WO2010113600A1 - Dérivé d'ester de type (méth)acrylate - Google Patents

Dérivé d'ester de type (méth)acrylate Download PDF

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WO2010113600A1
WO2010113600A1 PCT/JP2010/053860 JP2010053860W WO2010113600A1 WO 2010113600 A1 WO2010113600 A1 WO 2010113600A1 JP 2010053860 W JP2010053860 W JP 2010053860W WO 2010113600 A1 WO2010113600 A1 WO 2010113600A1
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group
meth
acrylate
acrylic acid
substituent
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PCT/JP2010/053860
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English (en)
Japanese (ja)
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明宏 近藤
ミヒャエル エンゲル
直也 生島
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Dic株式会社
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Priority to JP2010523636A priority Critical patent/JP4645925B2/ja
Publication of WO2010113600A1 publication Critical patent/WO2010113600A1/fr

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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton

Definitions

  • the present invention relates to a novel (meth) acrylic acid ester derivative that can be used as an optical material.
  • the liquid crystal display elements are reduced in size, increased in brightness, and increased in brightness.
  • Light resistance is required.
  • optical resins are often highly viscous or solid, and are currently used after being diluted with a solvent or a reactive diluent.
  • PTEA phenylthioethyl acrylate
  • O-phenylphenoxyethyl acrylate O-phenylphenoxyethyl acrylate
  • NTEA naphthylthioethyl acrylate
  • a reactive diluent that can be adjusted to an optimum viscosity for shaping while maintaining a high refractive index as an optical resin
  • a polymerizable monomer such as a (meth) acrylic acid ester derivative that has a high refractive index and a low viscosity is used. It was long-awaited.
  • Patent Document 1 discloses an acrylate ester having biphenyl and a polyethyleneoxy / polypropyleneoxy group in the molecule as a raw material for a high refractive index cured product that does not contain bromine and does not harden the cured product.
  • a (meth) acrylic acid oligomer having a high refractive index and a high viscosity is used.
  • the viscosity of the (meth) acrylic acid ester derivative described in 1 was not able to sufficiently reduce the viscosity of the resin composition.
  • Patent Document 2 discloses a (meth) (meth) acrylate derivative having a fluorenyl group as a novel (meth) acrylate having a low viscosity and a high refractive index. However, it was only 580 cps (25 degrees) in the examples, and it could not be said that sufficient low viscosity was obtained.
  • Patent Document 3 energy obtained by esterification reaction or transesterification reaction of monohydroxy compound obtained by addition reaction of cyclic ether compound with monophenol compound and (meth) acrylic acid or its lower ester.
  • a (meth) acrylic acid ester compound for a linear curable resin is described. However, although a refractive index of 1.56 or more is obtained, there is no specific description of the viscosity, and the low viscosity is unknown.
  • Patent Document 4 an acrylic and methacrylic resin composition is placed in a matrix, the resin composition is cured by heat or energy rays, and then the resin composition and the matrix are peeled to form an optical component. Accordingly, an optical component containing 5 to 100% by weight of a compound having a benzhydryl group in an acrylic or methacrylic resin composition is described. However, the viscosity of the (meth) acrylic acid ester derivative described in this document and the refractive index of the cured product obtained from the composition containing the (meth) acrylic acid ester derivative are not always sufficient.
  • the required performance for the current reactive diluent is as follows: high refractive index (eg, n> 1.55), low viscosity (eg, 100 mPa ⁇ s or less), high light resistance (eg, ⁇ Y ⁇ 1000 h at 1000 h). 10) Although it has high diluting ability, high light transmittance, and high UV curing property, no (meth) acrylic acid ester derivative that can be used for optical materials satisfying these required performances has been obtained so far. is the current situation.
  • high refractive index eg, n> 1.55
  • low viscosity eg, 100 mPa ⁇ s or less
  • high light resistance eg, ⁇ Y ⁇ 1000 h at 1000 h.
  • Japanese Laid-Open Patent Publication No. 5-58950 JP 2000-319336 A Japanese Laid-Open Patent Publication No. 2008-31355 Japanese Laid-Open Patent Publication No. 6-134772
  • An object of the present invention is to provide a novel (meth) acrylic acid ester derivative having a low viscosity and having a high refractive index, which can be used as an optical material.
  • R 1 and R 2 are each independently a group having a benzene ring which may have a substituent, n represents an integer of 1 to 4, 2)
  • X— is any group represented by the following formula (6) or (7),
  • R 1 and R 2 are each independently a group arbitrarily selected from a lower alkyl group having 1 to 4 carbon atoms or a group having a benzene ring which may have a substituent, and R 1 and R 2 At least one represents a group having a benzene ring which may have a substituent, R 3 represents a lower alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4. )
  • the (meth) acrylic acid ester derivative represented by the general formula (1) has a low viscosity
  • a cured product using the (meth) acrylic acid ester derivative has a high refractive index. Solve the problem.
  • the nitrogen-containing (meth) acrylic acid ester derivative having a group represented by the formula (6) or (7) has low viscosity
  • the nitrogen-containing ( Amount used when adjusting the viscosity according to the shaping conditions of ultraviolet ray or electron beam curable resin composition using (meth) acrylic acid oligomer with high refractive index and high viscosity by using (meth) acrylic acid ester derivative As a result, a cured product having a high refractive index can be obtained.
  • a low-viscosity (meth) acrylate derivative that has a high refractive index and can be used as an optical material.
  • the (meth) acrylic acid ester derivative used in the present invention has the general formula (1)
  • R 1 and R 2 are each independently a group having a benzene ring which may have a substituent, n represents an integer of 1 to 4, 2)
  • X— is any group represented by the following formula (6) or (7),
  • R 1 and R 2 are each independently a group arbitrarily selected from a lower alkyl group having 1 to 4 carbon atoms or a group having a benzene ring which may have a substituent, and R 1 and R 2 At least one is a group having a benzene ring which may have a substituent, R 3 is a lower alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 4.
  • the (meth) acrylic acid ester derivative of the present invention includes a methacrylic acid ester derivative.
  • Preferred examples of the group represented by R 1 and R 2 and having a benzene ring which may have a substituent include, for example, a phenyl group, a diphenyl ether group, a diphenylmethyl group, (2-phenyl) And groups such as an ethyl) phenyl group and a benzyloxyphenyl group.
  • a specific (meth) acrylic acid ester derivative of the present invention for example, 2,2-diphenylethyl acrylate, 3,3-diphenylpropyl acrylate, 4,4-diphenylbutyl acrylate, 2- (diphenylmethoxy) ethyl acrylate, 2-benzylphenyl acrylate, 3-benzylphenyl acrylate, 4-benzylphenyl acrylate 2-phenoxyphenyl acrylate, 3-phenoxyphenyl acrylate, 4-phenoxyphenyl acrylate, 2-benzylbenzyl acrylate, 3-benzylbenzyl acrylate, 4-benzylbenzyl acrylate, 2-phenoxybenzyl acrylate, 3-phenoxybenzyl acrylate, 4 -Phenoxybenzyl acrylate, 2- (2-phenoxyphenoxy) ethyl acrylate, 2-phenethylphenyl acrylate , 3-phenethylphenyl acrylate,
  • substituent of the benzene ring in these compounds may or may not have, but in the case of having it, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is preferable.
  • the lower alkyl group having 1 to 4 carbon atoms represented by R 1 and R 2 is preferably a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group or an n-butyl group. Differently, an ethyl group is preferable.
  • the group represented by R 1 and R 2 and having a benzene ring which may have a substituent may have, for example, a phenyl group which may have a substituent or a substituent. Examples thereof include a benzyl group, an optionally substituted naphthyl group, an optionally substituted diphenylmethyl group, and an optionally substituted diphenyl ether group.
  • R 1 and R 2 can be arbitrarily selected from the above-mentioned groups.
  • the object of the present invention is that the cured product has a high refractive index and can be used as an optical material.
  • At least one of them is preferably a group having a benzene ring which may have a substituent, and both R 1 and R 2 have a substituent. More preferably, it may be a group having a benzene ring.
  • the lower alkyl group having 1 to 4 carbon atoms is preferably a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and particularly preferably a methyl group or an ethyl group.
  • nitrogen-containing (meth) acrylic acid ester derivatives of the present invention for example, (N, N-diphenylamino) methyl acrylate, 2- (N, N-diphenylamino) ethyl acrylate, 3- (N, N-diphenylamino) propyl acrylate, 4- (N, N-diphenylamino) butyl acrylate, (N-benzyl-N-phenylamino) methyl acrylate, 2- (N-benzyl-N-phenylamino) ethyl acrylate, 3- (N-benzyl-N-phenylamino) propyl acrylate, 4- (N-benzyl- N-phenylamino) butyl acrylate, (N-diphenylmethyl-N-methylamino) methyl acrylate, 2- (N-diphenylmethyl-N-methylamino) ethyl acrylate, 3- (N-diphenylmethyl-N-N-
  • the acrylic acid derivative of the present invention can be produced by a generally known production method.
  • an esterification catalyst such as p-toluenesulfonic acid or sulfuric acid and a polymerization inhibitor such as hydroquinone or phenothiazine
  • a solvent for example, toluene, benzene, In the presence of cyclohexane, n-hexane, n-heptane, etc.
  • the acrylic acid is used in an amount of 1 to 5 mol, preferably 1.05 to 2 mol, per mol of the alcohol.
  • the esterification catalyst is present at a concentration of 0.1 to 15 mol%, preferably 1 to 6 mol%, based on the acrylic acid used.
  • a basic substance in the dehydrohalogenation reaction in the presence of a basic substance, it can be obtained, for example, by reacting acrylic acid chloride with a corresponding alcohol. At that time, it is preferable to add an amine basic substance such as triethylamine or pyridine. It can be obtained by reacting at a temperature of preferably 0 to 100 ° C. in the presence of solvents (for example, toluene, benzene, cyclohexane, n-hexane, n-heptane, acetone, tetrahydrofuran, etc.).
  • solvents for example, toluene, benzene, cyclohexane, n-hexane, n-heptane, acetone, tetrahydrofuran, etc.
  • the resin composition of the present invention comprises a (meth) acrylic acid ester derivative represented by the general formula (1) and other unsaturated group-containing compounds.
  • unsaturated group-containing compounds other than (meth) acrylic acid ester derivative components include reactive monomers and reactive oligomers, and (meth) acrylate-based reactive monomers and (meth) acrylate-based compounds. These reactive oligomers are preferred.
  • Examples of the reactive monomer include acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, Isobornyl (meth) acrylate, tribromophenyl (meth) acrylate, o-phenylphenyloxyethyl (meth) acrylate, o-phenylphenyloxyethyloxyethyl (meth) acrylate, 2-hydroxy-3- (dibromophenyl) oxypropyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, tetrabromobisphenol A polyethoxydi (meth) acrylate (Meth) acrylate-based reactive units such as poly
  • Examples of the reactive oligomer include epoxy (meth) acrylate which is a reaction product of epoxy resins and (meth) acrylic acid, urethane which is a reaction product of polyols, organic polyisocyanates and hydroxyl group-containing (meth) acrylates ( Examples include (meth) acrylate-based reactive oligomers such as (meth) acrylate.
  • epoxy resins used for obtaining epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, terminal glycidyl ether of bisphenol A propylene oxide adduct, and fluorene epoxy. Examples thereof include resins.
  • the reaction of epoxy resins with (meth) acrylic acid is preferably about 0.8 to 1.5 chemical equivalents, particularly preferably about 0.8 to 1.5 chemical equivalents per chemical equivalent of the epoxy groups of the epoxy resins.
  • the reaction is performed at a ratio of 0.9 to 1.1 chemical equivalents, and 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, phenoxy is used as a diluent during the reaction.
  • Photopolymerizable vinyl monomers such as ethyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate are used, and catalysts (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, Benzyltriethylammonium bromide, triphenylphos Fins, it is preferred to use triphenyl stibine, etc.)
  • the amount of the catalyst is preferably 0.1 to 10% by weight relative to the reaction mixture, particularly preferably 0.3 to 5 wt%.
  • a polymerization inhibitor for example, methoquinone, hydroquinone, phenothiazine, etc.
  • the amount used is preferably 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight, based on the reaction mixture.
  • the reaction temperature is preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C.
  • polyols used to obtain urethane (meth) acrylate include ethylene glycol, 1,4-butanediol, neopentyl glycol, polycaprolactone polyol, polyester polyol, polytetramethylene glycol, bisphenol A polyethoxydiol, and the like. can give.
  • organic polyisocyanates used for obtaining urethane (meth) acrylate include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate and the like.
  • hydroxyl group-containing (meth) acrylates examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
  • the urethane (meth) acrylate is reacted at a reaction temperature of preferably 1.1 to 2.0 chemical equivalents, preferably 70 to 90 ° C., of the isocyanate groups of the organic polyisocyanates per one chemical equivalent of hydroxyl groups of the polyols.
  • the urethane oligomer is synthesized, and then the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated compound is preferably 1 to 1.5 chemical equivalents, preferably 70 to 90 ° C. reaction temperature per chemical equivalent of isocyanate groups of the urethane oligomer. It can obtain by making it react.
  • (B) components particularly preferable examples include (meth) acrylate-based reactive oligomers such as epoxy (meth) acrylate and urethane (meth) acrylate.
  • the nitrogen-containing acrylic acid derivative of the present invention is produced.
  • it can be carried out by a generally known method.
  • 2- (N, N-diphenylamino) ethyl acrylate will be described below as an example.
  • the reaction of N, N-diphenylamine and halogenated ethanol is carried out to give 2- (N, N-diphenylamino) ethanol. Synthesize. This reaction can be performed by mixing two raw materials and performing a heating reaction by a generally known method.
  • the reaction temperature can be in the range of 50 to 150 ° C, preferably about 100 ° C.
  • the reaction time varies depending on the reaction temperature, but in the case of about 100 ° C., it can be carried out in about 10 to 15 hours.
  • 2- (N, N-diphenylamino) ethanol can be obtained by adding an organic solvent such as toluene and water, performing separation extraction and distilling off the solvent by a generally known method. .
  • the obtained 2- (N, N-diphenylamino) ethanol is reacted with acrylic acid chloride.
  • an amine basic substance such as triethylamine or pyridine.
  • nitrogen-containing (meth) acrylic acid ester derivatives of the present invention can be produced by reacting the corresponding amine compound with an amino alcohol obtained by the reaction of a halogenated alcohol and an acrylic acid halide, respectively. And a nitrogen-containing (meth) acrylic acid ester derivative. Reaction conditions such as reaction temperature and reaction time in each step vary depending on the amine and alcohol used, but can be adjusted as appropriate.
  • the resin composition of the present invention comprises a nitrogen-containing (meth) acrylic acid ester derivative represented by the general formula (1) and other unsaturated group-containing compounds.
  • unsaturated group-containing compounds other than the nitrogen-containing (meth) acrylic acid ester derivative (A) component include reactive monomers and reactive oligomers, and (meth) acrylate-based reactive monomers and A (meth) acrylate-based reactive oligomer is preferred.
  • Examples of the reactive monomer include acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, Isobornyl (meth) acrylate, tribromophenyl (meth) acrylate, o-phenylphenyloxyethyl (meth) acrylate, o-phenylphenyloxyethyloxyethyl (meth) acrylate, 2-hydroxy-3- (dibromophenyl) oxypropyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, tetrabromobisphenol A polyethoxydi (meth) acrylate (Meth) acrylate-based reactive units such as poly
  • Examples of the reactive oligomer include epoxy (meth) acrylate which is a reaction product of epoxy resins and (meth) acrylic acid, urethane which is a reaction product of polyols, organic polyisocyanates and hydroxyl group-containing (meth) acrylates ( Examples include (meth) acrylate-based reactive oligomers such as (meth) acrylate.
  • epoxy resins used for obtaining epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, terminal glycidyl ether of bisphenol A propylene oxide adduct, and fluorene epoxy. Examples thereof include resins.
  • the reaction of epoxy resins with (meth) acrylic acid is preferably about 0.8 to 1.5 chemical equivalents, particularly preferably about 0.8 to 1.5 chemical equivalents per chemical equivalent of the epoxy groups of the epoxy resins.
  • the reaction is performed at a ratio of 0.9 to 1.1 chemical equivalents, and 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, phenoxy is used as a diluent during the reaction.
  • Photopolymerizable vinyl monomers such as ethyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate are used, and catalysts (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, Benzyltriethylammonium bromide, triphenylphos Fins, it is preferred to use triphenyl stibine, etc.)
  • the amount of the catalyst is preferably 0.1 to 10% by weight relative to the reaction mixture, particularly preferably 0.3 to 5 wt%.
  • a polymerization inhibitor for example, methoquinone, hydroquinone, phenothiazine, etc.
  • the amount used is preferably 0.01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight, based on the reaction mixture.
  • the reaction temperature is preferably 60 to 150 ° C., particularly preferably 80 to 120 ° C.
  • polyols used to obtain urethane (meth) acrylate include ethylene glycol, 1,4-butanediol, neopentyl glycol, polycaprolactone polyol, polyester polyol, polytetramethylene glycol, bisphenol A polyethoxydiol, and the like. can give.
  • organic polyisocyanates used for obtaining urethane (meth) acrylate include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate and the like.
  • hydroxyl group-containing (meth) acrylates examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
  • the urethane (meth) acrylate is reacted at a reaction temperature of preferably 1.1 to 2.0 chemical equivalents, preferably 70 to 90 ° C., of the isocyanate groups of the organic polyisocyanates per one chemical equivalent of hydroxyl groups of the polyols.
  • the urethane oligomer is synthesized, and then the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated compound is preferably 1 to 1.5 chemical equivalents, preferably 70 to 90 ° C. reaction temperature per chemical equivalent of isocyanate groups of the urethane oligomer. It can obtain by making it react.
  • (B) components particularly preferable examples include (meth) acrylate-based reactive oligomers such as epoxy (meth) acrylate and urethane (meth) acrylate.
  • the resin composition of the present invention is cured by irradiation with ultraviolet rays, it is preferable to use a photopolymerization initiator (C).
  • the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. These can be used alone or in combination of two or more.
  • the proportion of each component used in the resin composition of the present invention is preferably 5 to 95% by weight, particularly preferably 10 to 80% by weight for the component (A).
  • the component (B) is preferably 5 to 95% by weight, particularly preferably 20 to 90% by weight.
  • the component (C) is preferably 0 to 15 parts by weight, particularly preferably 0 to 7 parts by weight, when the component (A) + (B) is 100 parts by weight.
  • the resin composition of the present invention comprises a release agent, an antifoaming agent, a leveling agent, a light stabilizer (for example, hindered amine), an antioxidant, a polymerization inhibitor, an antistatic agent, and a colorant (for example, a dye). , Pigments, etc.), inorganic fillers, organic fillers and the like can be used in combination.
  • the resin composition of the present invention can be obtained by uniformly mixing and dissolving the above components.
  • the resin composition of the present invention is useful for transmission screens such as Fresnel lenses and lenticular lenses, prism lens sheets for TFTs, and lenses such as spectacle lenses, but also various coating agents, casting agents, and adhesives. Alternatively, it is useful for printing inks and the like.
  • cured material of the composition of this invention can be obtained by irradiating energy rays, such as an electron beam and an ultraviolet-ray.
  • the resin composition of the present invention is applied on, for example, a stamper having the shape of a Fresnel lens or a lenticular lens, a layer of the resin composition is provided, and a hard transparent substrate is adhered on the layer, In this state, the resin composition is cured by irradiating ultraviolet rays from the hard transparent substrate side with a high-pressure mercury lamp or the like, and then peeled off from the stamper.
  • a soft Fresnel lens or lenticular lens having a refractive index (23 ° C.) of preferably 1.55 or more, particularly preferably 1.56 or more is obtained.
  • Example 1 Synthesis of 3,3-diphenylpropyl acrylate (A) In a 2000 mL four-necked flask equipped with a stirrer, thermometer, calcium chloride drying tube and dropping funnel, 70 parts of 3,3-diphenylpropyl alcohol and 352 of toluene 0.5 part, 40.3 parts of triethylamine and 0.0265 part of p-methoxyphenol were added and dissolved at room temperature. A dropping funnel was charged with 36.1 parts of acrylic acid chloride, and the entire amount of acrylic acid chloride was dropped over 30 minutes while maintaining the temperature in the flask at 0 to 10 ° C. with an ice bath. After completion of dropping, the temperature was returned to room temperature and stirring was continued for 1 hour.
  • Example 2 Synthesis of 2- (diphenylmethoxy) ethyl acrylate (B)
  • 2- (diphenylmethoxy) ethanol was used instead of 3,3-diphenylpropyl alcohol, and 2- (Diphenylmethoxy) ethyl acrylate was synthesized (yield 74 g, yield 80%).
  • the product obtained had a refractive index (nD, 25 ° C.) of 1.550 and a viscosity (25 ° C.) of 42 mPa ⁇ s.
  • Example 3 Synthesis of 2-benzylbenzyl acrylate (C) In the same manner as in Example 1, using (2-benzylphenyl) methanol instead of 3,3-diphenylpropyl alcohol, 2-benzylbenzyl acrylate was synthesized (yield 70 g, yield 85%). The product obtained had a refractive index (nD, 25 ° C.) of 1.564 and a viscosity (25 ° C.) of 20 mPa ⁇ s.
  • Example 4 Synthesis of 2-phenoxybenzyl acrylate (D) In the same manner as in Example 1, using (2-phenoxyphenyl) methanol instead of 3,3-diphenylpropyl alcohol, 2-phenoxybenzyl acrylate was synthesized (yield 69 g, yield 82%). The product obtained had a refractive index (nD, 25 ° C.) of 1.564 and a viscosity (25 ° C.) of 17 mPa ⁇ s.
  • Example 5 Synthesis of 2- (2-phenoxyphenoxy) ethyl acrylate (E)
  • 2- (2-phenoxyphenoxy) ethanol was used instead of 3,3-diphenylpropyl alcohol.
  • 2- (2-phenoxyphenoxy) ethyl acrylate was synthesized (yield 66 g, yield 70%).
  • the product obtained had a refractive index (nD, 25 ° C.) of 1.559 and a viscosity (25 ° C.) of 55 mPa ⁇ s.
  • Example 6 Synthesis of 1,2-diphenylethyl acrylate (F) 1,2-diphenylethanol was used in the same manner as in Example 1, except that 1,2-diphenylethanol was used instead of 3,3-diphenylpropyl alcohol.
  • Diphenylethyl acrylate was synthesized (70 g yield, 85% yield). The product obtained had a refractive index (nD, 25 ° C.) of 1.566 and a viscosity (25 ° C.) of 25 mPa ⁇ s.
  • Example 7 A composition was obtained by blending 50 parts of 3,3-diphenylpropyl acrylate obtained in Example 1 and 50 parts of Aronix M-211B (product name, EO-modified bisphenol A diacrylate, manufactured by Toagosei Co., Ltd.).
  • the refractive index (nD, 25 ° C.) of this composition was 1.549, and the viscosity (25 ° C.) was 230 mPa ⁇ s.
  • Example 8 to (Example 12) were carried out in the same manner as in Example 7, except that instead of 50 parts of 3,3-diphenylpropyl acrylate in Example 7, the (meth) acrylic acid ester derivatives shown in Table 1 were used. Table 1 shows the physical properties of the obtained cured product.
  • Example 14 Synthesis of 2- (N-benzyl-N-phenylamino) ethyl acrylate (H) In the same manner as in Example 13, instead of 2- (N, N-diphenylamino) ethanol, 2- (N 2- (N-benzyl-N-phenylamino) ethyl acrylate was synthesized using (N-benzyl-N-phenylamino) ethanol (yield 175 g, yield 80%). The product obtained had a refractive index (nD, 25 ° C.) of 1.581 and a viscosity (25 ° C.) of 215 mPa ⁇ s.
  • Example 15 Synthesis of 2- (N, N-dibenzylamino) ethyl acrylate (I)
  • 2- (N, N-diphenylamino) ethanol was used to synthesize 2- (N, N-dibenzylamino) ethyl acrylate (yield 195 g, yield 85%).
  • the product obtained had a refractive index (nD, 25 ° C.) of 1.548 and a viscosity (25 ° C.) of 38 mPa ⁇ s.
  • Example 16 Synthesis of 2- (N-diphenylmethyl-N-methylamino) ethyl acrylate (J) In the same manner as in Example 13, instead of 2- (N, N-diphenylamino) ethanol, 2- 2- (N-diphenylmethyl-N-methylamino) ethyl acrylate was synthesized using (N-diphenylmethyl-N-methylamino) ethanol (yield 217 g, yield 75%). The product obtained had a refractive index (nD, 25 ° C.) of 1.557 and a viscosity (25 ° C.) of 270 mPa ⁇ s.
  • Example 17 Synthesis of 2- (N-biphenyl-N-methylamino) ethyl acrylate (K) In the same manner as in Example 13, instead of 2- (N, N-diphenylamino) ethanol, 2- (N 2- (N-biphenyl-N-methylamino) ethyl acrylate was synthesized using (N-biphenyl-N-methylamino) ethanol (yield 153 g, yield 70%). The product obtained had a refractive index (nD, 25 ° C.) of 1.576 and a viscosity (25 ° C.) of 107 mPa ⁇ s.
  • Example 18 Composition comprising 50 parts of 2- (N, N-diphenylamino) ethyl acrylate obtained in Example 13 and 50 parts of Aronix M-211B (product name, EO-modified bisphenol A diacrylate, manufactured by Toagosei Co., Ltd.) Got.
  • the refractive index (nD, 25 ° C.) of this composition was 1.5628, and the viscosity (25 ° C.) was 134 mPa ⁇ s.
  • Example 19 to (Example 22) Instead of 50 parts of 2- (N, N-diphenylamino) ethyl acrylate in Example 18, the (meth) acrylic acid ester derivatives listed in Table 2 were used. 22 was performed. Table 2 shows the evaluation of physical properties of the obtained cured product.
  • novel (meth) acrylic acid ester derivative of the present invention can be used as an optical material.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Les propriétés requises pour un diluant réactif existant sont un indice de réfraction élevé, une faible viscosité, une aptitude élevée à la dilution, un facteur de transmission de la lumière élevé et une aptitude élevée au durcissement par des UV. Cependant, un dérivé d'ester de type acrylate qui satisfait à ces propriétés requises et qui peut être utilisé pour un matériau optique n'a pas encore été obtenu. Par conséquent, l'invention porte sur un nouveau dérivé d'ester de type (méth)acrylate, dont un produit durci a un indice de réfraction élevé et qui a une faible viscosité et qui peut être utilisé comme matériau optique. Le dérivé d'ester de type (méth)acrylate a un dérivé spécifique du benzène qui peut avoir un substituant dans le résidu ester.
PCT/JP2010/053860 2009-03-31 2010-03-09 Dérivé d'ester de type (méth)acrylate WO2010113600A1 (fr)

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JP2012219205A (ja) * 2011-04-11 2012-11-12 Kyoeisha Chem Co Ltd 光学材料用樹脂組成物及びその成形体
WO2012158317A2 (fr) 2011-05-13 2012-11-22 3M Innovative Properties Company Monomères de (méth)acrylate de benzyle appropriés pour des films optiques microstructurés
WO2012157324A1 (fr) * 2011-05-18 2012-11-22 Dic株式会社 Composition polymérisable par voie radicalaire, produit durci et lentille en plastique
WO2012172841A1 (fr) * 2011-06-13 2012-12-20 Dic株式会社 Composition polymérisable par voie radicalaire, produit durci et lentille plastique
JP2017214475A (ja) * 2016-05-31 2017-12-07 株式会社菱晃 光学部材用硬化性樹脂組成物、光学部材用樹脂、光学部材、レンズ及びカメラモジュール
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JP2012219205A (ja) * 2011-04-11 2012-11-12 Kyoeisha Chem Co Ltd 光学材料用樹脂組成物及びその成形体
JP2021176966A (ja) * 2011-05-13 2021-11-11 スリーエム イノベイティブ プロパティズ カンパニー ミクロ構造化光学フィルムに適したベンジル（メタ）アクリレートモノマー
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TWI629288B (zh) * 2011-05-13 2018-07-11 ３Ｍ新設資產公司 適用於微結構光學膜之（甲基）丙烯酸苄酯單體
JP7228628B2 (ja) 2011-05-13 2023-02-24 スリーエム イノベイティブ プロパティズ カンパニー ミクロ構造化光学フィルムに適したベンジル（メタ）アクリレートモノマー
JP2017125197A (ja) * 2011-05-13 2017-07-20 スリーエム イノベイティブ プロパティズ カンパニー ミクロ構造化光学フィルムに適したベンジル（メタ）アクリレートモノマー
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JP2017214475A (ja) * 2016-05-31 2017-12-07 株式会社菱晃 光学部材用硬化性樹脂組成物、光学部材用樹脂、光学部材、レンズ及びカメラモジュール
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