WO2017077932A1 - Composition de résine photodurcissable pour microlentilles - Google Patents

Composition de résine photodurcissable pour microlentilles Download PDF

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WO2017077932A1
WO2017077932A1 PCT/JP2016/081829 JP2016081829W WO2017077932A1 WO 2017077932 A1 WO2017077932 A1 WO 2017077932A1 JP 2016081829 W JP2016081829 W JP 2016081829W WO 2017077932 A1 WO2017077932 A1 WO 2017077932A1
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acrylate
group
meth
resin composition
photocurable resin
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PCT/JP2016/081829
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前田　大輔
直也 西村
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日産化学工業株式会社
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses

Definitions

  • the present invention relates to a photocurable resin composition for microlenses, and more specifically, a solvent-free photocurable resin for microlenses containing a triazine ring-containing polymer and a reactive diluent and no solvent. Relates to the composition.
  • microlenses In recent years, the demand for microlenses has increased as small lenses for digital cameras and smartphone-equipped cameras.
  • the resin has the advantages of being lighter and more workable than glass, it generally has the disadvantages that the optical distortion is larger and the refractive index is lower than that of glass. Since the curvature of the lens surface can be made smaller if the refractive index of the material is high, the amount of aberration that occurs on this surface can be reduced. As a result, the lens system can be reduced in size and weight by reducing the number of lenses, lens thickness, and eccentric sensitivity. Can be realized. Further, in designing an optical unit, it is known to correct chromatic aberration by using a plurality of lenses having different Abbe numbers, and in particular, development of a material having a low Abbe number is required.
  • the present invention has been made in view of such circumstances, and is a solvent-free photocurable resin composition for a microlens that can produce a microlens having a high refractive index and a low Abbe number by an optical nanoimprint method.
  • the purpose is to provide.
  • the present inventors have used a solvent-free composition containing a triazine ring-containing polymer having a predetermined molecular weight and a predetermined reactive diluent.
  • the inventors have found that microlenses having a high refractive index and a low Abbe number can be efficiently produced by an optical nanoimprint method, and thus completed the present invention.
  • R 1 to R 92 are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1
  • R 93 and R 94 independently of each other represent a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms
  • W 1 and W 2 are each independently a single bond
  • CR 95 R 96 R 95 and R 96 may be independently of each other a hydrogen atom or a branched structure having 1 to 10 carbon atoms.
  • R 97 is a hydrogen atom or Represents an alkyl group which may have a branched structure having 1 to 10 carbon atoms
  • X 1 and X 2 are each independently a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (14)
  • R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom
  • Y 1 and Y 2 each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms.
  • R 102 and R 104 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a polymerizable carbon-carbon double bond-containing group
  • R 103 represents a hydrogen atom
  • a photocurable resin composition for a microlens wherein R 102 and R 103 in the formula (A) are both hydrogen atoms, and R 104 is a polymerizable carbon-carbon double bond-containing group; 3. 1 or 2 photocurable resin composition for microlenses, wherein the reactive diluent is one or more selected from N-vinylformamide, 4-acryloylmorpholine, N-dimethylacrylamide, and N-diethylacrylamide. object, 4).
  • the photocurable resin composition for microlenses according to any one of 1 to 4 further comprising a crosslinking agent, 6).
  • the (meth) acrylic monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl acrylate, Octyl acrylate, isodecyl acrylate, 2-phenoxyethyl acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentadienyl (meth) ) Acry
  • 6 or 7 photocurable resin composition for microlens containing a photoradical initiator 9.
  • the photocurable resin composition for microlenses 6 to 8 is placed on a transparent substrate, a microlens-shaped mold is pressure-bonded thereon using a nanoimprinter, and then irradiated with light to form the composition.
  • Provided is a method of manufacturing a microlens characterized by curing.
  • the photocurable resin composition for a microlens of the present invention By using the photocurable resin composition for a microlens of the present invention, a microlens having a high refractive index and a low Abbe number can be obtained. Since this composition is a solvent-free and liquid composition containing a triazine ring-containing polymer having a predetermined molecular weight and a predetermined reactive diluent, it can be efficiently used in the optical nanoimprint method by using this composition. A microlens (array) can be produced.
  • the microlens obtained from the composition of the present invention can be suitably used as a lens for a digital camera, a video camera, a smartphone-mounted camera, or the like.
  • the photocurable resin composition for a microlens according to the present invention includes a triazine ring-containing polymer having a repeating unit structure represented by the formula (1) and having a weight average molecular weight of 500 to 7,000, and a formula (A). And a reactive diluent represented by the formula (1) without containing a solvent.
  • R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and are both hydrogen atoms from the viewpoint of further increasing the refractive index. It is preferable.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms in view of further improving the heat resistance of the polymer. Is even more preferable.
  • the structure may be any of a chain, a branch, and a ring.
  • alkyl group examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl.
  • N-pentyl 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2 , 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pe Til, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3- Dimethyl-n-butyl, 2,2-di
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms in view of further improving the heat resistance of the polymer. preferable.
  • the structure of the alkyl moiety may be any of a chain, a branch, and a ring.
  • alkoxy group examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n -Butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n -Hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy 3,3-dimethyl-n-butoxy, 1-ethoxy,
  • the number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 40. In view of further improving the heat resistance of the polymer, 6 to 16 carbon atoms are more preferable, and 6 to 13 are even more preferable. preferable.
  • aryl group examples include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, ⁇ -naphthyl, ⁇ -naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9-phenanthryl group and the like.
  • the number of carbon atoms of the aralkyl group is not particularly limited, but preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched or cyclic. Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, Examples include 4-isobutylphenylmethyl, ⁇ -naphthylmethyl group and the like.
  • Ar represents at least one selected from the group represented by formulas (2) to (13).
  • R 1 to R 92 are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group that may have a branched structure having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms.
  • R 93 and R 94 each independently represent a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms; 1 and W 2 are independently of each other, a single bond, CR 95 R 96 (R 95 and R 96 are each independently hydrogen atom or alkyl group which may have a branched structure having 1 to 10 carbon atoms Group (however, these may be combined to form a ring)), C ⁇ O, O, S, SO, SO 2 , or NR 97 (R 97 is a hydrogen atom or a carbon atom) Represents an alkyl group which may have a branched structure of formula 1-10. To express.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group and alkoxy group are the same as those described above.
  • X 1 and X 2 each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (14).
  • R 98 to R 101 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms.
  • An alkoxy group which may have a branched structure is represented, and Y 1 and Y 2 each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms.
  • Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
  • Examples of the alkylene group that may have a branched structure having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups.
  • R 1 to R 92 and R 98 to R 101 a hydrogen atom, a halogen atom, a sulfo group, an alkyl group which may have a branched structure having 1 to 5 carbon atoms, or a carbon number of 1 to The alkoxy group which may have 5 branched structures is preferable, and a hydrogen atom is more preferable.
  • Ar is preferably at least one of the formulas (2), (5) to (13), and the formulas (2), (5), (7), (8), (11) to (13) More preferably, at least one selected from Specific examples of the aryl group represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulae.
  • an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.
  • Ar is preferably an m-phenylene group represented by the formula (15).
  • the triazine ring-containing polymer of the present invention preferably has a repeating unit structure represented by the formula (16), and more preferably has a repeating unit structure represented by the formula (17).
  • a hyperbranched polymer (hyperbranched polymer) represented by the formula (18) is optimal.
  • the weight average molecular weight of the triazine ring-containing polymer represented by the formula (1) is 500 to 7 from the viewpoint of solubility in a reactive diluent and compatibility with a crosslinking agent used as necessary.
  • the upper limit is preferably 6,000 or less, and most preferably 5,000 or less.
  • 1,000 or more are preferable and 2,000 or more are more preferable from the point which improves heat resistance more and makes shrinkage
  • the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.
  • the triazine ring-containing polymer of the present invention can be produced according to a known method described in International Publication No. 2013/168787.
  • a hyperbranched polymer (hyperbranched polymer) having a repeating structure (21) is obtained by mixing cyanuric halide (19) and m-phenylenediamine compound (20) in a suitable organic solvent. It can obtain by making it react.
  • a hyperbranched polymer (hyperbranched polymer) having a repeating structure (21) is obtained by combining cyanuric halide (19) and m-phenylenediamine compound (20) in a suitable organic solvent. It can also be synthesized from the compound (22) obtained by reacting in an amount.
  • the amount of each raw material charged is arbitrary as long as the target polymer is obtained, but the diamino compound (20) 0. 01 to 10 equivalents are preferred.
  • the diamino compound (20) is used in an amount of less than 3 equivalents relative to 2 equivalents of cyanuric halide (19). Is preferred.
  • cyanuric halide (19) is used in an amount of less than 2 equivalents with respect to 3 equivalents of diamino compound (20). It is preferable.
  • the molecular weight of the resulting hyperbranched polymer (hyperbranched polymer) can be easily adjusted by appropriately adjusting the amounts of the diamino compound (20) and the cyanuric halide (19).
  • the concentration in an organic solvent As a method for adjusting the molecular weight of the hyperbranched polymer (hyperbranched polymer), it is possible to control the concentration in an organic solvent.
  • the reaction concentration solid content concentration
  • the reaction concentration solid content concentration
  • organic solvent various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, dimethyl sulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea.
  • N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixed system thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone are particularly preferable. Is preferred.
  • the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent used, and is preferably about 0 to 150 ° C., more preferably 60 to 100 ° C. preferable.
  • the reaction temperature is preferably 60 to 150 ° C., more preferably 80 to 150 ° C., and even more preferably 80 to 120 ° C. from the viewpoint of suppressing linearity and increasing the degree of branching.
  • the cyanuric halide (19) and the diamino compound (20) are preferably mixed at a low temperature. About 50 ° C.
  • the reaction temperature may be appropriately set in the range from the melting point of the solvent used to the boiling point of the solvent, but is preferably about ⁇ 50 to 50 ° C., and preferably about ⁇ 20 to 50 ° C. Is more preferably about ⁇ 10 to 50 ° C., and further preferably ⁇ 10 to 10 ° C.
  • it is preferable to employ a two-step process comprising a first step of reacting at ⁇ 50 to 50 ° C. and a second step of reacting at 60 to 150 ° C. following this step.
  • the order of blending the components is arbitrary, but in the reaction of Scheme 1, the solution containing cyanuric halide (19) or diamino compound (20) and an organic solvent is cooled, A method of adding a diamino compound (20) or a cyanuric halide (19) is preferred. In this case, the component previously dissolved in the solvent and the component added later may be either. However, in consideration of obtaining the above-mentioned polymer having the weight average molecular weight, the internal temperature is increased in the diamino compound (20) solution. A technique in which cyanuric halide (19) is dropped or charged while keeping at a low temperature is preferable. After mixing the two compounds, it is preferable to carry out the reaction at the above low temperature for about 0.5 to 3 hours, and then to polymerize by heating at 60 to 150 ° C. all at once.
  • a component previously dissolved in a solvent or a component added later may be used, but a method of adding a diamino compound (20) to a cooled solution of cyanuric halide (19) is preferable.
  • the addition may be gradually added by dropping or the like, or may be added all at once.
  • Components added later may be added neat or in a solution dissolved in an organic solvent as described above, but the latter method is preferred in view of ease of operation and ease of reaction control. It is.
  • this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxidized Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6 , 6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
  • the addition amount of the base is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents per 1 equivalent of cyanuric halide (19). These bases may be used as an aqueous solution. In any of the scheme methods, after completion of the reaction, the product can be easily purified by a reprecipitation method or the like.
  • a part of halogen atoms of at least one terminal triazine ring is substituted with alkyl, aralkyl, aryl, alkylamino, alkoxysilyl group-containing alkylamino, aralkylamino, arylamino, alkoxy, aralkyloxy, aryloxy.
  • alkylamino, alkoxysilyl group-containing alkylamino, aralkylamino, and arylamino groups are preferable, alkylamino and arylamino groups are more preferable, and arylamino groups are more preferable. Examples of the alkyl group and alkoxy group are the same as those described above.
  • ester group examples include methoxycarbonyl and ethoxycarbonyl groups.
  • aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, ⁇ -naphthyl, ⁇ -naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9-phenanthryl group and the like.
  • aralkyl group examples include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenyl.
  • examples include methyl, 4-isobutylphenylmethyl, ⁇ -naphthylmethyl group and the like.
  • alkylamino group examples include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, t-butylamino, n-pentylamino, 1-methyl- n-butylamino, 2-methyl-n-butylamino, 3-methyl-n-butylamino, 1,1-dimethyl-n-propylamino, 1,2-dimethyl-n-propylamino, 2,2-dimethyl -N-propylamino, 1-ethyl-n-propylamino, n-hexylamino, 1-methyl-n-pentylamino, 2-methyl-n-pentylamino, 3-methyl-n-pentylamino, 4-methyl -N-pentylamino, 1,1-dimethyl-n-butylamino, 1,2-
  • aralkylamino group examples include benzylamino, methoxycarbonylphenylmethylamino, ethoxycarbonylphenylmethylamino, p-methylphenylmethylamino, m-methylphenylmethylamino, o-ethylphenylmethylamino, m-ethylphenylmethyl.
  • arylamino group examples include phenylamino, methoxycarbonylphenylamino, ethoxycarbonylphenylamino, naphthylamino, methoxycarbonylnaphthylamino, ethoxycarbonylnaphthylamino, anthranylamino, pyrenylamino, biphenylamino, terphenylamino, fluorenyl An amino group etc. are mentioned.
  • the alkoxysilyl group-containing alkylamino group may be any of monoalkoxysilyl group-containing alkylamino, dialkoxysilyl group-containing alkylamino, trialkoxysilyl group-containing alkylamino group, and specific examples thereof include 3-trimethoxysilyl.
  • aryloxy group examples include phenoxy, naphthoxy, anthranyloxy, pyrenyloxy, biphenyloxy, terphenyloxy, and fluorenyloxy groups.
  • aralkyloxy group examples include benzyloxy, p-methylphenylmethyloxy, m-methylphenylmethyloxy, o-ethylphenylmethyloxy, m-ethylphenylmethyloxy, p-ethylphenylmethyloxy, 2-propyl Examples include phenylmethyloxy, 4-isopropylphenylmethyloxy, 4-isobutylphenylmethyloxy, ⁇ -naphthylmethyloxy groups and the like.
  • the organic monoamine is simultaneously charged, that is, by reacting the cyanuric halide compound with the diaminoaryl compound in the presence of the organic monoamine, the rigidity of the hyperbranched polymer is reduced, and the degree of branching is reduced.
  • a low soft hyperbranched polymer can be obtained.
  • the hyperbranched polymer obtained by this method has excellent solubility in a reactive diluent (aggregation suppression) and crosslinkability.
  • the organic monoamine any of alkyl monoamine, aralkyl monoamine, and aryl monoamine can be used as the organic monoamine.
  • Alkyl monoamines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, 1-methyl-n-butylamine, 2-methyl- n-butylamine, 3-methyl-n-butylamine, 1,1-dimethyl-n-propylamine, 1,2-dimethyl-n-propylamine, 2,2-dimethyl-n-propylamine, 1-ethyl-n -Propylamine, n-hexylamine, 1-methyl-n-pentylamine, 2-methyl-n-pentylamine, 3-methyl-n-pentylamine, 4-methyl-n-pentylamine, 1,1-dimethyl -N-butylamine, 1,2-dimethyl-n-butylamine, 1,3-dimethyl-n Butylamine, 2,
  • aralkyl monoamine examples include benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylphenylbenzyl, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine and the like.
  • aryl monoamine examples include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o- And phenylaniline, 4-amino-p-terphenyl, 2-aminofluorene, and the like.
  • the amount of the organic monoamine used is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, and even more preferably 0.05 to 50 equivalents based on the halogenated cyanuric compound.
  • the reaction temperature is preferably 60 to 150 ° C., more preferably 80 to 150 ° C., and still more preferably 80 to 120 ° C. from the viewpoint of suppressing linearity and increasing the degree of branching.
  • the mixing of the three components of the organic monoamine, the halogenated cyanuric compound, and the diaminoaryl compound is preferably performed at the above-described low temperature. It is preferable to carry out the reaction at an elevated temperature.
  • the organic monoamine is added at the low temperature, and the reaction is performed at a stretch (in one step) to the polymerization temperature. May be performed.
  • R 102 and R 104 are independently of each other a hydrogen atom, an alkyl group optionally having a branched structure having 1 to 10 carbon atoms, or polymerization.
  • sexual carbon - represents a carbon-carbon double bond-containing group
  • R 103 is a hydrogen atom, or represents an alkyl group which may have a branched structure of 1 to 10 carbon atoms
  • R 102 and R Any one of 104 is a polymerizable carbon-carbon double bond-containing group, and both R 102 and R 104 are not simultaneously a polymerizable carbon-carbon double bond-containing group.
  • R 102 is preferably a hydrogen atom or a methyl group
  • R 103 is preferably a hydrogen atom from the viewpoint of ensuring the ability to form a hydrogen bond with a triazine ring-containing polymer.
  • alkyl group which may have a branched structure having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and n-pentyl.
  • the polymerizable carbon-carbon double bond-containing group is not particularly limited, but a carbon-carbon double bond-containing hydrocarbon group (alkenyl group) having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms.
  • ethenyl vinyl
  • n-1-propenyl n-2-propenyl
  • allyl group 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl
  • the reactive diluent represented by the formula (A) include N-vinylformamide, N-vinylacetamide, N-allylformamide, N-allylacetamide, 4-acryloylmorpholine, (meth) acrylamide, N-methyl (Meth) acrylamide, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, etc.
  • N-vinylformamide, 4-acryloylmorpholine, N-dimethylacrylamide, and N-diethylacrylamide are preferred.
  • the amount of the reactive diluent represented by the formula (A) is not particularly limited, and is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Considering the degree of improvement, the lower limit is preferably 5 parts by mass, more preferably 10 parts by mass, and the upper limit is preferably 150 parts by mass, more preferably 100 parts by mass.
  • the photocurable resin composition for microlenses of this invention contains the triazine ring containing polymer shown by Formula (1), and the reactive diluent shown by Formula (A), these two components
  • other additives such as a crosslinking agent, a leveling agent, a surfactant, and a silane coupling agent may be included.
  • the cross-linking agent is not particularly limited, and can be appropriately selected from known photo-curing cross-linking agents.
  • the triazine ring-containing polymer used in the composition of the present invention is, in particular, allyl. It is preferable to use these monomers as a crosslinking agent since they are excellent in compatibility with a monomer and a (meth) acrylic monomer / oligomer.
  • Specific examples of the allylic monomer include triallyl cyanurate and triallyl isocyanurate.
  • (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (methyl) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl Acrylate, isooctyl acrylate, isodecyl acrylate, 2-phenoxyethyl acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentadi Enil (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, capro Click ton acrylate, morpholine (meth)
  • Examples of commercially available (meth) acrylic monomers include EBECRYL (registered trademark) 80, 436, 438, 446, 450, 505, 524, 525, 770, 800, 810, 811, 812, 830, 846, 851, 852, 853, 1870, 884, 885, 600, 605, 645, 648, 860, 1606, 3500, 3608, 3700, 3701, 3702, 3703, 3708, 6040, 303, 767 (Daicel Cytec Co., Ltd.) NK Ester A-200, A-400, A-600, A-1000, A-9300 (Tris (2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-DPH A-TMPT, A-DCP, A-HD-N, UA-53H, G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE
  • Urethane acrylate is a compound having one or more polymerizable unsaturated bonds and two or more urethane bonds, and is also available as a commercial product. Specific examples thereof include the trade name Beam Set (registered trademark). 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90, EM-92 (manufactured by Arakawa Chemical Industries, Ltd.); trade name Photomer (registered trademark) 6008, 6210 (San Nopco) Product name: NK Oligo U-2PPA, U-4HA, U-6HA, U-15HA, UA-32P, U-324A, U-4H, U-6H, UA-160TM (2-hydroxyethyl acrylate, isophorone) Reaction product of diisocyanate and polytetramethylene glycol), UA-122P, UA-2235PE, UA-340P UA-5201, UA-512 (manufactured by Shin-
  • the use ratio of the photocurable resin composition for microlenses and the crosslinking agent is particularly limited as long as the triazine ring-containing polymer and the crosslinking agent are compatible in the composition and a uniform solution can be prepared.
  • the triazine ring-containing polymer: crosslinking agent can be about 1:10 to 10: 1 by mass ratio.
  • 7 to 7: 1 is preferred, 1: 5 to 5: 1 is more preferred, and 1: 3 to 3: 1 is even more preferred.
  • radical photopolymerization initiator may be appropriately selected from known ones, such as acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime esters, oxime esters, tetramethylthiuram monosulfide, and thioxanthones. Is mentioned.
  • photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, Inc., published in 1991).
  • radical photopolymerization initiators examples include BASF Corporation trade names: Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850. , CG24-61, OXE01, OXE02, Darocur 1116, 1173, MBF, manufactured by BASF, Inc.
  • Product name Lucirin TPO, manufactured by UCB, Inc.
  • radical photopolymerization initiator When a radical photopolymerization initiator is used, it is preferably used in the range of 0.1 to 200 parts by weight, preferably in the range of 1 to 150 parts by weight, with respect to 100 parts by weight of the (meth) acrylic monomer. More preferred.
  • surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol Polyoxyethylene alkyl allyl ethers such as ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethyleneso Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name
  • surfactants may be used alone or in combination of two or more.
  • the amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Even more preferred.
  • the photocurable resin composition for a microlens of the present invention can be easily and efficiently formed into a microlens array by an optical nanoimprint method. Specifically, the composition of the present invention is placed on a transparent substrate, and after a microlens-shaped mold is pressure-bonded thereon using a nanoimprinter, the composition is cured by irradiation with light to form a microlens array. It can be. A microlens is obtained by appropriately cutting the obtained microlens array.
  • the method of placing the composition on the substrate is arbitrary, for example, spin coating method, flow coating method, ink jet method, jet dispenser method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer Methods such as printing, brush coating, blade coating, and air knife coating can be employed.
  • examples of the transparent substrate include base materials made of polyethylene terephthalate (PET), plastic, glass, quartz, ceramics, and the like.
  • the material of the mold used for molding is not particularly limited, but silicone resin is suitable.
  • Conditions for the light irradiation are not particularly limited, and an appropriate irradiation energy and time may be adopted depending on the triazine ring-containing polymer and the crosslinking agent to be used.
  • microlens of the present invention obtained as described above is not only excellent in transparency but also has a high refractive index and a low Abbe number, such as a digital camera, a video camera, a smartphone-mounted camera, etc. It can be suitably used as a lens.
  • Refractive index (thin film) Apparatus Multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan (4) Refractive index (thick film) and Abbe number Apparatus: Metricon 2010 / M prism coupler manufactured by Metricon (5) Differential thermal balance (TG-DTA) Equipment: TG-8120, manufactured by Rigaku Corporation Temperature increase rate: 10 ° C / min Measurement temperature: 20-500 ° C (6) DSC Device: DSC 204F1 Phoenix made by NETZSCH Temperature increase rate: 30 ° C / min Measurement temperature: 25-300 ° C (7) Nanoimprinter Device: Myeongchang Kiko Co., Ltd. NM-0801HB Lamp: Toshiba Corporation short arc mercury lamp
  • 1,3-phenylenediamine [1] (8.80 g, 81.3 mmol, manufactured by Aminochem), aniline (2.53 g, 27.1 mmol, manufactured by Junsei Chemical Co., Ltd.), N, N-dimethylacetamide (288.0 g, manufactured by Junsei Chemical Co., Ltd., hereinafter referred to as DMAc) was charged and cooled to ⁇ 15 ° C.
  • aniline (26.9 g, 288.5 mmol, manufactured by Junsei Chemical Co., Ltd.) was added and stirred for 3 hours to complete the reaction.
  • the reaction solution was reprecipitated into a mixed solution of 28% aqueous ammonia (65.9 g) and ion-exchanged water (1000 g).
  • the precipitate was filtered to obtain a polymer wet product.
  • the obtained polymer wet product was redissolved in a mixed solution of tetrahydrofuran (280 g, THF hereinafter) and 28% aqueous ammonia solution (65.9 g), stirred for 30 minutes, and then heated to 40 ° C. for liquid separation. .
  • HB-TmDAL-T The weight average molecular weight Mw measured in terms of polystyrene by GPC of HB-TmDAL-T was 3330, and the polydispersity Mw / Mn was 2.68.
  • the solute was completely dissolved to obtain a polymer varnish having a solid content of 20% by mass as a light yellow transparent solution.
  • the polymer varnish was spin-coated on a quartz substrate using a spin coater at 1000 rpm (30 seconds), and baked on a hot plate at 130 ° C. for 3 minutes in the air to obtain a thin film.
  • the refractive index of the thin film was 1.764 at a wavelength of 550 nm, indicating that it was a high refractive index material.
  • HB-TmDA target polymer compound [3]
  • the weight average molecular weight Mw measured in terms of polystyrene by GPC of HB-TmDA was 10200, and the polydispersity Mw / Mn was 6.5.
  • Tg glass transition temperature
  • Td 5% 5% weight loss temperature
  • Examples 1-2 and 1-3 A photocurable resin composition for each microlens was obtained in the same manner as in Example 1-1 except that the mass ratio of 40% by mass of varnish to IBXA was 5: 5 and 8: 2, respectively. .
  • Example 2-2 Under air, to the 10 mL sample bottle was added 5.0000 g of the triazine-based hyperbranched polymer HB-TmDAL-T obtained in Synthesis Example 1, and 4.0000 g of NVF and 4-acryloylmorpholine (hereinafter referred to as ACMO) as reactive diluents. 1.0000 g was added, and the mixture was stirred at room temperature using a mix rotor (110 rpm) until the polymer was completely dissolved and the solution was uniform. After stirring, a varnish containing 50% by mass of a triazine hyperbranched polymer was obtained as a light yellow transparent solution in which the polymer was completely dissolved.
  • ACMO 4-acryloylmorpholine
  • TN50-8UX and HB-TmDAL-TNA50 obtained in Examples 2-1 and 2-2 were spin-coated on a quartz substrate using a spin coater at 2000 rpm (30 seconds), and then Under nitrogen, UV curing was performed at an integrated light quantity of 1000 mJ / cm 2 to obtain a highly branched polymer thin film.
  • the refractive index and Abbe number of the thin film obtained above were measured with a prism coupler.
  • the refractive index at a wavelength of 550 nm was 1.6259 for TN50-8UX and 1.6428 for TNA50, both showing refractive indices exceeding 1.6.
  • the Abbe number was 22.2 for TN50-8UX and 19.6 for TNA50, both of which were low Abbe numbers.
  • microlens array 0.0100 g of each of TN50-8UX and HB-TmDAL-TNA50 prepared in Examples 2-1 and 2-2 was placed on a glass substrate, and a microlens-shaped silicon mold (( Kyodo International Co., Ltd. lens size: ⁇ 40 ⁇ m ⁇ depth 16.5 ⁇ m) was pressure-bonded at a pressure of 150 N. Thereafter, UV exposure was performed from the glass surface at 4 mW / cm 2 (detection of 365 nm) for 250 seconds to cure. After curing, the mold was peeled off to obtain a microlens array formed on the glass substrate. SEM observation of the obtained microlens array confirmed that the lens shape was clearly transferred as shown in FIGS.
  • a varnish (HB-TmDAL-TD50) containing 50% by mass of a triazine-based hyperbranched polymer was obtained as a light yellow transparent solution in which the polymer was completely dissolved.
  • TAC triallyl cyanurate
  • mass ratio 4: 1 was added to 4.0000 g of the varnish of 50% by mass
  • Irgacure-2959 manufactured by BASF
  • 0.25g (50 mass% varnish and TAC were 100 mass parts, and 5.00 mass parts is added to this).
  • Example 3-2 1.0000 g (mass ratio 4: 1) of NK ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to 4.0000 g of the varnish (HB-TmDAL-TD50) 50 mass% prepared in Example 3-1.
  • 0.25 g of Irgacure-2959 (manufactured by BASF) (100 parts by mass of 50% by mass varnish and A-DCP, with respect to 5.00 parts by mass) was added as a radical photopolymerization initiator. These were stirred until the solute was completely dissolved and the solution was uniform to obtain a photocurable resin composition for microlenses (TD50-DCP).
  • Example 3-3 1.0000 g (mass ratio 4: 1) of NK ester A-LEN-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.) to 4.0000 g of 50% by mass of varnish (HB-TmDAL-TD50) prepared in Example 3-1. ) And 0.25 g of Irgacure-2959 (manufactured by BASF) as a radical photopolymerization initiator (100 parts by mass of 50 mass% varnish and A-LEN-10, 5.00 parts by mass with respect to this) added. These were stirred until the solute was completely dissolved and the solution was uniform to obtain a photocurable resin composition for microlenses (TD50-LEN).
  • Example 3-4 1.4000 g of IBXA (mass ratio 4: 1) was added to 4.0000 g of 50% by mass of varnish (HB-TmDAL-TD50) prepared in Example 3-1, and Irgacure-2959 (BASF Corporation) was further used as a photoradical polymerization initiator. 0.25 g (50% by mass of varnish and IBXA as 100 parts by mass, with respect to 5.00 parts by mass) was added. These were stirred until the solute was completely dissolved and the solution was uniform to obtain a photocurable resin composition for microlenses (TD50-IB).
  • Example 3-5 1.0000 g (mass ratio 4: 1) of adamantyl acrylate (M-104, manufactured by Idemitsu Kosan Co., Ltd.) was added to 4.0000 g of the 50% by mass of varnish (HB-TmDAL-TD50) prepared in Example 3-1. Further, 0.25 g of Irgacure-2959 (manufactured by BASF) (50 mass% varnish and M-104 as 100 mass parts, 5.00 mass parts relative to this) was added as a radical photopolymerization initiator. These were stirred until the solute was completely dissolved and the solution was uniform to obtain a photocurable resin composition for microlenses (TD50-104).
  • M-104 mass ratio 4: 1

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Abstract

L'invention concerne une microlentille ayant un indice de réfraction élevé et un faible nombre d'Abbe, qui est apte à être produite par un procédé de nano-impression optique en utilisant, par exemple, une composition de résine photodurcissable pour microlentilles, qui contient un polymère contenant un cycle triazine comprenant une structure d'unité de répétition représentée par la formule (3) et ayant un poids moléculaire moyen en poids de 500 à 5000 et un diluant réactif tel que le N-vinylformamide, et qui ne contient pas de solvant.
PCT/JP2016/081829 2015-11-04 2016-10-27 Composition de résine photodurcissable pour microlentilles WO2017077932A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009012319A (ja) * 2007-07-05 2009-01-22 Dainippon Printing Co Ltd パターン形成体の製造方法
WO2012111682A1 (fr) * 2011-02-15 2012-08-23 日産化学工業株式会社 Composition filmogène photodurcissable et procédé de fabrication de film durci
WO2013168787A1 (fr) * 2012-05-11 2013-11-14 日産化学工業株式会社 Composition filmogène et matériau d'enrobement
WO2014136871A1 (fr) * 2013-03-08 2014-09-12 日産化学工業株式会社 Composition filmogène

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009012319A (ja) * 2007-07-05 2009-01-22 Dainippon Printing Co Ltd パターン形成体の製造方法
WO2012111682A1 (fr) * 2011-02-15 2012-08-23 日産化学工業株式会社 Composition filmogène photodurcissable et procédé de fabrication de film durci
WO2013168787A1 (fr) * 2012-05-11 2013-11-14 日産化学工業株式会社 Composition filmogène et matériau d'enrobement
WO2014136871A1 (fr) * 2013-03-08 2014-09-12 日産化学工業株式会社 Composition filmogène

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