KR20150109654A - Onium Salt Derivative and Photoacid Generator Comprising the Same - Google Patents
Onium Salt Derivative and Photoacid Generator Comprising the Same Download PDFInfo
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- KR20150109654A KR20150109654A KR1020140032673A KR20140032673A KR20150109654A KR 20150109654 A KR20150109654 A KR 20150109654A KR 1020140032673 A KR1020140032673 A KR 1020140032673A KR 20140032673 A KR20140032673 A KR 20140032673A KR 20150109654 A KR20150109654 A KR 20150109654A
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- South Korea
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- onium salt
- photoacid generator
- present
- salt derivative
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- 0 CC(C*C1)CC1(C)C(F)(F)F Chemical compound CC(C*C1)CC1(C)C(F)(F)F 0.000 description 2
- CVBASHMCALKFME-UHFFFAOYSA-N COc(cc1)ccc1[S+](c1ccccc1)c1ccccc1 Chemical compound COc(cc1)ccc1[S+](c1ccccc1)c1ccccc1 CVBASHMCALKFME-UHFFFAOYSA-N 0.000 description 1
- JTOWCKDEJVXWAR-UHFFFAOYSA-N Fc(cc1)ccc1[S+](c1ccccc1)c1ccccc1 Chemical compound Fc(cc1)ccc1[S+](c1ccccc1)c1ccccc1 JTOWCKDEJVXWAR-UHFFFAOYSA-N 0.000 description 1
- ROZFGYSIJVTDKH-UHFFFAOYSA-N c(cc1)ccc1[IH]c1ccccc1 Chemical compound c(cc1)ccc1[IH]c1ccccc1 ROZFGYSIJVTDKH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Abstract
Description
The present invention relates to an onium salt derivative capable of imparting excellent photosensitivity and remarkably improving a curing rate when used in a photosensitive resin composition and the like, and a photo acid generator containing the same.
In the display field, a photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photo-curable pattern. In order to improve process yield and physical properties of a subject to be applied in this process, A resin composition is required.
The onium salt compound to which the sulfonium salt compound and the iodonium salt compound belong is a substance which generates an acid by irradiation of energy ray such as light and is a resist composition for photolithography used for forming electronic circuits such as semiconductors, , A cationic polymerization initiator in a photopolymerizable composition such as a coating or an adhesive.
U.S. Patent No. 6,620,957 discloses that onium salt sulfonic acid derivatives and onium salt phosphoric acid derivatives are useful as photoacid generators, but they have insufficient sensitivity.
An object of the present invention is to provide an onium salt derivative which can improve the photosensitivity and increase the curing rate when used in a photosensitive resin composition or the like.
Another object of the present invention is to provide a photoacid generator comprising the onium salt derivative.
It is still another object of the present invention to provide a photosensitive resin composition comprising the photoacid generator.
It is still another object of the present invention to provide a photo-curable adhesive composition comprising the photoacid generator.
On the other hand, the present invention provides an onium salt derivative represented by the following general formulas (1) to (3).
[Chemical Formula 1]
(2)
(3)
In the above formulas,
R 1 to R 5 are each independently hydrogen, a C 1 -C 12 alkyl group, an aryl group, a halogen, a C 1 -C 6 alkoxy group, a C 1 -C 6 alkylcarbonyl group, an arylthio group, a cyano group or a nitro group Lt; / RTI &
R 1 to R 5 , when two or more are present, are the same or different and form an aromatic ring together with the carbon atoms to which they are bonded,
R 4 and R 5 are connected to each other to form a 5- to 7-membered ring,
p, q and r are each independently an integer of 1 to 4,
n is an integer of 0 to 5;
On the other hand, the present invention provides a photoacid generator comprising the onium salt derivative.
On the other hand, the present invention provides a photosensitive resin composition comprising the photoacid generator and a photopolymerizable compound.
On the other hand, the present invention provides a photocurable pattern formed using the photosensitive resin composition.
On the other hand, the present invention provides an image display device including the photocurable pattern.
On the other hand, the present invention provides an adhesive composition comprising the photoacid generator and a photopolymerizable monomer.
On the other hand, the present invention provides a polarizer comprising: a polarizer; An adhesive layer laminated on one side or both sides of the polarizer, the adhesive layer being formed from the adhesive composition; And a polarizer protective film laminated on the adhesive layer.
On the other hand, the present invention provides a liquid crystal display device including the polarizing plate.
The onium salt derivative according to the present invention imparts excellent photosensitivity to the photosensitive resin composition or adhesive composition and can significantly improve the curing rate.
Hereinafter, the present invention will be described in detail.
An embodiment of the present invention relates to an onium salt derivative represented by the following general formulas (1) to (3).
[Chemical Formula 1]
(2)
(3)
In the above formulas,
R 1 to R 5 are each independently hydrogen, a C 1 -C 12 alkyl group, an aryl group, a halogen, a C 1 -C 6 alkoxy group, a C 1 -C 6 alkylcarbonyl group, an arylthio group, a cyano group or a nitro group Lt; / RTI &
R 1 to R 5 , when two or more are present, are the same or different and form an aromatic ring together with the carbon atoms to which they are bonded,
R 4 and R 5 are connected to each other to form a 5- to 7-membered ring,
p, q and r are each independently an integer of 1 to 4,
n is an integer of 0 to 5;
As used herein, a C 1 -C 12 alkyl group means a linear or branched hydrocarbon group having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl, Butyl, t-butyl, n-pentyl, n-hexyl, and the like.
As used herein, an aryl group includes both an aromatic group and a heteroaromatic group and a partially reduced derivative thereof. The arometric group is a simple or fused ring group of 5 to 15-ary, and the heteroaromatic group means an arometric group containing at least one of oxygen, sulfur or nitrogen. Exemplary aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, But are not limited to, oxazolyl, thiazolyl, tetrahydronaphthyl, and the like.
As used herein, the C 1 -C 6 alkoxy group means a straight or branched alkoxy group having 1 to 6 carbon atoms, and includes, but is not limited to, methoxy, ethoxy, n-propaneoxy, and the like.
The C 1 -C 6 alkylcarbonyl group used in the present specification represents a group of the formula -COR (wherein R is hydrogen or a C 1 -C 5 alkyl group), and includes formyl, acetyl and the like, no.
As used herein, an arylthio group means a sulfur-bonded group that is bonded to an aryl group, and includes, but is not limited to, phenylthio, benzylthio, and the like.
In an embodiment of the present invention,
R 1 to R 5 are each independently hydrogen, C 1 -C 12 alkyl, halogen, C 1 -C 6 alkoxy, phenylthio or nitro,
R 1 to R 5 , when two or more are present, are the same or different and form a benzene ring together with the carbon atoms to which they are bonded,
R 4 and R 5 are connected to each other to form a 5- to 7-membered ring,
p, q and r are each independently an integer of 1 to 4,
n is an integer of 0 to 5;
In an embodiment of the present invention,
n is zero.
Specific examples of the cation in the onium salt derivative according to one embodiment of the present invention may include a cation represented by the following formula.
Specific examples of the anions in the onium salt derivatives according to one embodiment of the present invention may include anions represented by the following formulas.
Representative compounds among the onium salt derivatives according to one embodiment of the present invention may be selected from the compounds of the following formulas (4) and (5).
[Chemical Formula 4]
[Chemical Formula 5]
The onium salt derivative of the present invention can be easily prepared by a method known in the art.
The onium salt derivative according to the present invention can provide a photosensitive resin composition or a photo-curable adhesive composition with excellent photosensitivity and can significantly improve the curing rate, and thus can be useful as a photoacid generator.
Accordingly, one embodiment of the present invention relates to a photoacid generator comprising the onium salt derivative according to the present invention.
Further, one embodiment of the present invention relates to a photosensitive resin composition comprising a photoacid generator and a photopolymerizable compound according to the present invention.
The content of the photoacid generator is not particularly limited and may be, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight based on 100 parts by weight of the photopolymerizable compound. When it is included in the above range, the sensitivity is increased, the exposure time is shortened, productivity is improved, and the strength of the formed pattern and the smoothness of the surface can be improved. When the photoacid generator is contained in an amount exceeding 10 parts by weight, the pattern hardening rate may be improved, but the color of the pattern may change after curing by absorbing a part of visible light.
In one embodiment of the present invention, the photopolymerizable compound is not particularly limited as long as it is curable with the photoacid generator of the present invention. For example, it may be an epoxy compound, an oxetane compound or a vinyl ether compound, Based compound.
Specific examples of the epoxy compound may include monofunctional epoxy compounds, bifunctional epoxy compounds, trifunctional epoxy compounds and tetrafunctional epoxy compounds, preferably monofunctional epoxy compounds and bifunctional epoxy compounds have. These may be used alone or in combination of two or more.
Specific examples of the monofunctional epoxy compound include glycidylphenyl ether and 1,2-epoxyethylbenzene. Examples of the bifunctional epoxy compound include 3,4-epoxycyclohexylmethyl-3 ', 4' Epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) Adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate , epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane Carboxylate, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctylcyclohexahydrophthalate, epoxycyclohexahydrophthalic acid di-2-ethyl Hexyl and the like. These may be used alone or in combination of two or more.
Specific examples of the oxetane-based compound include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) (Methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) 4-trifluoromethyloxetane, etc. These may be used alone or in combination of two or more.
Specific examples of the monomer capable of synthesizing the vinyl ether-based resin include styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether. These may be used alone or in combination of two or more.
The photosensitive resin composition according to an embodiment of the present invention may further contain additives such as a colorant, a silane coupling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent as needed.
In addition, the photosensitive resin composition of the present invention may further comprise an alkali-soluble resin or the like as needed, and may be used as a composition capable of developing after curing. As the alkali-soluble resin, an alkali-soluble resin used in the art can be used without any particular limitation. In this case, it may further comprise an appropriate solvent used in the art.
One embodiment of the present invention relates to a photocurable pattern formed using the above-described photosensitive resin composition.
The photocurable pattern formed by using the photosensitive resin composition has excellent adhesion to a substrate. As a result, it can be used in various patterns such as an adhesive layer, an array planarizing film, a protective film, an insulating film pattern, and the like in an image display device, and can be used as a photoresist, a color filter, a black matrix, a column spacer pattern, But is not limited thereto.
The photocurable pattern according to an embodiment of the present invention can be produced by applying the above-described photosensitive resin composition of the present invention onto a substrate and forming a photocured pattern (after the development process if necessary).
First, a photosensitive resin composition is coated on a substrate and then heated and dried to remove a volatile component such as a solvent to obtain a smooth coated film. The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure, volatile components such as solvents are volatilized. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m.
Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and to precisely align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured. The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto.
If desired, the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, and a desired pattern shape can be formed. The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.
The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant and a cationic surfactant.
Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.
Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.
The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, it may be rinsed, and if necessary, post-baking may be performed at 150 to 230 ° C for 10 to 60 minutes.
An embodiment of the present invention relates to an image display apparatus including the above-described photocurable pattern.
The image display device having the photo-curable pattern may be a liquid crystal display device, an OLED, a flexible display, or the like, but is not limited thereto, and all image display devices known in the art that can be applied are exemplified.
Further, one embodiment of the present invention relates to an adhesive composition comprising a photoacid generator and a photopolymerizable monomer according to the present invention.
The content of the photoacid generator is not particularly limited and may be 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the photopolymerizable monomer. When it is contained within the above range, the sensitivity is increased, the exposure time is shortened, productivity is improved, and the surface smoothness can be improved. If the photoacid generator is contained in an amount exceeding 10 parts by weight, the curing rate of the adhesive may be improved, but the color of the adhesive layer may change after curing by absorbing a part of visible light.
In one embodiment of the present invention, the photopolymerizable monomer may be at least one selected from the group consisting of acrylic monomers and epoxy monomers.
The acrylic monomer is a compound having a (meth) acryloyl group as a photocurable functional group, and specifically includes acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- But are not limited to, one or more selected from the group consisting of hydroxypropylmethacrylate, hydroxypropylmethacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 4-morpholinyl acrylate and 4-morpholinyl methacrylate. It is not.
The photoacid generator of the present invention can be applied as a copolymerization initiator of the acrylic monomer because it undergoes a radical intermediate step in the process of generating an acid by light.
The epoxy monomer may be an epoxy compound containing at least one epoxidized aliphatic ring group, an epoxy compound containing at least one glycidyl ether group, or a compound having at least two epoxy groups and at least one aromatic ring in the molecule.
The epoxy compound containing at least one epoxidized aliphatic ring group may be at least one selected from the group consisting of 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate dicyclopentadienedioxy But is not limited to, at least one selected from the group consisting of a radical, a radical, a limonene dioxide and a 4-vinylcyclohexene dioxyde.
The epoxy compound containing at least one of the glycidyl ether groups may be 1,4-cyclohexanedimethanol diglycidyl ether, novolac epoxy, bisphenol A epoxy, bisphenol F epoxy, brominated bisphenol epoxy, 1,6- Hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, n-butyl glycidyl ether, aliphatic glycidyl ether (C 12 -C 14 ), 2-ethylhexyl glycidyl ether, phenylglycidyl Butylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, and ethylene glycol diglycidyl ether. In addition, it is also possible to use ethylene glycol diglycidyl ether such as ethylene glycol diglycidyl ether, diallyl ether, o-cresyl glycidyl ether, nonylphenyl glycidyl ether, , But is not limited thereto.
The photopolymerizable monomer is preferably contained in an amount of 90 to 99 parts by weight based on 100 parts by weight of the total adhesive composition based on the solid content. When the content is within the above range, it is suitable for exhibiting an adhesive force and a cohesive force.
The adhesive composition according to one embodiment of the present invention may further include a radical photopolymerization initiator.
The radical photopolymerization initiator preferably has an absorption wavelength at a wavelength of 340 nm or more and is preferably included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photopolymerizable monomer based on the solid content. Examples of the radical photopolymerization initiator include benzophenone, benzyldimethylketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,2-dimethoxy-1,2-diphenylethanone, 4- (2-hydroxyethoxy) Phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6- dimethoxybenzoyl) (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like, and they may be used alone or in combination of two or more.
In addition to the onium salt derivative of the present invention, the adhesive composition according to one embodiment of the present invention is a compound which produces a cationic species or Lewis acid by irradiation with an active energy ray, and examples thereof include aromatic diazonium salts, aromatic iodine An onium salt such as an aluminum salt and an aromatic sulfonium salt, an iron-arene complex, and the like may be further used, but the present invention is not limited thereto.
The adhesive composition according to one embodiment of the present invention may further contain one or more kinds of photo-sensitizers, antioxidants, and the like known in the art as needed.
One embodiment of the present invention relates to a polarizer comprising: a polarizer; An adhesive layer laminated on one side or both sides of the polarizer, the adhesive layer being formed from the adhesive composition; And a polarizer protective film laminated on the adhesive layer.
In one embodiment of the present invention, the polarizer is one in which a dichroic dye is adsorbed and oriented on a stretched polyvinyl alcohol-based film.
The polyvinyl alcohol-based resin constituting the polarizer can be obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. Other monomers copolymerizable with vinyl acetate include acrylamide monomers having an unsaturated carboxylic acid type, an unsaturated sulfonic acid type, an olefin type, a vinyl ether type, and an ammonium group. The polyvinyl alcohol resin may also be modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The saponification degree of the polyvinyl alcohol-based resin is usually 85 to 100 mol%, preferably 98 mol% or more. The degree of polymerization of the polyvinyl alcohol-based resin is usually from 1,000 to 10,000, and preferably from 1,500 to 5,000.
Such a polyvinyl alcohol-based resin film is used as the original film of the polarizer. The method of forming the film of the polyvinyl alcohol-based resin is not particularly limited, and a known method can be used. The thickness of the original film is not particularly limited, and may be, for example, 10 to 150 mu m.
In one embodiment of the present invention, the polarizer is a film obtained by continuously uniaxially stretching a polyvinyl alcohol-based film in an aqueous solution, dyeing with a dichroic dye and adsorbing it, treating with an aqueous solution of boric acid, .
The uniaxial stretching of the polyvinyl alcohol film may be performed before dyeing, concurrently with dyeing, or may be performed after dyeing. If uniaxial stretching is carried out after dyeing, it may be carried out before the boric acid treatment, or may be carried out during the boric acid treatment. Of course, it is also possible to perform uniaxial stretching in a plurality of such steps. For uniaxial stretching, other rolls or rolls of different circumferences may be used. The uniaxial stretching may be either dry stretching in air or wet stretching in the state of being swollen with a solvent. The stretching ratio is usually 4 to 8 times.
As a step of dyeing a stretched polyvinyl alcohol film with a dichroic dye, for example, a method of immersing a polyvinyl alcohol film in an aqueous solution containing a dichroic dye can be used. As the dichroic dye, iodine or a dichroic dye is used. It is preferable that the polyvinyl alcohol film is pre-immersed in water before dyeing to swell.
When iodine is used as the dichroic dye, a method in which a polyvinyl alcohol-based film is dipped in an aqueous solution for dyeing usually containing iodine and potassium iodide may be used. Usually, the content of iodine in an aqueous solution for dyeing is 0.01 to 1 part by weight with respect to 100 parts by weight of water (distilled water), and the content of potassium iodide is 0.5 to 20 parts by weight with respect to 100 parts by weight of water. The temperature of the aqueous solution for dyeing is usually 20 to 40 占 폚, and the immersion time (dyeing time) is usually 20 to 1,800 seconds.
When a dichroic dye is used as the dichroic dye, a method in which a polyvinyl alcohol film is dipped in an aqueous solution containing a water-soluble dichroic dye is generally employed. The content of the dichroic dye in this aqueous solution is usually 1 × 10 -4 to 10 parts by weight, preferably 1 × 10 -3 to 1 part by weight, per 100 parts by weight of water. The aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The dye aqueous solution used for dyeing usually has a temperature of 20 to 80 캜, and the immersion time for this aqueous solution is usually 10 to 1,800 seconds.
The step of treating the dyed polyvinyl alcohol film with boric acid can be carried out by immersing it in an aqueous solution containing boric acid. Normally, the content of boric acid in an aqueous solution containing boric acid is 2 to 15 parts by weight, preferably 5 to 12 parts by weight, based on 100 parts by weight of water. When iodine is used as the dichroic dye, it is preferable that the aqueous solution containing boric acid contains potassium iodide. The content thereof is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, based on 100 parts by weight of water. The temperature of the boric acid-containing aqueous solution is usually 50 ° C. or higher, preferably 50 to 85 ° C., more preferably 60 to 80 ° C. The immersing time is usually 60 to 1,200 seconds, preferably 150 to 600 seconds, 200 to 400 seconds.
After the boric acid treatment, the polyvinyl alcohol film is usually washed with water and dried. The washing treatment can be carried out by immersing the boric acid-treated polyvinyl alcohol-based film in water. The water temperature of the water treatment is usually 5 to 40 占 폚, and the immersion time is usually 1 to 120 seconds. After washing with water, the polarizer can be obtained. The drying treatment can be usually carried out using a hot air dryer or a far infrared ray heater. The drying treatment temperature is usually 30 to 100 占 폚, preferably 50 to 80 占 폚, and the drying time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
The thickness of the polarizer produced as described above is typically 5 to 40 탆.
In one embodiment of the present invention, the polarizer-protective film is not particularly limited as long as it is excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. Specifically, acrylic, cellulose or polyester can be used.
Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and polybutylene terephthalate; Cellulose-based resins such as diacetylcellulose and triacetylcellulose, and the like.
The thickness of the polarizer protective film is 10 to 200 탆, preferably 10 to 150 탆. Further, when the polarizer protective film is laminated on both sides of the polarizer, the same or different thickness can be maintained.
An easy joining process can be performed on the surface of the protective film to be bonded to the polarizer. Examples of the easy-to-bond treatment include a dry treatment such as a primer treatment, a plasma treatment and a corona treatment, a chemical treatment such as an alkali treatment (saponification treatment), and a coating treatment for forming an easy adhesive layer.
The polarizing plate according to an embodiment of the present invention generally includes a coating step of coating the protective film with the photo-curing adhesive of the present invention in an uncured state to form an adhesive coated surface, and a polarizer attached to the coated film of the protective film And a curing step of curing the photo-curable adhesive.
As another method of producing the polarizing plate in the present invention, the photo-curable adhesive of the present invention is dripped between the polarizer and the protective film in an uncured state, and is uniformly spread and pressed by a roll or the like, followed by curing the photo- Thereby forming an adhesive layer.
In one embodiment of the present invention, there is no particular limitation on the coating method of the photocurable adhesive for the protective film, and various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used . In addition, in the method of dropping the photo-curing adhesive between the polarizer and the protective film, and then pressing the film with a roll or the like to spread out uniformly, metal or rubber can be used as the material of the roll. In the method in which the photo-curable adhesive is dropped between the polarizer and the protective film and passed between the rolls and the rolls to pressurize the rolls, the rolls may be made of the same material or different materials.
The thickness of the adhesive layer formed by curing the photocurable adhesive of the present invention is preferably 50 占 퐉 or less, more preferably 20 占 퐉 or less, and even more preferably 10 占 퐉 or less. When the thickness of the adhesive layer is 50 占 퐉 or less, there is less risk of damaging the appearance of the polarizing plate. The thickness of the adhesive layer is usually 0.1 占 퐉 or more, preferably 0.5 占 퐉 or more.
When the photocurable adhesive of the present invention is applied to the protective film, the polarizer is subsequently adhered to the adhesive coated surface. Further, when a photo-curable adhesive is applied between the polarizer and the protective film, they are adhered as they are.
As described above, the polarizer and the protective film are adhered to each other through the photo-curable adhesive in an uncured state, and then the active energy ray is irradiated to cure the photo-curing adhesive to fix the protective film on the polarizer.
Although a light source of an active energy ray is not particularly limited, an active energy ray having a light emission distribution with a wavelength of 400 nm or less is preferable. Specific examples thereof include low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, Mercury lamp, metal halide lamp and the like are preferable. The light irradiation intensity for the photo-curing adhesive is appropriately determined according to the composition of the photo-curable adhesive and is not particularly limited, but the irradiation intensity in the wavelength range effective for activating the polymerization initiator is preferably 0.1 to 6000 mW / cm < 2 & . When the irradiation intensity is 0.1 mW / cm < 2 > or more, the reaction time does not become too long, and when the irradiation intensity is less than 6000 mW / cm < 2 >, there is little possibility that heat radiated from the light source and deterioration of the yellowing and the polarizer due to heat generation upon curing of the photo- . The light irradiation time for the photo-curable adhesive is controlled for each curable photo-curing adhesive, and is not particularly limited, but it is preferable that the accumulated light quantity as a product of the irradiation intensity and the irradiation time is set to 10 to 10,000 mJ / . When the total amount of light for the photo-curing adhesive is 10 mJ / cm 2 or more, a sufficient amount of active species originating from the polymerization initiator can be sufficiently generated to promote the curing reaction more surely. When the amount is less than 10000 mJ / cm 2, Productivity can be maintained.
When the photo-curing adhesive is cured by irradiation of an active energy ray, it is preferable to cure under the condition that the function of the polarizing plate such as the polarizing degree, transmittance and hue of the polarizer, and transparency of the protective film is not deteriorated.
The polarizing plate according to the present invention can be applied to all liquid crystal display devices. Therefore, one embodiment of the present invention relates to a liquid crystal display device including the polarizing plate.
Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Experimental Examples. It should be apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
Preparation Example 1: Preparation of the compound of formula (4)
A solution obtained by dissolving triphenylsulfonium bromide (34.3 g, 0.1 mol) in distilled water and dissolving potassium trifluoromethyltrifluoroborate (TCI, 26.4 g, 0.15 mol) in distilled water (100 g) The mixture was stirred at room temperature for 2 hours and then extracted with toluene (200 mL). The toluene layer was distilled under reduced pressure to remove the solvent to obtain the compound of Formula 4 (59.2 g).
And analyzed using an elemental analyzer (Flash EA 1112, manufactured by Thermo Electron Scientific Instrument) to confirm that the compound was represented by the following formula (4).
Elemental analysis data: C, 57.19; H, 3.78; S, 8.02
Preparation Example 2: Preparation of the compound of formula (5)
Diphenyliodonium bromide (31.6 g, 0.1 mol) was dissolved in 200 mL of distilled water, and potassium trifluoromethyltrifluoroborate (26.4 g, 0.15 mol, manufactured by TCI) was dissolved in 100 g of distilled water The mixture was stirred at room temperature for 2 hours, extracted with toluene (200 mL), and then the toluene layer was distilled under reduced pressure to remove the solvent to obtain the compound of Formula 5 (59.2 g).
After analysis using an elemental analyzer (Thermo Electron Scientific Instrument, Flash EA 1112), it was confirmed that the compound represented by Chemical Formula 5 was obtained.
Elemental analysis data: C, 37.36; H, 2.41
Examples 1 to 3 and Comparative Examples 1 to 3: Preparation of photocurable composition
The photocurable composition was prepared in the composition shown in Table 1 below.
A-1: glycidyl phenyl ether (manufactured by TCI)
A-2: 1,2-Epoxyethylbenzene (manufactured by TCI)
B-1: Compound (4)
B-2: Compound (5)
B-3: Triphenylsulfonium triflate (manufactured by Aldrich)
B-4: Diphenyllodonium triflate (manufactured by TCI)
Experimental Example 1: Evaluation of hardening rate
The photocurable compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were coated on glass with a thickness of 10 mu m using a Meyer bar and exposed to light of 100 mJ / cm < 2 > using a high-pressure mercury lamp, For 10 minutes, and a part of the cured film was taken out and dissolved in a solvent of CDCl 3. The content of residual epoxy group was analyzed by NMR analysis, and the reaction rate was calculated according to the following formula.
Reaction rate = (Epoxy content before exposure-Epoxy content after exposure) / Epoxy content before exposure * 100
The results are shown in Table 2 below.
The epoxy content before and after the exposure was calculated from the NMR integral of the phenyl group in the molecule and the integral of the epoxy on the spectrum.
As shown in Table 2, the compositions of Examples 1 to 3, in which an onium salt derivative containing trifluoromethyltrifluoroborate as an anion was used as a photoacid generator, exhibited excellent curing rates, I did.
However, the compositions of Comparative Examples 1 to 3, in which an onium salt derivative containing triflate (trifluoromethanesulfonate) as an anion was used as a photoacid generator, showed a very low curing rate.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.
Claims (13)
[Chemical Formula 1]
(2)
(3)
In the above formulas,
R 1 to R 5 are each independently hydrogen, a C 1 -C 12 alkyl group, an aryl group, a halogen, a C 1 -C 6 alkoxy group, a C 1 -C 6 alkylcarbonyl group, an arylthio group, a cyano group or a nitro group Lt; / RTI &
R 1 to R 5 , when two or more are present, are the same or different and form an aromatic ring together with the carbon atoms to which they are bonded,
R 4 and R 5 are connected to each other to form a 5- to 7-membered ring,
p, q and r are each independently an integer of 1 to 4,
n is an integer of 0 to 5;
R 1 to R 5 are each independently hydrogen, C 1 -C 12 alkyl, halogen, C 1 -C 6 alkoxy, phenylthio or nitro,
R 1 to R 5 , when two or more are present, are the same or different and form a benzene ring together with the carbon atoms to which they are bonded,
R 4 and R 5 are connected to each other to form a 5- to 7-membered ring,
p, q and r are each independently an integer of 1 to 4,
and n is an integer of 0 to 5.
[Chemical Formula 4]
[Chemical Formula 5]
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140032673A KR20150109654A (en) | 2014-03-20 | 2014-03-20 | Onium Salt Derivative and Photoacid Generator Comprising the Same |
| PCT/KR2015/002493 WO2015142000A1 (en) | 2014-03-20 | 2015-03-16 | Onium salt derivative and photoacid generator containing same |
| TW104109046A TW201536728A (en) | 2014-03-20 | 2015-03-20 | Onium salt derivative and photoacid generator comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140032673A KR20150109654A (en) | 2014-03-20 | 2014-03-20 | Onium Salt Derivative and Photoacid Generator Comprising the Same |
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| KR20150109654A true KR20150109654A (en) | 2015-10-02 |
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| KR1020140032673A KR20150109654A (en) | 2014-03-20 | 2014-03-20 | Onium Salt Derivative and Photoacid Generator Comprising the Same |
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| Country | Link |
|---|---|
| KR (1) | KR20150109654A (en) |
| TW (1) | TW201536728A (en) |
| WO (1) | WO2015142000A1 (en) |
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| JP7012424B2 (en) * | 2016-03-25 | 2022-02-14 | 東京応化工業株式会社 | Energy-sensitive compositions, cured products and methods for producing cured products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004123631A (en) * | 2002-10-03 | 2004-04-22 | Tokuyama Corp | Onium salt |
| JP5208573B2 (en) * | 2008-05-06 | 2013-06-12 | サンアプロ株式会社 | Sulfonium salt, photoacid generator, photocurable composition and cured product thereof |
| JP2010185986A (en) * | 2009-02-10 | 2010-08-26 | Tokyo Ohka Kogyo Co Ltd | Chemically amplified positive photoresist composition for thick film and method for manufacturing thick film resist pattern |
| JP2011201803A (en) * | 2010-03-25 | 2011-10-13 | San Apro Kk | Onium borate salt, photoacid generator and photosensitive resin composition |
-
2014
- 2014-03-20 KR KR1020140032673A patent/KR20150109654A/en not_active Application Discontinuation
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2015
- 2015-03-16 WO PCT/KR2015/002493 patent/WO2015142000A1/en active Application Filing
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| WO2015142000A1 (en) | 2015-09-24 |
| TW201536728A (en) | 2015-10-01 |
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