WO2013180419A1 - Composé photoactif et composition de résine sensible à la lumière le comprenant - Google Patents

Composé photoactif et composition de résine sensible à la lumière le comprenant Download PDF

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Publication number
WO2013180419A1
WO2013180419A1 PCT/KR2013/004496 KR2013004496W WO2013180419A1 WO 2013180419 A1 WO2013180419 A1 WO 2013180419A1 KR 2013004496 W KR2013004496 W KR 2013004496W WO 2013180419 A1 WO2013180419 A1 WO 2013180419A1
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Prior art keywords
group
resin composition
photosensitive resin
formula
ocor
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PCT/KR2013/004496
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English (en)
Korean (ko)
Inventor
조창호
김성현
김한수
김선화
카르바쉬라이사
박종호
Original Assignee
주식회사 엘지화학
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Priority claimed from KR20130054473A external-priority patent/KR101489067B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201380006359.3A priority Critical patent/CN104066741B/zh
Priority to US14/347,165 priority patent/US8883398B2/en
Priority to JP2014551211A priority patent/JP5831776B2/ja
Publication of WO2013180419A1 publication Critical patent/WO2013180419A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems

Definitions

  • the present application relates to a photoactive compound comprising an oxime ester group and a phosphonate group and a photosensitive resin composition comprising the same.
  • the present application relates to a photoactive compound comprising an oxime ester group and a phosphonate group and a photosensitive resin composition comprising the same.
  • the photosensitive resin composition may be applied to a substrate to form a coating film, and a specific portion of the coating film may be exposed by light irradiation using a photomask or the like, and then used to form a pattern by developing and removing the non-exposed portion. . Since such a photosensitive resin composition can irradiate, superpose
  • the transparent photosensitive resin composition is used for column spacers, overcoats, and passivation membranes, and it is generally possible to use an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a solvent without using a colorant such as a pigment. Include.
  • the colored photosensitive resin composition is used for a color filter photoresist and a photoresist for a resin black matrix, and is usually a colorant of red, green, blue, and black, an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, and photopolymerization. Initiator and solvent.
  • the photosensitive resin composition has been manufactured for the purpose of constituting liquid crystal display devices such as TVs and monitors in addition to the conventional notebooks and mobiles as the use of LCDs has been advanced and diversified, and responds quickly to light for improving productivity and durability.
  • the demand for mechanically excellent physical properties is increasing.
  • a property that reacts quickly to light that is, light sensitivity becomes a very important factor.
  • the overcoat and passivation film serving as a column spacer or a protective film, which serves as a support, to exhibit the original performance without damage to the liquid crystal display device due to an external impact should have excellent mechanical properties.
  • a photopolymerization initiator with excellent photosensitivity can solve these problems.
  • a photoinitiator with excellent photosensitivity sufficient sensitivity can be realized even with a small amount of photopolymerization initiator, thereby reducing the contamination of liquid crystals, increasing the residual film ratio of the pattern, and increasing the usable width of other raw materials when preparing the composition. It has the advantage of being.
  • the problem to be solved by the present application is to overcome all the disadvantages of the conventional photopolymerization initiator, easy to store without degrading sensitivity, chemical resistance, developability, and excellent fume (fume) properties in high temperature process It is to provide a photoactive compound and a photosensitive resin composition comprising the same.
  • One embodiment of the present application provides a photoactive compound represented by the following Chemical Formula 1.
  • Y is a C 1 to C 15 alkylene group unsubstituted or substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR,
  • M 1 is an alkyl group of C 1 ⁇ C 8 ; Or an aryl group of C 6 ⁇ C 12 ,
  • R 1 is a C 1 ⁇ C 8 alkyl group; Or an aryl group of C 6 ⁇ C 12 ,
  • At least one of R 2 to R 6 is XA, and the others are each independently selected from the group consisting of halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′,
  • A is a C 6 -C 20 aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR ', and CONRR',
  • R and R ' are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl group, C 1 -C 10 haloalkyl group and C 7 -C 13 arylalkyl group, wherein R and R' together are a ring Can be formed.
  • One embodiment of the present application is a photoactive compound represented by Formula 1; Alkali-soluble binder resins; Polymeric compounds containing ethylenically unsaturated bonds; And it provides a photosensitive resin composition comprising a solvent.
  • One embodiment of the present application provides a photosensitive material prepared using the photosensitive resin composition.
  • One embodiment of the present application provides an electronic device manufactured using the photosensitive resin composition.
  • the compound provided through the present application is easy to store without degrading sensitivity, chemical resistance, and developability, and has excellent fume generation suppression property in a high temperature process. Accordingly, the photosensitive resin composition according to the present application is advantageous not only for curing the column spacer, overcoat and passivation material of the liquid crystal display device, but also in manufacturing the electronic device.
  • the inventors of the present application synthesized a compound having a structure containing both an oxime ester group and a phosphonate group in one molecule, and confirmed that the compound absorbs ultraviolet rays more efficiently than other photoinitiators and has excellent sensitivity and high temperature processing characteristics. .
  • the compounds initially developed have low photoinitiation efficiency and are not effective in absorbing UV light sources when the color characteristics are good.
  • Compounds published after the late 1990s have significantly improved photoinitiation efficiency but do not fully satisfy the recently enhanced process time reductions.
  • there is still a difficulty in forming a fine pattern because the pigment concentration is high or the thickness of the coating film is 2.5 ⁇ m or more. Can't satisfy
  • Conventionally known oxime derivative compounds have a disadvantage of low photoinitiation efficiency, poor processing time, weak mechanical strength, and poor storage stability.
  • the photoactive compound according to the embodiment of the present application has superior photoinitiation efficiency, shorter processing time, superior mechanical strength, superior economical advantages, and improved storage stability compared to the conventional oxime ester photopolymerization initiator. And, there is an advantage in developing. Moreover, it has the advantage of being excellent in sensitivity, having sufficient solubility with respect to the polymeric compound which has an ethylenically unsaturated bond, and being stable also over time. In addition, the efficiency of generating radicals by efficiently absorbing ultraviolet rays of i-line (365 nm), and excellent solubility and compatibility with the binder, has the advantage of excellent high temperature process characteristics.
  • One embodiment of the present application provides a photoactive compound represented by the following Chemical Formula 1.
  • Chemical Formula 1 may be Chemical Formula 2.
  • Y is a C 1 to C 15 alkylene group; Or a C 1 to C 15 alkylene group substituted with one or more substituents selected from the group consisting of R, OR, SR, COR and OCOR, and preferably an alkylene group of C 2 to C 6 .
  • an ethylene group or a propylene group is more preferable in view of solubility and compatibility.
  • M 1 is an alkyl group of C 1 ⁇ C 8 ; Or an aryl group of C 6 to C 12 , preferably an alkyl group of C 1 to C 10 , and more preferably a methyl group or an ethyl group.
  • R 1 is an alkyl group of C 1 ⁇ C 8 ; Or a C 6 -C 12 aryl group, preferably a methyl group or a phenyl group.
  • R 1 is a part which is decomposed into radicals which are active species at the time of exposure, and is not particularly limited in structure, but the simpler the structure, the better the movement and the photoinitiation efficiency is improved.
  • R 2 To R 6 At least one of may be XA, preferably R 4 May be XA.
  • R 2 To R 6 Except XA The remainder may be each independently selected from the group consisting of halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
  • A may be a C 6 to C 20 aryl group which is unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR ′ and CONRR ′. And preferably a phenyl group unsubstituted or substituted with one or more groups selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
  • Substituents corresponding to A in Formula 2 are R 7 , R 8 , R 9 , and R 10 to R 11 .
  • R 7 , R 8 , R 9 , R 10 and R 11 may be each independently selected from the group consisting of a halogen group, CN, R, OR, SR, COR, OCOR, NRR 'and CONRR'.
  • R and R ' may each be selected from the group consisting of hydrogen, C 1 ⁇ C 10 alkyl group, C 1 ⁇ C 10 haloalkyl group and C 7 ⁇ C 13 arylalkyl group, or R and R' together May form a ring.
  • R and R 'together form a ring it may form a 5-membered, 6-membered or 7-membered ring, may be monocyclic or polycyclic, and may be aromatic, aliphatic ring, heteroaromatic or heteroaliphatic ring. have.
  • the halogen group may be fluorine, chlorine, bromine or iodine.
  • the aryl group may be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group when the aryl group is a monocyclic aryl group, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like, but is not limited thereto.
  • the aryl group may be specifically naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perrylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.
  • the alkyl group may be straight, branched or cyclic. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. may be, but is not limited thereto.
  • the alkoxy group may be linear, branched or cyclic, and may be substituted or unsubstituted.
  • Examples of the alkoxy group may be methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, cyclopentyloxy group and the like, but is not limited thereto.
  • the alkylene group may be linear or branched, and may be substituted or unsubstituted. Specific examples of the alkylene group include methylene, ethylene, propylene, isopropylene, butylene, t-butylene, but are not limited thereto.
  • substituted or unsubstituted means substituted with one or more substituents or no substituent.
  • the substituent is not particularly defined may be hydrogen.
  • the photoactive compound of the present application represented by Formula 1 or Formula 2 includes an oxime ester group and a phosphonate group (-Y-PO (OM 1 ) 2 ) in its structure and includes a substituted or unsubstituted phenyl group. There is a characteristic.
  • the phosphonate group increases the solubility of the compound represented by Formula 1 or Formula 2, and improves the solubility of the photosensitive resin composition with high compatibility with the binder resin by forming a hydrogen bond with an alkali-soluble binder resin in the photosensitive resin composition. It also lowers volatility.
  • the photoactive compound of the present application represented by Formula 1 or Formula 2 has a high melting point and has an advantage of easy storage, and has an effect of preventing generation of fume in a high temperature process.
  • a photosensitive resin composition containing a conventional photoactive compound fumes are generated in the exposure process, volatilized into the air, and then adhered to a portion such as a mask, which may cause defects. .
  • the fume may be a foreign substance, which may cause a defect.
  • One embodiment of the present application is a photoactive compound represented by Formula 1; Alkali-soluble binder resins; Polymeric compounds containing ethylenically unsaturated bonds; And it provides a photosensitive resin composition comprising a solvent.
  • the compound of Formula 1 may be a compound of Formula 2.
  • the compound of Formula 1 or Formula 2 may be a compound of any one of Formulas 3 to 6.
  • the amount of the photoactive compound represented by Formula 1 may be included in 0.1 to 5% by weight of the total photosensitive resin composition, but is not limited thereto. If it is less than 0.1% by weight may not give sufficient sensitivity, if it exceeds 5% by weight high UV absorption may not be able to transmit the UV light to the bottom.
  • the photosensitive resin composition according to the exemplary embodiment of the present application has an effect of adjusting the viscosity by including a binder resin, and has an effect of enabling patterning using an alkaline developer.
  • a binder resin those generally used in the art such as an alkali-soluble polymer resin may be used.
  • the alkali-soluble resin binder is a copolymer of a monomer containing an acid functional group and a monomer giving a film strength copolymerizable with the monomer, or a polymer reaction with an ethylenically unsaturated compound containing an epoxy group. It may be a compound prepared through.
  • the alkali-soluble resin binder used in the present application may have an acid value of about 30 to 300 KOH mg / g. If the acid value is less than 30 KOH mg / g is not well developed to obtain a clean pattern, and if it exceeds 300 KOH mg / g, the washing characteristics are excessively improved and the pattern may fall off.
  • the weight average molecular weight of the alkali-soluble resin binder is preferably in the range of 1,000 to 200,000, more preferably may be in the range of 5,000 to 100,000. If the weight average molecular weight of the alkali-soluble binder resin is less than 1,000, the heat resistance and chemical resistance deteriorate. If the weight-average molecular weight of the alkali-soluble binder resin is more than 200,000, the solubility in the developing solution is lowered, so that the development is not possible, and the viscosity of the solution is excessively increased, making it difficult to apply uniformly. Can not do it.
  • Non-limiting examples of the monomer containing an acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2-carboxylic acid, mono 2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, ⁇ -carboxy polycaprolactone mono (meth) acrylate, or mixtures thereof have.
  • Non-limiting examples of monomers copolymerizable with the monomer containing the acid group include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) ) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (Meth) acrylate, tetrahydroperpryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, acyloc
  • Aromatic vinyls such as styrene, ⁇ -methylstyrene, (o, m, p) -vinyl toluene, (o, m, p) -methoxy styrene, (o, m, p) -chloro styrene;
  • Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
  • N-vinyl tertiary amines such as N-vinyl pyrrolidone, N-vinyl carbazole, and N-vinyl morpholine
  • Unsaturated imides such as N-phenyl maleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide
  • Maleic anhydrides such as maleic anhydride and methyl maleic anhydride;
  • Unsaturated glycidyl compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or mixtures thereof.
  • allyl glycidyl ether, glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) acrylate, glycidyl 5-norbornene-2 One or more selected from the group consisting of -methyl-2-carboxylate (endo, exo mixture), 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene.
  • the content of the binder resin may be 1 to 30% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.
  • the content of the binder resin is 1% by weight or more, the effect of patterning using an alkali aqueous solution is well effected, and the problem of difficulty in forming a pattern due to the lack of solubility in a developer is prevented. There is an effect that can prevent the loss of, and the viscosity of the entire solution is too high to prevent problems that may be difficult to coat.
  • the photosensitive resin composition according to the embodiment of the present application may include a crosslinkable compound, and specifically, a polymerizable compound including an ethylenically unsaturated bond may be used. More specifically, a crosslinkable compound including two or more unsaturated acrylic groups and a crosslinkable compound including three or more unsaturated acrylic groups may be used.
  • ethylene glycol di (meth) acrylate an ethylene group having 2 to 14 polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethylethylphthalic acid, propylene glycol di (meth) acrylate with 2 to 14 propylene groups, dipentaerythritol penta A mixture of an acidic modification of (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate (trade name TO- 2348, TO-2349) compound obtained by
  • silica dispersions may be used for these compounds, for example, Nanocryl XP series (0596, 1045, 21/1364) and Nanopox XP series (0516, 0525) manufactured by Hanse Chemie.
  • the content of the crosslinkable compound, specifically, the polymerizable compound including an ethylenically unsaturated bond may be 0.5 to 30% by weight based on the total weight of the photosensitive resin composition.
  • the present invention is not limited thereto. If the content is less than 0.5% by weight is not preferable because the cross-linking reaction is not progressed by light, when the content exceeds 30% by weight is difficult to form a pattern of the poor solubility in alkali.
  • non-limiting examples of the solvent include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclo Pentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxy propionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, and
  • the content of the solvent may be 40 to 95 wt% based on the total weight of the photosensitive resin composition, but is not limited thereto.
  • Photosensitive resin composition is a transparent photosensitive resin composition, 0.1 to 5% by weight of the photoactive compound represented by the formula (1), 0.5 to 30% by weight of a polymerizable compound containing an ethylenically unsaturated bond, alkali soluble It may include 1 to 30% by weight of the binder resin and 40 to 95% by weight of the solvent.
  • the photosensitive resin composition according to the embodiment of the present application may further include a colorant.
  • the coloring agent may be used one or more pigments, dyes or mixtures thereof.
  • a metal oxide such as carbon black, graphite, titanium black, or the like may be used.
  • Examples of carbon black include cysto 5HIISAF-HS, cysto KH, cysto 3HHAF-HS, cysto NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, cysto 116MAF, cysto FMFEF-HS , Sisto SOFEF, Sisto VGPF, Sisto SVHSRF-HS and Sisto SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, # 25, # CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, MA
  • examples of the colorant to be colored are carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), perylene black (BASF K0084. K0086), cyanine black, linole yellow (CI21090), Linol yellow GRO (CI 21090), benzidine yellow 4T-564D, Victoria pure blue (CI42595), CI PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202, 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I.
  • a white pigment, a fluorescent pigment, etc. can also be used.
  • a substance containing zinc as the center metal may be used.
  • the content of the colorant may be 1 to 20% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.
  • Photosensitive resin composition is a colored photosensitive resin composition, 0.1 to 5% by weight of the photoactive compound represented by the formula (1), 0.5 to 30% by weight of a polymerizable compound containing an ethylenically unsaturated bond, alkali soluble It may include 1 to 30% by weight of the binder resin, 1 to 20% by weight of the colorant and 40 to 95% by weight of the solvent.
  • the photosensitive resin composition according to the exemplary embodiment of the present application may include, as necessary, a second photoactive compound, a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, a UV absorber, a plasticizer, an adhesion promoter, a filler, a surfactant, and the like, as necessary. It may further comprise one or two or more additives of.
  • the second photoactive compound is contained in an amount of 0.1 to 5% by weight, and the other additives in amounts of 0.01 to 5% by weight, respectively.
  • the second photoactive compound is specifically, a triazine compound, a biimidazole compound, an acetophenone compound, an O-acyl oxime compound, a benzophenone compound, It may be selected from the group consisting of a thioxanthone compound, a phosphine oxide compound and a coumarin compound.
  • the second photoactive compound is more specifically 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6 -Triazine, 2,4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- ⁇ 4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio ⁇ propanoic acid, 2,4-trichloromethyl- (4'-ethylbiphenyl) -6-tri Triazine compounds such as azine and 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine;
  • O-acyl oxime compounds such as Irgacure OXE 01 from BASF, Irgacure OXE 02, N-1919, NCI-831, NCI-930 from ADEKA Corporation;
  • Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone;
  • Thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone;
  • 2,4,6-trimethylbenzoyl diphenylphosphine oxide bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide
  • Phosphine oxide compounds such as these;
  • examples of the curing accelerator, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimer Capto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate ), Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate) , Trimethylolethane tris (2-mercaptoacetate), and trimethylolethane tris (3-mercaptopropionate) may include one or more selected from the group
  • the thermal polymerization inhibitor p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, N-nitroso It may include one or more selected from the group consisting of phenylhydroxyamine ammonium salt, N-nitrosophenylhydroxyamine aluminum salt and phenothiazine, but are not limited thereto, and those known in the art It may include.
  • the dispersant may be a polymer type, nonionic, anionic, or cationic dispersant.
  • Non-limiting examples of such dispersants include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, esteralkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxes Acid salts, alkylamide alkylene oxide adducts, alkylamines, and the like, and one or a mixture of two or more selected from these may be used, but is not limited thereto.
  • non-limiting examples of the antioxidant are 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-g, t- It may include one or more selected from butylphenol, but is not limited thereto.
  • non-limiting examples of the ultraviolet absorber are 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole And it may include one or more selected from alkoxy benzophenone, but is not limited thereto.
  • the surfactant may include MCF 350SF, F-475, F-488, F-552 (hereinafter referred to as DIC), but are not limited thereto. no.
  • plasticizers adhesion promoters, fillers, and the like can also be used for all compounds that can be included in conventional photosensitive resin compositions.
  • One embodiment of the present application provides a photosensitive material including the photosensitive resin composition.
  • One embodiment of the present application provides a photosensitive material prepared using the photosensitive resin composition.
  • the photosensitive resin composition is present in a state in which at least a part of the solvent is removed or photocured by drying and / or curing in the photosensitive material.
  • the photosensitive resin composition according to the present application is used in a roll coater (curtain coater), curtain coater (curtain coater), spin coater (spin coater), slot die coater, various printing, deposition, etc., metal, paper, glass plastic substrate It can be applied on a support such as.
  • mercury vapor arc arc
  • carbon arc arc
  • Xe arc etc. which emit light of 250-450 nm in wavelength, etc. are mentioned, for example.
  • the photosensitive resin composition comprising the compound of the present application is a pigment dispersion type photosensitive material for manufacturing a TFT LCD color filter, a photosensitive material for forming a black matrix of a TFT LCD or an organic light emitting diode, a photosensitive material for forming an overcoat layer, a column spacer photosensitive material, a printed circuit board
  • a photocurable paint a photocurable ink, a photocurable adhesive agent, a printing plate, and a PDP, and the use is not specifically limited.
  • One embodiment of the present application provides an electronic device manufactured using the photosensitive resin composition.
  • the photoactive compound containing the phosphonate structure according to the present invention has a higher melting point than the compound of the similar structure (comparative compounds 1 to 2), and is stable and easy to handle.
  • PMEA propylene glycol monomethyl ether acetate
  • a photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound of Formula 4 prepared in Synthesis Example 2 was used instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1.
  • a photosensitive resin composition was prepared in the same manner as in Example 1, except that BAOX's OXE-02 compound was used instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1.
  • a photosensitive resin composition was prepared in the same manner as in Example 1 except for using the compound of Formula 7 shown in the Example of Korean Patent Publication No. 10-2010-0092904 instead of the compound of Formula 3 prepared in Synthesis Example 1 in Example 1. Prepared.
  • the photoactive compound according to the present invention exhibits excellent effects in terms of luminance than when using the conventional photoactive compound because of its good heat resistance without causing yellowing.

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Abstract

La présente invention concerne : un composé photoactif comprenant simultanément un groupe d'ester d'oxime et un groupe de phosphonate ; et une composition de résine sensible à la lumière le comprenant, et le composé de la présente invention présente des caractéristiques exceptionnelles de stabilité au stockage et de traitement à température élevée.
PCT/KR2013/004496 2012-05-30 2013-05-22 Composé photoactif et composition de résine sensible à la lumière le comprenant WO2013180419A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201380006359.3A CN104066741B (zh) 2012-05-30 2013-05-22 光活性化合物及包含其的光敏树脂组合物
US14/347,165 US8883398B2 (en) 2012-05-30 2013-05-22 Photoactive compound and light-sensitive resin composition comprising same
JP2014551211A JP5831776B2 (ja) 2012-05-30 2013-05-22 光活性化合物、感光性樹脂組成物および感光材

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2012-0057757 2012-05-30
KR20120057757 2012-05-30
KR10-2013-0054473 2013-05-14
KR20130054473A KR101489067B1 (ko) 2012-05-30 2013-05-14 광활성 화합물 및 이를 포함하는 감광성 수지 조성물

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WO2013180419A1 true WO2013180419A1 (fr) 2013-12-05

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005080337A1 (fr) * 2004-02-23 2005-09-01 Mitsubishi Chemical Corporation Ester d'oxime, composition photopolymérisable et filtre coloré les utilisant
KR20080104287A (ko) * 2006-03-28 2008-12-02 후지필름 가부시키가이샤 광중합 개시제, 감광성 조성물, 감광성 필름, 감광성 적층체, 영구 패턴 형성 방법, 및 프린트 기판
KR20110059525A (ko) * 2009-11-27 2011-06-02 가부시키가이샤 아데카 옥심에스테르 화합물 및 상기 화합물을 함유하는 광중합 개시제
JP2011141413A (ja) * 2010-01-07 2011-07-21 Toppan Printing Co Ltd 青色感光性樹脂組成物ならびにカラーフィルタ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005080337A1 (fr) * 2004-02-23 2005-09-01 Mitsubishi Chemical Corporation Ester d'oxime, composition photopolymérisable et filtre coloré les utilisant
KR20080104287A (ko) * 2006-03-28 2008-12-02 후지필름 가부시키가이샤 광중합 개시제, 감광성 조성물, 감광성 필름, 감광성 적층체, 영구 패턴 형성 방법, 및 프린트 기판
KR20110059525A (ko) * 2009-11-27 2011-06-02 가부시키가이샤 아데카 옥심에스테르 화합물 및 상기 화합물을 함유하는 광중합 개시제
JP2011141413A (ja) * 2010-01-07 2011-07-21 Toppan Printing Co Ltd 青色感光性樹脂組成物ならびにカラーフィルタ

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