic acid etc], etc., such as 4,4-bis (diethylamino) benzophenone (Michler's ketone) And bis (dialkylamino) benzophenones, dialkylaminobenzophenones such as 4- (dimethylamino) benzophenone, and the like.
  • These photosensitizers may be used alone or,
  • the amount of the polymerization initiator used may be the same as that of the general formula (1), in the case where another multifunctional (meth) acrylate compound is used in combination with 100 parts by weight of the (meth) acrylate compound represented by the general formula (1)
  • the compound is usually 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to the total amount of 100 parts by weight of the (meth) acrylate compound and the other polyfunctional (meth) acrylate compound represented by .5 to 10 parts by weight.
  • the amount of the photosensitizer used is 5 to 200 parts by weight with respect to 100 parts by weight of the polymerization initiator (photopolymerization initiator)
  • the amount is preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight.
  • a reactive diluent and / or a nonreactive diluent is exemplified.
  • the reactive diluent include polymerizable monomers such as alkyl (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.
  • Acid C 1-20 alkyl preferably (meth) acrylic acid C 1-10 alkyl, etc.], methacrylic acid cycloalkyl [eg, (meth) acrylic acid C 5-8 cycloalkyl such as cyclohexyl (meth) acrylic acid, etc.], Aryl (meth) acrylate [phenyl (meth) acrylate, etc.], hydroxyalkyl (meth) acrylate [(2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Hydroxy C2-10 alkyl (meth) acrylates such as acrylates], ( Li) oxyalkylene glycol mono (meth) acrylate (diethylene glycol mono (meth) acrylate, methoxy tetraethylene glycol mono (meth) acrylate, such as polyethylene glycol mono (meth) acrylate (poly) oxy-C 2-6 alkylene glycol mono (meth
  • reactive diluents monofunctional (meth) acrylate compounds are preferable because adhesion of a cured product is easily improved, and 2-phenoxyethyl (meth) acrylate and 2- (2-phenylphenoxy) ethyl are particularly preferable.
  • (Meth) acrylate and cyclohexyl (meth) acrylate are preferred.
  • These reactive diluents may be used alone or, if necessary, in combination of two or more.
  • the amount used is that when 100 parts by weight of the (meth) acrylate compound represented by the above general formula (1) is used in combination with another polyfunctional (meth) acrylate compound To the total of 100 parts by weight of the (meth) acrylate compound represented by the general formula (1) and other polyfunctional (meth) acrylate compounds), usually 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, Preferably, it is 10 to 200 parts by weight.
  • non-reactive diluents include aliphatic hydrocarbons, ketones, aromatic hydrocarbons, glycol ethers, esters, petroleum solvents and the like.
  • Aliphatic hydrocarbons such as hexane, heptane, octane etc., ketones such as ethyl methyl ketone, cyclohexanone etc., aromatic hydrocarbons such as toluene, xylene etc., glycol ethers such as ethyl cellosolve, methyl cellosolve , Carbitol, methyl carbitol, propylene glycol monomethyl ether etc.
  • the petroleum solvents include, for example, petroleum ether, petroleum naphtha, solvent naphtha and the like. These non-reactive diluents may be used alone or, if necessary, in combination of two or more.
  • the amount used in the case of using a non-reactive diluent is (when another polyfunctional (meth) acrylate compound is used in combination with 100 parts by weight of the (meth) acrylate compound represented by the above general formula (1), To the total of 100 parts by weight of the (meth) acrylate compound represented by the above general formula (1) and other polyfunctional (meth) acrylate compounds), usually 1 to 500 parts by weight, preferably 20 to 300 parts by weight, More preferably, it is 30 to 200 parts by weight.
  • the curable composition of the present invention includes, in addition to the above-mentioned other polyfunctional (meth) acrylate compounds, polymerization initiators and diluents, conventional additives such as colorants, stabilizers (thermal stabilizers, oxidation Inhibitors, ultraviolet absorbers, etc., fillers, antistatic agents, flame retardants, flame retardant aids, leveling agents, silane coupling agents, polymerization inhibitors (or thermal polymerization inhibitors), etc. may be included. These additives may be used alone or in combination of two or more as needed.
  • the cured product of the curable composition containing the (meth) acrylate compound represented by the above general formula (1) of the present invention is obtained by performing the curing treatment described later on the curable composition of the present invention described above.
  • a curable composition containing a (meth) acrylate compound represented by the above general formula (1) to form a coating (or thin film) It can be manufactured by applying a curing treatment.
  • the thickness of the film-like coating can be selected according to the application, and is, for example, 0.1 to 1000 ⁇ m, preferably 1 to 500 ⁇ m, and more preferably 5 to 300 ⁇ m.
  • a cured product having a three-dimensional shape for example, a prism shape, a lens shape, etc.
  • the viscosity of the curable composition containing the (meth) acrylate compound represented by the above general formula (1) may be reduced by heating prior to the curing treatment.
  • the curing treatment examples include heat treatment and light irradiation treatment. Further, the heat treatment and the light irradiation treatment may be combined.
  • the heating temperature in the heat treatment is, for example, 50 to 250 ° C., preferably 60 to 200 ° C., and more preferably 70 to 150 ° C.
  • the amount of light irradiation energy varies depending on the application, film thickness of the coating film, etc., but is usually 0.1 to 10000 mJ / cm 2 , preferably 1 to 8000 mJ / cm 2 , More preferably, it is 10 to 5000 mJ / cm 2 .
  • the (meth) acrylate compound represented by the above general formula (1) of the present invention is excellent in compatibility or solubility with a diluent such as an organic solvent or a monofunctional (meth) acrylate compound, so that a large amount of dilution is performed. It is characterized in that the cured product can be easily produced without performing dilution by the agent.
  • a cured product can be easily produced as compared with the case of using a difunctional (meth) acrylate compound derived from a conventionally known bisphenol compound having a fluorene skeleton, and it is represented by the above general formula (1)
  • a cured product which can sufficiently exhibit the characteristics (high refractive index, low Abbe, etc.) of the (meth) acrylate compound is obtained.
  • the refractive index and Abbe number at each of the following wavelengths measured as follows are the refractive index and Abbe index of the difunctional (meth) acrylate compound obtained in the following Examples and the like. It was a number. 5 wt%, 10 wt% and 15 wt% solutions of each difunctional (meth) acrylate compound in N-methyl-2-pyrrolidone (for Comparative Example 1 and Comparative Example 2, it is difficult to dissolve in an organic solvent Therefore, 1% by weight, 3% by weight and 5% by weight) were prepared, and the refractive index at each wavelength was measured for each solution under the following apparatus and conditions.
  • Mass spectrum value (M + NH 4 ) + : 788.3746 (Calculated molecular weight of the compound represented by the above formula (2-1) (TOF MS APCI + ; C 55 H 46 O 4 + NH 4 ): 788.3740)
  • Mass spectrometry (M + NH 4 ) + : 896.3946 (Calculated molecular weight of the compound represented by the above formula (1-1) (TOF MS APCI + ; C 57 H 42 O 4 + NH 4 ): 896. 3951)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un composé (méth)acrylate représenté par la formule générale (1) et son procédé de production. Dans la formule, R1 à R4 sont chacun identiques ou différents et représentent un groupe alkyle, un groupe aryle ou un atome d'halogène, R5 et R6 sont chacun identiques ou différents et représentent un groupe alkylène ayant de 2 à 4 atomes de carbone, qui peut être ramifié, et R7 et R8 sont chacun identiques ou différents et représentent un atome d'hydrogène ou un groupe méthyle. k1 à k4 sont identiques ou différents et sont un nombre entier de 0 à 4, n1 et n2 sont identiques ou différents et sont un nombre entier supérieur ou égal à 1, et p1 et p2 sont identiques ou différents et sont un nombre entier supérieur ou égal à 1. Lorsque k1 à k4 sont 2 ou plus, les groupes R1 à R4 correspondant respectivement peuvent être identiques ou différents.
PCT/JP2018/041645 2017-12-12 2018-11-09 Composé (méth)acrylate ayant un squelette fluorène WO2019116798A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006152115A (ja) * 2004-11-29 2006-06-15 Omron Corp 硬化型樹脂組成物、耐光性光学部品および光学機器
JP2011126991A (ja) * 2009-12-17 2011-06-30 Kyoeisha Chem Co Ltd 光学材料用樹脂組成物
US20150376355A1 (en) * 2014-06-27 2015-12-31 Chi Mei Corporation Photosensitive resin composition, protective film and element having the same
WO2017135123A1 (fr) * 2016-02-03 2017-08-10 田岡化学工業株式会社 Bisphénol ayant un squelette fluorène et son procédé de production, résine polyarylate dérivée dudit bisphénol, composé de (méth)acrylate et résine époxy

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3130555B2 (ja) * 1991-04-26 2001-01-31 三菱レイヨン株式会社 プラスチックレンズ材料、プラスチックレンズおよび眼鏡用レンズ
JP2977714B2 (ja) * 1993-10-04 1999-11-15 鐘紡株式会社 ポリエステル成形体
JP2001122828A (ja) 1999-10-27 2001-05-08 Shinnakamura Kagaku Kogyo Kk ２官能（メタ）アクリル酸エステル組成物とそのための２価アルコール
JP4671231B2 (ja) 2005-06-16 2011-04-13 田岡化学工業株式会社 フルオレン誘導体の製造方法
JP5588105B2 (ja) 2007-12-26 2014-09-10 大阪瓦斯株式会社 フルオレン骨格を有する二官能性（メタ）アクリレート
JP5325627B2 (ja) 2008-03-27 2013-10-23 大阪瓦斯株式会社 フルオレン骨格を有するアルコールの製造方法
TWI474118B (zh) 2012-05-15 2015-02-21 Chi Mei Corp 感光性聚矽氧烷組成物、保護膜及具有保護膜的元件
JP5704736B1 (ja) 2013-10-07 2015-04-22 田岡化学工業株式会社 フルオレン構造を有するポリカーボネート樹脂の解重合方法
JP6470620B2 (ja) 2014-04-01 2019-02-13 大阪ガスケミカル株式会社 フルオレン骨格を有する（メタ）アクリレート化合物及びその製造方法
TWI524150B (zh) 2014-06-27 2016-03-01 奇美實業股份有限公司 感光性樹脂組成物、保護膜及具有保護膜之元件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006152115A (ja) * 2004-11-29 2006-06-15 Omron Corp 硬化型樹脂組成物、耐光性光学部品および光学機器
JP2011126991A (ja) * 2009-12-17 2011-06-30 Kyoeisha Chem Co Ltd 光学材料用樹脂組成物
US20150376355A1 (en) * 2014-06-27 2015-12-31 Chi Mei Corporation Photosensitive resin composition, protective film and element having the same
WO2017135123A1 (fr) * 2016-02-03 2017-08-10 田岡化学工業株式会社 Bisphénol ayant un squelette fluorène et son procédé de production, résine polyarylate dérivée dudit bisphénol, composé de (méth)acrylate et résine époxy

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