WO2014065517A1 - Composition de résine durcissante et film optique fabriqué avec cette composition - Google Patents

Composition de résine durcissante et film optique fabriqué avec cette composition Download PDF

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Publication number
WO2014065517A1
WO2014065517A1 PCT/KR2013/008783 KR2013008783W WO2014065517A1 WO 2014065517 A1 WO2014065517 A1 WO 2014065517A1 KR 2013008783 W KR2013008783 W KR 2013008783W WO 2014065517 A1 WO2014065517 A1 WO 2014065517A1
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group
carbon atoms
formula
resin composition
monomer
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PCT/KR2013/008783
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English (en)
Korean (ko)
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송병훈
권태창
김은영
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동우화인켐 주식회사
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Publication of WO2014065517A1 publication Critical patent/WO2014065517A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/105—Esters of polyhydric alcohols or polyhydric phenols of pentaalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • 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
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements

Definitions

  • the present invention relates to a curable resin composition and an optical film produced using the same. More specifically, the present invention relates to a curable resin composition capable of photocuring and thermosetting, which can produce a resin layer having low energy consumption and excellent interlayer adhesion, and an optical film manufactured using the same.
  • optical films such as a polarizing film and a retarder, are used for the various image display apparatuses currently used.
  • Such an optical film is formed by stacking a plurality of thin films.
  • a retarder is normally formed by laminating
  • a base film the transparent film formed from TAC, COP, etc. is used, but the use of the base film which uses PMMA is increasing in recent years.
  • the filler when the filler is applied during the manufacturing process of the base film and the retarder, such a filler may be driven to the surface of the base film.
  • the surface roughness of the base film may increase.
  • the adhesive force between the base film and the alignment film is lowered, or the flatness of the cured liquid crystal layer is lowered on the alignment film, thereby degrading the function as a retarder. Penetration problems will occur.
  • An object of the present invention is to provide a curable resin composition capable of forming a resin layer having excellent interlayer adhesion.
  • an object of the present invention is to provide a curable resin composition capable of both photocuring and thermal curing to reduce energy during the manufacturing process.
  • an object of this invention is to provide the optical film provided with the resin layer formed from the said curable resin composition.
  • a photopolymerization initiator having at least two photoactive oxime ester backbones in one molecule;
  • Polyfunctional second monomer having a hydroxy group or a carboxy group;
  • an organic solvent
  • R 1 , R 2 and R 3 independently of one another represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN,
  • R 4 and R 5 are each independently R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , CN Represents a halogen atom or a hydroxy group,
  • a and b are each independently an integer of 0 to 3
  • R 11 , R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms
  • R 21 , R 22 and R 23 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms Indicates,
  • the methylene group of the alkylene moiety of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 is an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane It may be interrupted 1 to 5 times by a bond, the alkyl moiety of the substituent may have a branched chain, a cyclic alkyl, the alkyl terminal of the substituent may be an unsaturated bond, and R 12 , R 13 and R 22 and R 23 may each form a ring together, and R 3 may form a ring together with an adjacent benzene ring.)
  • R 1 to R 5 are as defined in 2 above.
  • the first monomer capable of photocuring and thermosetting including the isocyanate group and the (meth) acrylate group at its terminals is one or more selected from the group consisting of compounds of the formula Curable Resin Composition:
  • R 1 and R 2 are each independently hydrogen or a methyl group
  • R 3 and R 7 are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,
  • R 4 and R 6 are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of an amide group, a ketone group, an ester group and a thiol group,
  • R 5 is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 8 carbon atoms,
  • R 7 and R 8 are each independently hydrogen or a methyl group
  • R 9 and R 11 are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,
  • R 10 is (a) Or (b) E 1 and E 3 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and E 2 is an alkoxy group having 1 to 8 carbon atoms. Substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
  • R 12 is hydrogen or a methyl group
  • R 13 is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group;
  • R 14 is hydrogen or a methyl group
  • R 15 is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group.
  • R 1 , R 2 , R 3 and R 4 is hydrogen or a carboxy group and the rest are independently selected from methyl or acryloyl groups, and A is , , , , or Is a integer of 1 to 3, b is an integer of 0 to 12).
  • the second monomer is a polystyrene reduced weight average molecular weight of 200 to 3,000 curable resin composition.
  • SP SUB is SP value of a base film
  • SP SOL is SP value of a solvent.
  • the base film is an optical film formed including the PMMA resin.
  • Image display device having the optical film of the above 10.
  • the curable resin composition of the present invention is excellent in interlayer adhesion, and in particular, when a reactive group having a carbon double bond is left in the adjacent film, it may also form a chemical bond therewith.
  • the curable resin composition of the present invention is capable of both photocuring and thermosetting, it is possible to advance the thermal curing during the drying process after applying the curable resin composition, and thus only the uncured portion after the drying process photocured Since it is possible to cure with only a low exposure amount can be saved energy.
  • the curable resin composition of the present invention when applied to a retarder using PMMA as the base film, when used as a resin layer between the alignment film and the base film, the surface of the base film becomes flat, so that the alignment film can be thickly formed. There is no need.
  • the present invention provides a photopolymerization initiator comprising a compound having at least two photoactive oxime ester skeletons in one molecule;
  • it comprises an organic solvent, excellent in interlayer adhesion, and a curable resin composition capable of photocuring and thermosetting, and relates to an optical film produced using the same.
  • Curable resin composition of this invention is a photoinitiator; A first monomer capable of photocuring and thermosetting; And polyfunctional second monomers.
  • the curable resin composition of the present invention comprises a photopolymerization initiator comprising a compound having at least two photoactive oxime ester skeletons in one molecule; A first monomer capable of photocuring and thermosetting by including an isocyanate group and a (meth) acrylate group at its terminals; And a polyfunctional second monomer having a hydroxy group or a carboxy group.
  • the photopolymerization initiator of the present invention includes a compound having two or more photoactive oxime esters skeleton in one molecule. Having two or more photoactive oxime ester skeletons in one molecule results in excellent polymerization initiation efficiency since two radicals are generated from one compound at the start of the polymerization reaction.
  • the compound having two or more photoactive oxime ester skeletons in one molecule is dimerized through R 1 or R 2 .
  • R 1 , R 2 and R 3 independently of one another represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN,
  • R 4 and R 5 are each independently R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , CN Represents a halogen atom or a hydroxy group,
  • a and b are each independently an integer of 0 to 3.
  • R 11 , R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms
  • R 21 , R 22 and R 23 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms Indicates,
  • the methylene group of the alkylene moiety of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 is an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane It may be interrupted 1 to 5 times by a bond, the alkyl moiety of the substituent may have a branched chain, a cyclic alkyl, the alkyl terminal of the substituent may be an unsaturated bond, and R 12 , R 13 and R 22 and R 23 may each form a ring together, and R 3 may form a ring together with an adjacent benzene ring.)
  • aryl group represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 for example, phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, And phenyl, biphenylyl, naphthyl, anthryl and the like substituted with one or more of the above alkyl groups.
  • Examples of the arylalkyl group represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 include benzyl, chlorobenzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and phenylethenyl Etc. can be mentioned.
  • heterocyclic group represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazole- 2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidil, pyrazolidyl, thiazolidyl, isothiazolidil, oxazolidyl, isoxazolidyl, piperidyl, piperazil, morpholinyl 5-7 membered heterocycles, such as these, are illustrated preferably.
  • ring which may be formed with a ring of benzene which R 12 and R 13 rings, which can be formed with R 22 and R 23 the ring, and R 3 which can form with the adjacent, for example, a cyclopentyl bullet, 5-7 membered rings, such as a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring, are mentioned.
  • Examples of the halogen atom that may be substituted for R 11 , R 12 , R 13 , R 21 , R 22 and R 23 and the halogen atom represented by R 4 , R 5 include fluorine, chlorine, bromine and iodine.
  • the methylene group of the alkylene moiety of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and at this time, one or more bond groups are interrupted Two or more types of contribution may also be sufficient, and when it is the group which can be interrupted continuously, you may interrupt 2 or more consecutively.
  • the alkyl part of the said substituent may have a branched side chain, cyclic alkyl may be sufficient, and the alkyl terminal of the said substituent may be an unsaturated bond.
  • R 1 is an alkyl group having 11 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and a complex having 2 to 20 carbon atoms.
  • R 3 is an alkyl group having 1 to 12 carbon atoms interrupted 1 to 5 times by ether or ester bond, 13 to 20 carbon atoms
  • the methylene group of the moiety is a branched alkyl group having 8 or more carbon atoms which may be interrupted 1 to 5 times by an ether bond or ester bond;
  • the methylene group of the alkylene portion of the alkyl group is an alkyl group of 13 or more small atoms which may be interrupted 1 to 5 times by an ether bond or ester bond;
  • R 3 is an alkyl group interrupted 1 to 5 times by an ether bond; It is
  • the compound represented by Chemical Formula 1 is preferably dimerized through R 1 or R 2 .
  • R 1 to R 5 are as defined in Formula 1 above.
  • Preferred specific examples of the oxime ester compound of the present invention represented by Formula 1 include, but are not limited to, the compounds of Formulas 4 to 10 shown below.
  • the photopolymerization initiator having two or more photoactive oxime ester skeletons in one molecule may be included in an amount of 0.1 to 40% by weight based on the total weight of the curable resin composition of the present invention. Preferably, it may be included in an amount of 1 to 30% by weight. When included in the above content range, it exhibits high sensitivity to light, and thus the polymerization reaction proceeds sufficiently even at a low exposure amount, so that the interlayer adhesion is excellent.
  • the photopolymerization initiator contained in the curable resin composition of the present invention includes, but is not limited to, a triazine-based compound, an acetophenone-based compound, a biimidazole-based compound, and an oxime compound, in addition to the compound having two or more photoactive oxime ester skeletons in one molecule.
  • One or more compounds selected from the group can be used together.
  • Curable resin composition containing the said photoinitiator is highly sensitive, and the film
  • triazine type compound it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethyla
  • acetophenone type compound for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- ( 2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] And oligomers of propane-1-one.
  • R 1 to R 4 are independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms.
  • the naphthyl group which may be substituted by the benzyl group or C1-C12 alkyl group which may be substituted by this is shown.
  • Specific examples of the compound represented by Formula 12 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-die
  • biimidazole compound 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole or a phenyl group at the 4,4', 5,5 'position
  • 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.
  • Examples of the oxime compound include 0-ethoxycarbonyl- ⁇ -oxyimino-1-phenylpropan-1-one and the compounds represented by the following formulas (13) to (15).
  • photoinitiator etc. which are normally used in this field can also be used together, without departing from the scope of the present invention.
  • a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.
  • benzoin type compound benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.
  • benzophenone type compound for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.
  • thioxanthone type compound 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.
  • anthracene-based compound examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.
  • curable resin composition containing these is more sensitive and productivity at the time of forming a resin layer using this composition is preferable, it is preferable.
  • an amine compound and a carboxylic acid compound are preferably used.
  • amine compound in the photopolymerization initiation aid examples include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanol amine, 4-dimethylaminobenzoate methyl, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid, and pediatric wheat.
  • carboxylic acid compound examples include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethyl phenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.
  • the content of the photopolymerization initiation aid may be usually 0.1 to 40% by weight based on the total weight of the curable resin composition. Preferably it may be included in 0.5 to 30% by weight.
  • the content of the photopolymerization initiation aid is in the above range, the sensitivity of the curable resin composition is higher, and thus the formation of the resin layer formed by using the composition is preferable.
  • the first monomer according to the present invention is characterized by including an isocyanate group and a (meth) acrylate group at its terminals to enable photocuring and thermosetting.
  • the (meth) acrylate group participates in the photocuring reaction
  • the isocyanate group participates in the thermosetting reaction.
  • (Meth) acrylate groups react with carbon-carbon double bonds of other molecules to form carbon-carbon saturated bonds
  • isocyanate groups react with hydroxyl or carboxyl groups of the second monomer to form urethane bonds.
  • the isocyanate group of the first monomer is reacted with a hydroxyl group or a carboxyl group at a temperature of about 80 to 130 ° C., which is the temperature of a typical drying step carried out in the process of producing an optical film (thermosetting).
  • the first monomer is crosslinked with the second monomer, the hardness and the adhesion of the resin layer can be enhanced.
  • the (meth) acrylate group of the first monomer reacts with the unreacted carbon-carbon unsaturated bond reactive group remaining on the surface of the PMMA when the base film to which the resin layer is in contact is made of PMMA to form a carbon-carbon saturated bond. It may be formed. In this case, the resin layer and the base film may be connected by chemical bonding to have a stronger interlayer adhesion.
  • Examples of the first monomer according to the present invention include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 16 to 19.
  • R 1 and R 2 are each independently hydrogen or a methyl group
  • R 3 and R 7 are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,
  • R 4 and R 6 are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of an amide group, a ketone group, an ester group and a thiol group,
  • R 5 is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 8 carbon atoms,
  • R 7 and R 8 are each independently hydrogen or a methyl group
  • R 9 and R 11 are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group,
  • R 10 is (a) Or (b) E 1 and E 3 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and E 2 is an alkoxy group having 1 to 8 carbon atoms. Substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
  • R 12 is hydrogen or a methyl group
  • R 13 is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group;
  • R 14 is hydrogen or a methyl group
  • R 15 is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with a group selected from the group consisting of a ketone group, an ester group and a thiol group.
  • the first monomer represented by the above formulas (16) to (19) is at least one of the compounds represented by the formulas (17) to (19) and the compound represented by the formula (16) in order to ensure better interlayer adhesion It can be used as a mixture of.
  • More specific examples of the first monomer of Formula 16 to Formula 19 may include at least one selected from the group consisting of compounds represented by Formula 20 to Formula 30:
  • the first monomer according to the present invention is preferably included in 5 to 90% by weight, preferably 10 to 70% by weight relative to the total weight of the composition. It is possible to secure sufficient adhesive strength in the above range, when excessively added, the adhesive strength is improved, but when applied to the optical film, other physical properties may be lowered.
  • composition for forming a curable resin layer of the present invention may further include a thermal polymerization initiator to promote thermal curing.
  • the thermal polymerization initiator usable in the present invention can be used without particular limitation as long as it is used in the art.
  • the second monomer according to the invention is characterized in that the polyfunctional monomer having a hydroxy group or a carboxyl group. As described above, the second monomer performs a crosslinking reaction through a hydroxy group or a carboxyl group, and, if necessary, also has a carbon-carbon unsaturated bond as a functional group, and may also perform a polymerization reaction.
  • R 1 , R 2 , R 3 and R 4 is hydrogen or a carboxy group and the rest are independently selected from methyl or acryloyl groups, and A is , , , , or Is a integer of 1 to 3, b is an integer of 0 to 12).
  • More specific examples of the compound represented by Chemical Formula 31 may include a compound represented by Chemical Formula 32 to Chemical Formula 39, but are not limited thereto.
  • the weight average molecular weight of polystyrene conversion of the 2nd monomer which concerns on this invention is 200-3,000, More preferably, it may be 500-1,000. If the weight average molecular weight of the second monomer exceeds 3,000, the dispersibility may be reduced, or the brightness of the optical film may be lowered because a stable dispersion is not obtained. If the molecular weight is less than 200, the brightness of the optical film may be lowered.
  • the second monomer according to the invention is preferably included in 5 to 60% by weight relative to the total weight of the composition. If the content is less than 5% by weight, the degree of curing may be lowered, and if it is more than 60% by weight, it may be detrimental to heat curing.
  • Curable resin composition of this invention contains the organic solvent which can melt
  • the organic solvent maintains the dissolution and proper viscosity of the components so that the composition exhibits the desired coating properties, processability, and the like.
  • organic solvent examples include a component capable of dissolving the above components, but preferably a solvent containing an oxygen atom, a solvent having an SP DS value of 1 or less and a solvent of 15 or more, represented by Equation 1 below. It is preferable to use a mixed solvent of
  • the degree of miscibility and corrosion between the solvent used in the curable composition and the base film to which the curable composition is applied can be known by correlation of the solubility parameter (SP) of the solvent and the base film.
  • SP solubility parameter
  • a solvent having an SP DS value of 1 or less represented by Equation 1 may corrode the surface of the base film to a predetermined amount or more.
  • the rainbow phenomenon may be prevented due to the occurrence of irregularities between the interfaces, and adhesion, coating property, and the like may be improved.
  • the degree of corrosion is large and the unevenness between the interfaces is too large, the haze value may increase, or whitening may occur, and mechanical properties, in particular, film strength and flex resistance may be reduced.
  • the SP of the base film and the solvent may use values known in the art, for example, the values set forth in VII / 671-VII / 714 of the Polymer Handbook (4th Ed. J. Brandrup et al.). Can be used.
  • SP can be defined as ( ⁇ H / V) 1/2, ⁇ H is the molar evaporation enthalpy, and V is the molar volume.
  • solvent that can be used include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl a
  • the organic solvent in the present invention may be included as the balance of the content of the components based on 100% by weight of the total weight of the composition in order to maintain an appropriate viscosity.
  • Curable resin composition of this invention may further contain additives, such as a filler, a hardening
  • additives such as a filler, a hardening
  • Curable resin composition of the present invention containing the above components are used in the optical film to improve the interlayer adhesion, in particular can be useful for the surface planarization of the film is not flat surface.
  • a resin layer is formed between the PMMA substrate and the alignment film to cover the irregularities on the surface of the PMMA substrate by the polymer beads, thereby securing flatness and ensuring the PMMA substrate and the alignment film. Adhesion between can be strengthened.
  • the retarder has a structure in which a base film, a resin layer formed of the composition of the present invention, an alignment film, and a cured liquid crystal layer are sequentially stacked, which will be described in detail below.
  • the base film according to the present invention can be used without particular limitation the base film commonly used in the art.
  • a transparent film is generally used as the base film in the art, and is, for example, a film including a triacetyl cellulose (TAC), a cyclo-olefin polymer (COP), a poly (methyl methacrylate) polymer, or the like.
  • the base film may be surface treated such as safonification treatment, remote plasma treatment, direct plasma treatment, monomer plasma treatment, or the like.
  • PMMA type base film it is preferable to disperse
  • the alignment film according to the present invention may be formed of a composition for forming an alignment film including an alignment agent, a polymerization initiator, and an organic solvent commonly used in the art.
  • an alignment agent an alignment agent conventionally used in the art may be used without particular limitation.
  • a polymer having a cinnamate group and having a weight average molecular weight of about 10,000-500,000 may be used, but is not limited thereto.
  • the polymerization initiator a photopolymerization initiator or a thermal polymerization initiator commonly used in the art may be used.
  • the photopolymerization initiator the photopolymerization initiators exemplified above may be used.
  • An organic solvent may also be appropriately selected from among the organic solvents exemplified above.
  • the cured liquid crystal layer according to the present invention may be prepared by curing a composition comprising a liquid crystal compound, a polymerization initiator, and an organic solvent having a polymerizable functional group at the terminal, and as a polymerization initiator, a photopolymerization initiator commonly used in the art or A thermal polymerization initiator may be used, and the photopolymerization initiator exemplified above may be used as the photopolymerization initiator.
  • An organic solvent may also be appropriately selected from among the organic solvents exemplified above.
  • a curable resin composition was prepared by mixing a photopolymerization initiator, a first monomer, a second monomer, a leveling agent, and an organic solvent in the composition shown in Table 1 below (unit: g).
  • Example 1-6 and Comparative Examples 1-5 were applied to the PMMA film, dried at 100 ° C. for 30 seconds, and then exposed to 30 mJ, respectively, to form a resin layer. After apply
  • RMS curable liquid crystal composition
  • the retarder of the embodiments provided with a cured layer according to the present invention can be confirmed that the overall excellent in terms of curing degree, surface roughness and interlayer adhesion of the resin layer compared to the retarder of the comparative examples.
  • Example 1 since the photopolymerization initiator has a dimerized structure, the photoactive site is twice as large as that in the conventional case, and it can be confirmed that other components are more excellent in curing degree than Example 2, which was used in the same manner.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Cette invention concerne une composition de résine durcissante et un film optique fabriqué avec cette composition, ladite composition de résine durcissante comprenant : un initiateur de photopolymérisation comprenant un composé ayant au moins deux structures d'ester d'oxime photoactif par molécule ; un premier monomère comprenant un groupe isocyanate et un groupe (méth)acrylate à son extrémité et permettant ainsi le durcissement par photopolymérisation et par polymérisation thermique ; un second monomère multifonctionnel ayant un groupe hydroxy ou un groupe carboxyle ; et un acide organique, ce qui permet une plus grande force adhésive entre les couches et le durcissement par photopolymérisation et par polymérisation thermique.
PCT/KR2013/008783 2012-10-23 2013-10-01 Composition de résine durcissante et film optique fabriqué avec cette composition WO2014065517A1 (fr)

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KR20120117990A KR20140052233A (ko) 2012-10-23 2012-10-23 경화성 수지 조성물 및 이를 사용하여 제조된 광학필름
KR10-2012-0117990 2012-10-23

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
JP2014177641A (ja) * 2014-05-29 2014-09-25 Shinnakamura Kagaku Kogyo Kk ウレタン（メタ）アクリレートおよびそれを含有する光硬化性樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016194563A (ja) * 2015-03-31 2016-11-17 太陽インキ製造株式会社 導電性樹脂組成物及び導電回路
CN109970885B (zh) * 2019-03-21 2021-03-23 江南大学 一种长共轭咔唑基肟酯光引发剂及其制备方法

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Publication number Priority date Publication date Assignee Title
JPH11349947A (ja) * 1998-06-05 1999-12-21 Nippon Mitsubishi Oil Corp 光硬化型液晶性組成物および液晶フィルム
JP2005097141A (ja) * 2003-09-24 2005-04-14 Asahi Denka Kogyo Kk 二量体オキシムエステル化合物及び該化合物を有効成分とする光重合開始剤
US20110045290A1 (en) * 2008-03-03 2011-02-24 Lintec Corporation Adhesive Sheet
KR20120019619A (ko) * 2010-08-26 2012-03-07 동우 화인켐 주식회사 착색 감광성 수지 조성물, 컬러 필터 및 이를 구비한 액정 표시 장치

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349947A (ja) * 1998-06-05 1999-12-21 Nippon Mitsubishi Oil Corp 光硬化型液晶性組成物および液晶フィルム
JP2005097141A (ja) * 2003-09-24 2005-04-14 Asahi Denka Kogyo Kk 二量体オキシムエステル化合物及び該化合物を有効成分とする光重合開始剤
US20110045290A1 (en) * 2008-03-03 2011-02-24 Lintec Corporation Adhesive Sheet
KR20120019619A (ko) * 2010-08-26 2012-03-07 동우 화인켐 주식회사 착색 감광성 수지 조성물, 컬러 필터 및 이를 구비한 액정 표시 장치

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014177641A (ja) * 2014-05-29 2014-09-25 Shinnakamura Kagaku Kogyo Kk ウレタン（メタ）アクリレートおよびそれを含有する光硬化性樹脂組成物

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