WO2013008652A1 - 光重合開始剤、感光性組成物及び硬化物 - Google Patents

光重合開始剤、感光性組成物及び硬化物 Download PDF

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WO2013008652A1
WO2013008652A1 PCT/JP2012/066763 JP2012066763W WO2013008652A1 WO 2013008652 A1 WO2013008652 A1 WO 2013008652A1 JP 2012066763 W JP2012066763 W JP 2012066763W WO 2013008652 A1 WO2013008652 A1 WO 2013008652A1
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photopolymerization initiator
photosensitive composition
indole skeleton
substituent
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PCT/JP2012/066763
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English (en)
French (fr)
Japanese (ja)
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山田　裕章
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新日鉄住金化学株式会社
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Priority to JP2013523889A priority Critical patent/JP5944898B2/ja
Publication of WO2013008652A1 publication Critical patent/WO2013008652A1/ja

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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
    • G03F7/027—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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • the present invention relates to a novel photopolymerization initiator, a photosensitive composition containing the same, and a cured product thereof.
  • Photosensitive compositions are widely used in a form in which a photopolymerization initiator is blended with a polymerizable compound having an olefinic bond.
  • Photoresist, photocurable ink, photocurable paint, photocurable adhesive, photofabrication Have been put to practical use in applications such as photosensitive resins, photosensitive printing plates, and recording materials.
  • Such a photosensitive composition can be cured by causing a polymerization reaction by irradiating with ultraviolet light or visible light using a mercury lamp, xenon lamp, laser or the like as a light source (referred to as exposure), but can be cured efficiently with a small exposure amount.
  • a highly sensitive photosensitive composition is desired, and a highly sensitive photopolymerization initiator for that purpose is required.
  • a number of compounds have been proposed as photopolymerization initiators so far, including acetophenone compounds, benzophenone compounds, benzoin ether compounds, ⁇ -aminoalkylphenone compounds, thioxanthone compounds, organic peroxides, biimidazole compounds, titanocene compounds, Triazine compounds, acylphosphine oxide compounds, quinone compounds, oxime ester compounds and the like are known. However, none of these has sufficient sensitivity.
  • Another problem is that the solubility in propylene glycol monomethyl ether acetate is low. Furthermore, many of the oxime ester compounds having a carbazole skeleton also have the disadvantage that the molecular structure is relatively complex and the production cost is high.
  • the present invention has been made in view of the problems of the prior art, and an object thereof is to provide a photopolymerization initiator having high sensitivity and excellent solubility and a photosensitive composition using the photopolymerization initiator.
  • the present inventors focused on an oxime ester compound having an indole skeleton having one less condensed ring than the carbazole skeleton, and further replacing the indole skeleton with a specific functional group.
  • the present invention has been completed by finding that the object can be achieved.
  • the present invention provides a light having a group having an oxime ester bond bonded to an indole skeleton which may have a substituent, and the indole skeleton is substituted with at least one nitro group. It is a polymerization initiator.
  • a group having an oxime ester bond represented by the following general formula (1) is bonded directly or via a carbonyl group to the 3-position of the indole skeleton, and the indole skeleton 5 It is preferred that the position is substituted with a nitro group.
  • R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent.
  • R 11 and R 12 represent a branched structure or a ring structure.
  • a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom.
  • the present invention is a photosensitive composition containing a polymerizable compound having an olefin bond and the photopolymerization initiator, and a cured product obtained by curing the photosensitive composition.
  • the photosensitive composition preferably contains propylene glycol monomethyl ether acetate as a solvent.
  • the photopolymerization initiator of the present invention is formed by bonding a group having an oxime ester bond to an indole skeleton which may have a substituent.
  • the indole skeleton needs to be substituted with at least one nitro group, and the substitution position is preferably the 5-position.
  • the group having an oxime ester bond a group represented by the following general formula (1) is advantageous, and the group having the oxime ester bond is bonded directly to the 3-position of the indole skeleton or via a carbonyl group. Preferably it is.
  • R 11 and R 12 each represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent.
  • R 11 and R 12 represent a branched structure or a ring structure. And a hetero atom may be present at any position, R 11 may be bonded to a substituent on the indole skeleton, and R 11 may be a hydrogen atom.
  • the oxime moiety of the structure represented by the general formula (1) and the formula described later represents a mixture of these geometric isomers or any one of them.
  • a preferable structure is the following general formula (2), It is represented by
  • R 1 , R 2 , R 4 , R 6 and R 7 may be any substituent, but may be a saturated or unsaturated group having 1 to 20 carbon atoms which may have a substituent. It is preferably a valent organic group, or a hydrogen atom, a halogen atom or a nitro group. In the case of such a monovalent organic group, R 1 , R 2 , R 4 , R 6 and R 7 may form a branched structure or a ring structure, and a hetero atom may exist at an arbitrary position. Or may be bonded to each other.
  • R 11 and R 12 are the same as those in the general formula (1).
  • saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent in the general formulas (1) and (2) include a methyl group and an ethyl group.
  • a halogen atom a hydroxy group, a sulfanyl group, a carbonyl group, a thiocarbonyl group, a carboxy group, a thiocarboxy group, a dithiocarboxy group, a formyl group, a cyano group , Nitro group, nitroso group, sulfo group, amino group, imino group, silyl group, ether group, thioether group, ester group, thioester group, dithioester group, amide group, thioamide group, urethane group, thiourethane group, ureido group Moreover, the structure which introduce
  • the monovalent organic group includes not only a monovalent organic group on a carbon atom such as a methyl group, but also a monovalent organic group on a heteroatom such as a methoxy group, a methylsulfanyl group, or a dimethylamino group. Groups are also included.
  • the monovalent organic group carboxy group, thiocarboxy group, dithiocarboxy group, formyl group, cyano group, primary amide group, primary thioamide group, ureido group, thioureido group, etc.
  • the functional group may be directly bonded.
  • the monovalent organic group may be appropriately selected according to the molecular weight, sensitivity, solubility, etc. of the target photopolymerization initiator, but is saturated or saturated with 1 to 20 carbon atoms from the viewpoint of performance and economy.
  • An unsaturated monovalent hydrocarbon group is preferable, a saturated or unsaturated monovalent hydrocarbon group having 1 to 12 carbon atoms is more preferable, and further, a saturated one having 1 to 4 carbon atoms. Or, it is most preferably an unsaturated monovalent hydrocarbon group.
  • the monovalent hydrocarbon group can be used regardless of the presence or absence of a saturated or unsaturated, branched structure or ring structure.
  • the photopolymerization initiator of the present invention may be obtained by multiplying it through an appropriate substituent as in the structures represented by the following general formulas (19) and (20).
  • R 1a and R 11a represent a saturated or unsaturated divalent organic group having 1 to 20 carbon atoms which may have a substituent.
  • R 1 , R 2 , R 4 , R 6 , R 7 , R 11 and R 12 are the same as those in the general formulas (1) and (2).
  • the photopolymerization initiator of the present invention may have a structure represented by the following general formulas (21), (22), and (23).
  • R 1 , R 2 , R 4 , R 6 , R 7 , R 11 and R 12 are the same as those in the general formulas (1) and (2), and R 1a and R 11a are the same as those in the general formula (19) and (Same as (20).)
  • the production method of the photopolymerization initiator of the present invention is not particularly limited.
  • the following procedure is applied using commercially available 5-nitroindole as a raw material. It is economically advantageous to do.
  • R 1 is introduced into the 1-position of 5-nitroindole by a nucleophilic substitution reaction or the like
  • R 11 CO is introduced into the 3-position by Friedel-Crafts acylation reaction to obtain a ketone body. This is converted into an oxime with hydroxylamine, and further esterified with an acid halide or acid anhydride of R 12 COOH to lead to a target photopolymerization initiator.
  • a nitrite is allowed to act on the ketone body to form an ⁇ -oxooxime, and the oxime is esterified in the same manner.
  • 5-nitroindole may not be used as a starting material, and R 1 or R 11 CO may be first introduced into the indole, followed by nitration.
  • the photopolymerization initiator of the present invention has an indole skeleton, which is a skeleton having a smaller number of condensed rings and a smaller plane spread than the carbazole skeleton. Therefore, the photopolymerization initiator of the present invention is excellent in solubility and has an effect of improving the degree of freedom in designing the photosensitive composition. For example, even in applications where photocuring is difficult, such as a light-shielding photoresist used in the production of a black matrix for a color filter, good sensitivity can be obtained by being present at a high concentration in the photosensitive composition. It becomes like this. On the other hand, in order for the photopolymerization initiator to exhibit its function, it needs to absorb light and be in an excited state.
  • the photopolymerization initiator of the present invention can overcome this problem by substituting the indole skeleton with at least one nitro group, and can cause light absorption in a wide wavelength range from ultraviolet light to visible light.
  • the photosensitive composition of the present invention contains a polymerizable compound having an olefin bond in addition to the above photopolymerization initiator.
  • a polymerizable compound having an olefin bond known compounds conventionally used in photosensitive compositions can be used without particular limitation, but acrylic acid and methacrylic acid (hereinafter referred to as “(meth)” Acrylic acid "etc.) derivatives are advantageous, for example, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta (Meth) acrylic acid ester derivatives such as erythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth)
  • a reaction product of the (meth) acrylic acid derivative and a compound having an (preferably plural) isocyanate group or an acid anhydride group in the structure is also suitable.
  • vinyl resins acrylic acid (co) polymer, methacrylic acid (co) polymer, maleic acid (co) polymer, styrene (co) polymer, etc.
  • polyester resins which are known resins
  • polyamide resins Resins in which a (meth) acryloyl group is introduced into the main chain or side chain of a polyimide resin, polyurethane resin, polyether resin or the like by an ester bond, an amide bond, a urethane bond, or the like can also be used.
  • (meth) acrylic acid derivatives maleic acid derivatives, maleimide derivatives, crotonic acid derivatives, itaconic acid derivatives, cinnamic acid derivatives, vinyl derivatives, vinyl alcohol derivatives, vinyl ketone derivatives, vinyl aromatic derivatives, etc. it can.
  • These polymerizable compounds having an olefinic bond may further have a heat-functional functional group such as an epoxy group, an alkali-soluble functional group such as a carboxy group, etc., and a composite function. .
  • These polymerizable compounds having an olefinic bond may be used alone or in combination.
  • the mixing ratio of the photopolymerization initiator in the photosensitive composition of the present invention is not particularly limited, but the photopolymerization initiator is 0.01 to 50 parts by weight with respect to 100 parts by weight of the polymerizable compound having an olefin bond.
  • the amount is preferably 0.1 to 20 parts by weight.
  • the photosensitive composition of the present invention may contain a solvent, and in particular, propylene glycol monomethyl ether acetate can be preferably used.
  • Propylene glycol monomethyl ether acetate is a safe solvent having moderate solubility and drying properties, and is widely used in photoresists and the like used in the production of color filters, but the photopolymerization initiator of the present invention is used in the solvent system. It is difficult to cause problems such as poor dissolution, and a photosensitive composition can be advantageously produced.
  • solvent known compounds other than propylene glycol monomethyl ether acetate can also be used, for example, ester solvents, ketone solvents, ether solvents, alcohol solvents, aromatic solvents, aliphatic solvents, amine solvents, An amide solvent or the like can be used without any particular limitation.
  • the photosensitive composition of the present invention may contain other optional components as necessary.
  • a coloring material a filler, a resin, an additive and the like can be blended.
  • coloring materials dyes, organic pigments, inorganic pigments, carbon black pigments, etc., as fillers, silica, talc, etc.
  • resins vinyl resins (acrylic acid (co) polymer, methacrylic acid (co) heavy) Coalesce, maleic acid (co) polymer, styrene (co) polymer, etc.), polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, epoxy resin, melamine resin, etc.
  • Crosslinking agents, dispersants, surfactants, silane coupling agents, viscosity modifiers, wetting agents, antifoaming agents, antioxidants and the like can be mentioned.
  • known compounds can be used without particular limitation.
  • a well-known photoinitiator, a dye sensitizer, etc. can also be used together for the photosensitive composition of this invention.
  • acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, benzophenone, 2,4,6-trimethylbenzophenone, 4,4′-bis (N, N Benzophenone compounds such as -diethylamino) benzophenone, benzoin ether compounds such as benzoin ethyl ether and benzoin-tert-butyl ether, 2-methyl-1- [4- (methylsulfanyl) phenyl] -2-morpholinopropan-1-one, ⁇ -aminoalkylphenone compounds such as benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one,
  • a method for producing a cured product of the photosensitive composition of the present invention a known method can be used. After the photosensitive composition is applied or injected onto an appropriate substrate or mold suitable for the purpose or application, it is cured by exposure. Should just be done. Here, by performing selective exposure using a photomask or the like, and further performing development, processing such as image formation or modeling can be performed. Since the photopolymerization initiator of the present invention is excellent in solubility in a developer, it has an effect of shortening the time required for developing the photosensitive composition, and is preferable in terms of improving production efficiency. After performing exposure and development, a treatment such as baking may be further performed as necessary.
  • the photopolymerization initiator of the present invention is extremely useful because it is excellent in sensitivity and can provide a highly sensitive photosensitive composition that can be cured efficiently with a small amount of exposure.
  • the photopolymerization initiator of the present invention absorbs ultraviolet light and visible light and enters an excited state, the oxime ester bond is rapidly cleaved to generate a highly active radical species, and the olefin bond contained in the photosensitive composition It is considered that a polymerizable compound having a high molecular weight undergoes a polymerization reaction at high speed.
  • the photopolymerization initiator of the present invention is excellent in solubility and can be suitably used in a solvent system such as propylene glycol monomethyl ether acetate.
  • Step 1 Using N, N-dimethylformamide as a solvent, 0.100 mol of 5-nitroindole, 0.110 mol of bromoethane and 0.110 mol of potassium hydroxide were reacted at 35 ° C. for 2 hours. After cooling, the reaction solution was dropped into water, and the precipitated solid was collected, washed thoroughly and dried to obtain 0.099 mol of 1-ethyl-5-nitroindole.
  • Step 2 Using nitromethane as a solvent, the total amount of the product of Step 1, 0.120 mol of acetyl chloride and 0.120 mol of aluminum chloride were reacted at room temperature for 2 hours. The reaction solution was dropped into ice water, and the precipitated solid was collected, washed thoroughly and dried to obtain 0.095 mol of 1- (1-ethyl-5-nitroindol-3-yl) ethanone.
  • ⁇ 9.29 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.57 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 6.01 (ddt, 1H, R 1 ), 5.33 (ddt, 1H, R 1 ), 5.15 (ddt, 1H, R 1 ), 4.81 (ddd, 2H, R 1 ), 2. 42 (s, 3H, R 11 ), 2.39 (s, 3H, R 12 ).
  • Step 1 The product of Step 1 is 1-allyl-5-nitroindole, the product of Step 2 is 1- (1-allyl-5-nitroindol-3-yl) ethanone, and the product of Step 3 is 1- ( 1-allyl-5-nitroindol-3-yl) ethanone oxime.
  • ⁇ 9.27 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.56 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 4.19 (t, 2H, R 1 ), 2.42 (s, 3H, R 11 ), 2.39 (s, 3H, R 12 ), 1.87 (tt, 2H, R 1 ), 1. 37 (tq, 2H, R 1 ), 0.97 (t, 3H, R 1 ).
  • Step 1 is 1-butyl-5-nitroindole
  • the product of Step 2 is 1- (1-butyl-5-nitroindol-3-yl) ethanone
  • the product of Step 3 is 1- ( 1-butyl-5-nitroindol-3-yl) ethanone oxime.
  • Step 2 is 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one
  • the product of Step 3 is 1- (1-ethyl-5-nitroindole-3- Yl) propan-1-one oxime.
  • ⁇ 9.28 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.68 (q, 2H, R 12 ), 2.41 (s, 3H, R 11 ), 1.54 (t, 3H, R 1 ), 1. 31 (t, 3H, R 12 ).
  • ⁇ 9.30 (d, 1H, R 4 ), 8.18 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 4.25 (q, 2H, R 1 ), 2.44 (s, 3H, R 11 ), 1.96 (tt, 1H, R 12 ), 1.54 (t, 3H, R 1 ), 1. 21 (dt, 2H, R 12 ), 1.03 (dt, 2H, R 12 ).
  • ⁇ 9.32 (d, 1H, R 4 ), 8.18 (dd, 1H, R 6 ), 7.59 (s, 1H, R 2 ), 7.37 (d, 1H, R 7 ), 4.24 (q, 2H, R 1 ), 2.41 (s, 3H, R 11 ), 1.54 (t, 3H, R 1 ), 1.37 (s, 9H, R 12 ).
  • ⁇ 9.32 (d, 1H, R 4 ), 8.19 (dd, 1H, R 6 ), 7.60 (s, 1H, R 2 ), 7.38 (d, 1H, R 7 ), 6.61 (dd, 1H, R 12 ), 6.40 (dd, 1 H, R 12 ), 5.98 (dd, 1 H, R 12 ), 4.26 (q, 2H, R 1 ), 2. 86 (q, 2H, R 11 ), 1.55 (t, 3H, R 1 ), 1.31 (t, 3H, R 11 ).
  • Step 2 is 1- (1-ethyl-5-nitroindol-3-yl) propan-1-one
  • the product of Step 3 is 1- (1-ethyl-5-nitroindole-3- Yl) propan-1-one oxime.
  • Example 11 (Preparation of photosensitive composition) 56.5% by weight of propylene glycol monomethyl ether of 0.10% by weight of the photopolymerization initiator synthesized in Example 1 and 56.5% by weight of an alkali-developable photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure Acetate solution (“V-259ME” manufactured by Nippon Steel Chemical Co., Ltd.) 26.20% by weight, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 5.00% by weight, silicone surfactant (Toray Dow Corning) "FZ-2122" manufactured by the company) 0.05 wt%, 3- (glycidyloxy) propyltrimethoxysilane (silane coupling agent) 0.05 wt% and propylene glycol monomethyl ether acetate (solvent) 68.60 wt% Mix in proportion and
  • the photosensitive composition was applied to an alkali-free glass substrate using a spin coater, and dried on an 80 ° C. hot plate for 1 minute to prepare a test piece. At this time, the coating conditions (spin rotation speed) were adjusted so that a cured film having a thickness of 1.0 ⁇ m was obtained. Next, an ultra-high pressure mercury lamp with an illuminance of 30 mW / cm 2 (based on i-line) through a photomask whose transmittance is changed stepwise between 0 and 100% and a cut filter that absorbs light of 350 nm or less And 100 mJ / cm 2 (i-line basis) was irradiated with ultraviolet rays to perform image exposure on the test piece.
  • test piece was treated with an alkaline developer at 23 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. This image can read the exposure amount required for photocuring. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition. The exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
  • Example 12 The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 2, and the others were prepared and evaluated in the same manner as in Example 11.
  • the exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
  • Example 13 The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 3, and the others were prepared and evaluated in the same manner as in Example 11.
  • the exposure amount required for photocuring determined from the image was 26 mJ / cm 2 (i-line reference).
  • Example 14 The photopolymerization initiator in Example 11 was changed to the photopolymerization initiator synthesized in Example 4, and the others were prepared and evaluated in the same manner as in Example 11.
  • the exposure necessary for photocuring determined from the image was 23 mJ / cm 2 (i-line reference).
  • the exposure amount required for photocuring determined from the image was 37 mJ / cm 2 (i-line basis), and it was shown that the sensitivity was lower than in Examples 11 to 14 (exposure amount necessary for curing). The smaller the number, the higher the sensitivity.)
  • a photosensitive composition was prepared and evaluated. As a result, the photosensitive composition was completely undissolved in the alkali developer without being photocured, indicating that the sensitivity was lower than in Examples 11-14.
  • Example 21 (Preparation of photosensitive composition) 0.60% by weight of the photopolymerization initiator synthesized in Example 1, 56.5% by weight of propylene glycol monomethyl ether of an alkali development type photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure Acetate solution (“V-259ME” manufactured by Nippon Steel Chemical Co., Ltd.) 8.23 wt%, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 1.35 wt%, carbon black pigment (colorant) cationic 26.69 wt% dispersion (carbon black pigment concentration 30.0 wt%, solid content concentration 34.5 wt%) dispersed in propylene glycol monomethyl ether acetate with a polymer dispersant, fluorosurfactant (manufactured by DIC) “Megafuck F-556”) 0.05% by weight,
  • the said photosensitive composition was apply
  • test piece was treated with an alkaline developer at 23 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition.
  • a high-quality black matrix having a line width of 5 ⁇ m with good linearity and no development residue was formed on the test piece.
  • the optical density of the black matrix was 4.4 / ⁇ m and had high light shielding properties.
  • Example 22 The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 2, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 ⁇ m with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / ⁇ m and had high light shielding properties.
  • Example 23 The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 3, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 ⁇ m with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / ⁇ m and had high light shielding properties.
  • Example 24 The photopolymerization initiator in Example 21 was changed to the photopolymerization initiator synthesized in Example 4, and the others were prepared and evaluated in the same manner as in Example 21. A high-quality black matrix having a line width of 5 ⁇ m with good linearity and no development residue was formed on the test piece. The optical density of the black matrix was 4.4 / ⁇ m and had high light shielding properties.
  • a photosensitive composition was prepared and evaluated.
  • the foreign matter was an undissolved photopolymerization initiator.
  • the photopolymerization initiator of the present invention is highly sensitive and excellent in solubility, a photoresist, a photocurable ink, a photocurable paint, a photocurable adhesive, a photopolymerization photosensitive resin, a photosensitive printing plate, It can be used suitably for recording materials and the like. In particular, it is optimal for applications that require high performance, such as photoresists used in the manufacture of color filters.

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JPWO2017051680A1 (ja) * 2015-09-25 2018-07-12 株式会社Adeka オキシムエステル化合物及び該化合物を含有する重合開始剤
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KR102604868B1 (ko) 2015-09-25 2023-11-22 가부시키가이샤 아데카 옥심에스테르 화합물 및 그 화합물을 함유하는 중합 개시제
WO2018191237A1 (en) * 2017-04-12 2018-10-18 Sun Chemical Corporation Stable photoresist compositions comprising organosulphur compounds
WO2021049489A1 (ja) * 2019-09-10 2021-03-18 株式会社Adeka 化合物、酸発生剤、組成物、硬化物及びパターン、並びに硬化物及びパターンの製造方法
CN113727971A (zh) * 2019-09-10 2021-11-30 株式会社艾迪科 化合物、产酸剂、组合物、固化物及图案以及固化物及图案的制造方法

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