WO2006059458A1 - Oxime ester compound and photopolymerization initiator comprising the compound - Google Patents

Oxime ester compound and photopolymerization initiator comprising the compound Download PDF

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Publication number
WO2006059458A1
WO2006059458A1 PCT/JP2005/020416 JP2005020416W WO2006059458A1 WO 2006059458 A1 WO2006059458 A1 WO 2006059458A1 JP 2005020416 W JP2005020416 W JP 2005020416W WO 2006059458 A1 WO2006059458 A1 WO 2006059458A1
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WIPO (PCT)
Prior art keywords
compound
oxime ester
photopolymerization initiator
meth
photosensitive composition
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PCT/JP2005/020416
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French (fr)
Japanese (ja)
Inventor
Mitsuo Akutsu
Daisuke Sawamoto
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Adeka Corporation
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Application filed by Adeka Corporation filed Critical Adeka Corporation
Priority to CN2005800373260A priority Critical patent/CN101048377B/en
Publication of WO2006059458A1 publication Critical patent/WO2006059458A1/en

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    • 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
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a novel oxime ester compound useful as a photopolymerization initiator for use in a photosensitive composition, a photopolymerization initiator containing the compound as an active ingredient, and a polymerizable compound having an ethylenically unsaturated bond
  • the present invention relates to a photosensitive composition comprising the above photopolymerization initiator.
  • a photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and is polymerized by irradiating the photosensitive composition with light of 405 nm or 365 nm. Because it can be cured, it is used in photocurable inks, photosensitive printing plates, and various photoregisters. Since a photosensitive composition sensitive to a short wavelength light source can be finely printed, a photopolymerization initiator having excellent sensitivity particularly to a 365 nm light source is desired.
  • Patent Document 1 As a photopolymerization initiator used in the photosensitive composition, Patent Document 1 below proposes to use an oxime ester derivative. Patent Documents 2 to 4 listed below also describe oxime ester compounds. When these known oxime ester compounds are used as a photopolymerization initiator, decomposition products generated by light during exposure adhere to the mask, resulting in a pattern during printing. This resulted in poor shape and reduced yield. In addition, the decomposition temperature was 240 ° C. or lower, and the photopolymerization initiator was decomposed in the thermosetting step after the development process, thereby lowering the adhesion and alkali resistance of the photosensitive composition.
  • Patent Documents 5 to 7 below propose O-acyloxime photoinitiators having higher reactivity.
  • these ⁇ 1 acyloxime photopolymerization initiators also had poor alkali resistance due to insufficient mask dirt and heat resistance.
  • Patent Document 7 describes force S, which describes an O-acyloxime compound having a force rubazolyl structure.
  • a carbazolyl compound substituted with a cycloalkyloxybenzoyl similar to the compound of the present invention could not be synthesized because the cycloalkyl ether has secondary hydrogen.
  • Patent Document 1 US Pat. No. 3,558,309 Specification
  • Patent Document 2 US Patent No. 4255513
  • Patent Document 3 US Patent No. 4590145 Specification
  • Patent Document 4 US Patent No. 4202697
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2000-80068
  • Patent Document 6 Japanese Patent Laid-Open No. 2001-233842
  • Patent Document 7 International Publication No. 02/100903 Pamphlet
  • the problem to be solved is that the obtained polymer is not colored or does not contaminate the polymer or equipment, and is excellent in developability, adhesion, alkali resistance, and sensitivity. This means that the photopolymerization initiator has been used so far.
  • An object of the present invention is to provide a photopolymerization initiator that has high sensitivity and does not cause a coloration of a polymer or contaminate a polymer and an apparatus.
  • the present invention achieves the above object by providing an oxime ester compound represented by the following general formula (I) and a photopolymerization initiator containing the compound as an active ingredient.
  • X represents a hydrogen atom, a halogen atom or an alkyl group, and when m is 2 or more, a plurality of Xs may be different groups, and R 2 and R 3 may be R, OR, C0R, SR,
  • CONRR ′ or CN represents R and R ′ each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these may be substituted with a halogen atom and / or a heterocyclic group,
  • the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and R and R ′ may be joined together to form a ring.
  • A represents a cycloalkylalkyl group, and m represents a positive number of 1 to 4.
  • FIG. 1 is a photograph of the quartz plate used in Example 7 before exposure.
  • FIG. 2 is a photograph of the quartz plate used in Example 7 after exposure.
  • FIG. 3 is a photograph of the quartz plate used in Comparative Example 5 before exposure.
  • FIG. 4 is a photograph of the quartz plate used in Comparative Example 5 after exposure.
  • examples of the halogen atom represented by X include fluorine, chlorine, bromine, and iodine.
  • alkyl group represented by X include methinole, ethyl, propyl, Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-aminole, hexyl, heptyl, octyl, isooctyl, 2-ethyl hexyl, tert-octyl, noninore, isonoel, decyl, isodecyl , Bulle, arryl, butur, ethur, propyninore, methoxyethinole, ethoxyethinole, propiroxychechinole, methoxyethoxyl, ethoxyethoxyethyl, prop
  • Examples of the aralkyl group represented by R and R ′ include benzyl, Examples of the heterocyclic group represented by R 1 and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl, and the like. Examples of the ring that can be formed by combining R and R ′ include a piperidine ring and a morpholine ring.
  • Examples of the cycloalkylalkyl group represented by ⁇ include cyclopropinoremethinole, 2-cyclopropylethyl, 3-cyclopropylpropyl, cyclobutylmethyl, 2-cyclobutylethyl, 3-cyclobutylpropyl, cyclopentylmethyl, Examples include 2-cyclopentylethanol, 3-cyclopentylpropyl, cyclohexylmethyl, 3-cyclohexylpropyl, 2-chloro-3-cyclohexylpropyl, and the like.
  • oxime ester compounds of the present invention in the above general formula (I), those in which X is an alkyl group, particularly a methyl group; those in which R is an alkyl group, particularly a methyl group;
  • R is alkyl group, especially ethyl group
  • oxime ester compound of the present invention represented by the above general formula (I) include the following compounds No .:! To No. 3.
  • the present invention Is not limited by the following compounds.
  • the oxime ester compound of the present invention represented by the general formula (I) can be generally produced by the following method. First, carbazole compound 1 and carboxylic acid chloride 3 in which one of carboxylic acid chlorides 2 and X is a halogen atom are reacted simultaneously or sequentially in the presence of zinc chloride to obtain acyl compound 4. Next, the acyl compound 4 and alcohol Compound 5 is reacted in the presence of potassium butoxide to give acyl 6 The alcohol compound may be added to the carboxylic acid chloride before the acylation reaction. Next, the acyl compound 6 and hydroxylamine hydrochloride are reacted in the presence of DMF to obtain the oxime compound 7.
  • oxime compound 7 and the acid anhydride 8 or the acid chloride 8 ′ are reacted to obtain the oxime ester compound of the present invention represented by the above general formula (I).
  • Compound No. 1 can be produced by a method represented by the following reaction formula [Chemical Formula 5]
  • the oxime ester compound of the present invention is useful as a photopolymerization initiator for a polymerizable compound having an ethylenically unsaturated bond.
  • polymerizable compound having an ethylenically unsaturated bond examples include styrene compounds such as styrene, monomethylstyrene, and chlorostyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-pro Pyr (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tetrahydrofuryl (Meth) Atarylate, 2-Ethylhexyl (Meth) Atylate, Laurinole (Meth) Atarylate, Stearinore (Meth) At
  • styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, hydroxyethyl (meth) acrylate, and photopolymerization starting with the oxime ester compound of the present invention as an active ingredient Agents are preferred.
  • thermoplastic organic polymer examples include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer. , (Meth) acrylic acid-methyl methacrylate copolymer, polybutyral, Examples include, but are not limited to, polystyrene, polyacrylolamide, saturated polyester, and epoxy resin. Among these, polystyrene, (meth) acrylic acid monomethyl methacrylate copolymer, and epoxy resin are preferable.
  • the photopolymerization initiator in addition to the oxime ester compound of the present invention, another photopolymerization initiator can be used in combination, if necessary. In some cases, other photopolymerization initiators may be used in combination to produce a remarkable synergistic effect.
  • photopolymerization initiator that can be used in combination with the oxime ester compound of the present invention
  • conventionally known compounds can be used.
  • the photosensitive composition of the present invention includes, as necessary, thermal polymerization inhibitors such as p_anisole, hydroquinone, pyrocatechol, tert-butylcatechol, and funothiazine; plasticizer; adhesion promoter; filling Conventional additives such as agents can be added.
  • the photosensitive composition of the present invention usually contains a solvent capable of dissolving or dispersing each of the above components (the oxime ester compound of the present invention and the polymerizable compound having an ethylenically unsaturated bond), if necessary.
  • a solvent capable of dissolving or dispersing each of the above components for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methineless cellosolve, ethyl acetate sorb, black mouth form, methylene chloride, hexane, heptane, Octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol can be added.
  • the photosensitive composition of the present invention is applied onto a support substrate such as metal, paper, plastic, and the like by a known means such as a roll coater, a curtain coater, various types of printing and dipping.
  • a support substrate such as metal, paper, plastic, and the like
  • a curtain coater various types of printing and dipping.
  • the photosensitive composition of the present invention can be used for various applications such as a photocurable paint, a photocurable ink, a photocurable adhesive, a printing plate, a photoresist for a printed wiring board, and the like. There are no particular restrictions on its use.
  • a light source of active light used when curing the photosensitive composition containing the oxime ester compound of the present invention it is possible to use a light source that emits light having a wavelength of 300 to 450 nm.
  • a light source that emits light having a wavelength of 300 to 450 nm.
  • ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be used.
  • the additive amount of the photopolymerization initiator is not particularly limited, but the oxime ester compound of the present invention is an ethylenically unsaturated compound.
  • the amount is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymerizable compound having a bond.
  • the oil layer was separated and washed in the order of 40 g of 5% HC1 aqueous solution, 40 g of water, and 40 g of 2% NaOH aqueous solution.
  • Dichloroethane is distilled off and acetic acid n Recrystallization was performed from 74.6 g of propyl. Filtration and washing with a mixed solvent of n-propyl acetate / n-heptane gave 22.4 g of a pale yellow solid (yield 60%, HPLC purity 98%).
  • the obtained pale yellow crystal had a melting point of 175 ° C and the NMR chemical shift and IR measurement results were as follows, confirming that it was the target acyl compound.
  • the acrylic copolymer is composed of 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate and 55 parts by mass of butyl methacrylate. It was obtained by dissolving 0.75 parts by mass of azobisisobutyl nitrile in a nitrogen atmosphere and reacting at 70 ° C for 5 hours.
  • Photosensitive composition No. 3 was obtained by adding 1.3 g of 5,4 ′, 5, monotetraphenyl_1_2, monobiimidazole and 83 g of ethyl acetate and stirring well.
  • the styrene-acrylic photosensitive copolymer is composed of 26.3 parts by mass of styrene and 2-hydride. Loxymetatalylate 43.8 parts by weight, 35 parts by weight of methacrylic acid and 70 parts by weight of ethyl acetate are dissolved in 175 parts by weight of ethyl acetate sorb, and 0.775 parts by weight of azobisisobutyl nitrile is dissolved in a nitrogen atmosphere.
  • the mixture was reacted at 90 ° C for 5 hours, and then 23.5 parts by weight of isocyanatoethyl methacrylate and 0.11 part of tin octylate dissolved in 20 parts by weight of ethyl acetate sorb were added dropwise over about 10 minutes. Then, it was obtained by reacting for 2 hours after dropping.
  • Decomposition temperature measurement (in nitrogen gas atmosphere, heating rate 10 Z min, 5% weight loss temperature) 1 9 1.2 V
  • Styrene-acrylic photosensitive copolymer used in Example 4 instead of acrylic copolymer Photosensitive composition No. 7 was obtained under the same conditions as in Comparative Example 1 except that the coalescence was used.
  • Photosensitive composition No. 9 was obtained under the same conditions as in Comparative Example 3 except that the styrene-acrylic photosensitive copolymer used in Example 4 was used instead of the acrylic copolymer.
  • the obtained photosensitive composition was evaluated as follows. That is, after spin-coating r-glycidoxypropylmethylethoxysilane on a substrate and spin-drying it well, the above photosensitive composition No .:! ⁇ 9 was spin-coated (1300 rpm, 50 seconds). Dried. After pre-beta for 20 minutes at 70 ° C, a 5% by mass solution of polyvinyl alcohol was coated to form an oxygen barrier film. After drying at 70 ° C for 20 minutes, using a specified mask, using an ultra-high pressure mercury lamp as the light source, after exposure, immerse in 2.5% sodium carbonate solution at 25 ° C for 30 seconds, develop, and rinse thoroughly .
  • Coating film heated to 200 ° C for 30 minutes after exposure and development according to JIS D 0202 test method A cross cut was made in the shape of the substrate, and a peeling test was conducted with cellophane tape at the next stage, and the state of peeling of the substrate was visually evaluated. The case where peeling was not recognized at all was marked as ⁇ , and the case where peeling was observed was marked as X.
  • the adhesion of the photosensitive composition using the oxime ester compound of the present invention is equal to or better than that of the known oxime ester compound.
  • the alkali resistance is excellent.
  • Photosensitivity composition due to decomposition of comparative compound 1 in heat curing treatment at 230 ° C due to excellent potency and basic performance difference from comparative compound 1 or low heat resistance of comparative compound 1 It is thought that the performance of the object has deteriorated.
  • the oxime ester ich compound of the present invention has a decomposition temperature of 240 ° C. or higher, better heat resistance of 9 to 50 ° C. than known oxime ester compounds, and is stable at the thermosetting temperature.
  • FIG. 1 is a photograph before exposure of the quartz plate used in Example 7, and FIG. 2 is a photograph after exposure of the stone plate used in Example 7.
  • FIG. 3 is a photograph of the quartz plate used in Comparative Example 5 before exposure
  • FIG. 4 is a photograph of the quartz plate used in Comparative Example 5 after exposure. No attachments are observed on the quartz plates in Figs. 1, 2 and 3. In Fig. 4, countless crystalline attachments are observed.
  • Example 7 and Comparative Example 5 it can be inferred that the compound of the present invention is a mask stain that sublimates after exposure do not have.
  • the known photoinitiator has a large amount of sublimation and causes mask contamination. Therefore, the curable composition using the photoinitiator of the present invention can be used continuously.
  • a conventional photoinitiator it is necessary to clean an apparatus such as a mask. The use of can be expected to improve productivity.
  • the oxime ester ricin compound of the present invention is highly sensitive and has a high thermal decomposition temperature and does not impair the adhesion and alkali resistance of the photosensitive composition. Is useful as a photopolymerization initiator that does not adhere to the mask.

Abstract

An oxime ester compound characterized by being represented by the following general formula (I). It is useful as a photopolymerization initiator. The oxime ester compound has high sensitivity and a high heat decomposition temperature. It does not impair the adhesion and alkali resistance of a photosensitive composition. The decomposition products generated from the compound by light irradiation do not adhere to a mask. (I) (In the formula, X represents alkyl, etc., provided that when m is 2 or larger, then the X's may be different; R1, R2, and R3 each represents, e.g., an alkyl or another group, which may be substituted by a halogen atom, etc. and in which the alkylene moiety may be separated by an unsaturated bond, ether bond, etc.; A represents cycloalkylalkyl; and m is 1-4.)

Description

明 細 書  Specification
ォキシムエステル化合物及び該化合物を含有する光重合開始剤 技術分野  Oxime ester compound and photopolymerization initiator containing the compound
[0001] 本発明は、感光性組成物に用いられる光重合開始剤として有用な新規なォキシム エステル化合物、該化合物を有効成分とする光重合開始剤、及びエチレン性不飽和 結合を有する重合性化合物に該光重合開始剤を含有させてなる感光性組成物に関 する。  The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator for use in a photosensitive composition, a photopolymerization initiator containing the compound as an active ingredient, and a polymerizable compound having an ethylenically unsaturated bond The present invention relates to a photosensitive composition comprising the above photopolymerization initiator.
背景技術  Background art
[0002] 感光性組成物は、エチレン性不飽和結合を有する重合性化合物に光重合開始剤 を加えたものであり、この感光性組成物に 405nmや 365nmの光を照射することによ つて重合硬化させることができるので、光硬化性インキ、感光性印刷版、各種フオトレ ジスト等に用いられている。短波長の光源に感度を持つ感光性組成物は微細な印刷 が可能であるため、特に 365nmの光源に優れた感度を有する光重合開始剤が望ま れている。  [0002] A photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and is polymerized by irradiating the photosensitive composition with light of 405 nm or 365 nm. Because it can be cured, it is used in photocurable inks, photosensitive printing plates, and various photoregisters. Since a photosensitive composition sensitive to a short wavelength light source can be finely printed, a photopolymerization initiator having excellent sensitivity particularly to a 365 nm light source is desired.
[0003] この感光性組成物に用いられる光重合開始剤として、下記特許文献 1には、ォキシ ムエステル誘導体を用いることが提案されている。また、下記特許文献 2〜4にもォキ シムエステル化合物が記載されている。し力、し、これらの公知のォキシムエステル化 合物は、光重合開始剤として用いた場合に、露光時の光により発生する分解物がマ スクに付着し、その結果、焼付け時のパターン形状不良を引き起こし、収率の低下を 招いていた。また、分解温度が 240°C以下であり、現像処理後の熱硬化工程におい て光重合開始剤が分解することにより感光性組成物の密着性及び耐アルカリ性を低 下させていた。そのため、熱分解温度が高ぐ光照射による開始剤の分解物が揮散 して重合物や装置等を汚染したりしない光重合開始剤が望まれていた。  [0003] As a photopolymerization initiator used in the photosensitive composition, Patent Document 1 below proposes to use an oxime ester derivative. Patent Documents 2 to 4 listed below also describe oxime ester compounds. When these known oxime ester compounds are used as a photopolymerization initiator, decomposition products generated by light during exposure adhere to the mask, resulting in a pattern during printing. This resulted in poor shape and reduced yield. In addition, the decomposition temperature was 240 ° C. or lower, and the photopolymerization initiator was decomposed in the thermosetting step after the development process, thereby lowering the adhesion and alkali resistance of the photosensitive composition. Therefore, there has been a demand for a photopolymerization initiator that does not contaminate the polymer or the apparatus due to volatilization of the decomposition product of the initiator caused by light irradiation with a high thermal decomposition temperature.
[0004] また、下記特許文献 5〜7には、より高い反応性を有する O—ァシルォキシム光開 始剤が提案されている。しかし、これらの〇一ァシルォキシム光重合開始剤も、マスク 汚れや耐熱性が不十分で耐アルカリ性を低下させていた。また、特許文献 7には、力 ルバゾリル構造を有する O—ァシルォキシム化合物が記載されている力 S、本発明者ら が検討の結果、本発明の化合物に類似のシクロアルキルォキシベンゾィルで置換さ れたカルバゾリル化合物は、シクロアルキルエーテルが 2級水素を持っために合成 できなかった。 [0004] In addition, Patent Documents 5 to 7 below propose O-acyloxime photoinitiators having higher reactivity. However, these ○ 1 acyloxime photopolymerization initiators also had poor alkali resistance due to insufficient mask dirt and heat resistance. Patent Document 7 describes force S, which describes an O-acyloxime compound having a force rubazolyl structure. However, as a result of investigation, a carbazolyl compound substituted with a cycloalkyloxybenzoyl similar to the compound of the present invention could not be synthesized because the cycloalkyl ether has secondary hydrogen.
[0005] 特許文献 1：米国特許第 3558309号明細書 [0005] Patent Document 1: US Pat. No. 3,558,309 Specification
特許文献 2：米国特許第 4255513号明細書  Patent Document 2: US Patent No. 4255513
特許文献 3：米国特許第 4590145号明細書  Patent Document 3: US Patent No. 4590145 Specification
特許文献 4：米国特許第 4202697号明細書  Patent Document 4: US Patent No. 4202697
特許文献 5：特開 2000— 80068号公報  Patent Document 5: Japanese Unexamined Patent Publication No. 2000-80068
特許文献 6：特開 2001— 233842号公報  Patent Document 6: Japanese Patent Laid-Open No. 2001-233842
特許文献 7：国際公開 02/100903号パンフレット  Patent Document 7: International Publication No. 02/100903 Pamphlet
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 解決しょうとする問題点は、上述したように、得られる重合物を着色したり重合物や 装置等を汚染したりすることがなく且つ現像性、密着性、耐アルカリ性、感度に優れ た光重合開始剤がこれまでな力、つたということである。 [0006] As described above, the problem to be solved is that the obtained polymer is not colored or does not contaminate the polymer or equipment, and is excellent in developability, adhesion, alkali resistance, and sensitivity. This means that the photopolymerization initiator has been used so far.
[0007] 本発明の目的は、高感度であり、重合物を着色したり重合物及び装置等を汚染し たりするおそれのない、光重合開始剤を提供することにある。 [0007] An object of the present invention is to provide a photopolymerization initiator that has high sensitivity and does not cause a coloration of a polymer or contaminate a polymer and an apparatus.
課題を解決するための手段  Means for solving the problem
[0008] 本発明は、下記一般式 (I)で表されるォキシムエステル化合物及び該化合物を有 効成分とする光重合開始剤を提供することにより、上記目的を達成したものである。 The present invention achieves the above object by providing an oxime ester compound represented by the following general formula (I) and a photopolymerization initiator containing the compound as an active ingredient.
[0009] [化 1] [0009] [Chemical 1]
Figure imgf000004_0001
Figure imgf000004_0001
(式中、 Xは水素原子、ハロゲン原子又はアルキル基を表し、 mが 2以上の場合、 複数の Xは各々異なる基でもよく、 R 2及び R 3は R、 O R、 C〇R、 S R、 (In the formula, X represents a hydrogen atom, a halogen atom or an alkyl group, and when m is 2 or more, a plurality of Xs may be different groups, and R 2 and R 3 may be R, OR, C0R, SR,
C O N R R ' 又は C Nを表し、 R及び R ' は、 アルキル基、 ァリール基、 ァラル キル基又は複素環基を表し、 これらはハロゲン原子及び 又は複素環基で置換さ れていてもよく、これらのうちアルキル基及びァラルキル基のアルキレン部分は、 不飽和結合、 エーテル結合、 チォエーテル結合、 エステル結合により中断されて いてもよく、 また、 R及び R ' は一緒になつて環を形成していてもよい。 Aはシ クロアルキルアルキル基を表し、 mは 1 ~ 4の正数を表す。） 図面の簡単な説明  CONRR ′ or CN represents R and R ′ each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these may be substituted with a halogen atom and / or a heterocyclic group, The alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and R and R ′ may be joined together to form a ring. A represents a cycloalkylalkyl group, and m represents a positive number of 1 to 4. Brief description of the drawings
[0010] [図 1]図 1は実施例 7に用いた石英板の露光前の写真である。  FIG. 1 is a photograph of the quartz plate used in Example 7 before exposure.
[図 2]図 2は実施例 7に用いた石英板の露光後の写真である。  FIG. 2 is a photograph of the quartz plate used in Example 7 after exposure.
[図 3]図 3は比較例 5に用いた石英板の露光前の写真である。  FIG. 3 is a photograph of the quartz plate used in Comparative Example 5 before exposure.
[図 4]図 4は比較例 5に用いた石英板の露光後の写真である。  FIG. 4 is a photograph of the quartz plate used in Comparative Example 5 after exposure.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0011] 以下、本発明のォキシムエステル化合物及び該化合物を有効成分とする光重合開 始剤について詳細に説明する。  Hereinafter, the oxime ester compound of the present invention and the photopolymerization initiator containing the compound as an active ingredient will be described in detail.
[0012] 上記一般式 (I)中、 Xで表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素 が挙げられ、 Xで表されるアルキル基としては、例えば、メチノレ、ェチル、プロピル、ィ ソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、ァミル、イソァミル、第三 アミノレ、へキシル、ヘプチル、ォクチル、イソォクチル、 2 _ェチルへキシル、第三オタ チル、ノニノレ、イソノエル、デシル、イソデシル、ビュル、ァリル、ブテュル、ェチュル、 プロピニノレ、メトキシェチノレ、エトキシェチノレ、プロピロキシェチノレ、メトキシェトキシェ チル、エトキシエトキシェチル、プロピロキシエトキシェチル、メトキシプロピル、モノフ ノレオロメチル、ジフルォロメチル、トリフルォロメチル、トリフルォロェチル、パーフルォ ロェチル、 2— (ベンゾォキサゾール— 2 '—ィル）ェテニル等が挙げられる。 In the above general formula (I), examples of the halogen atom represented by X include fluorine, chlorine, bromine, and iodine. Examples of the alkyl group represented by X include methinole, ethyl, propyl, Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-aminole, hexyl, heptyl, octyl, isooctyl, 2-ethyl hexyl, tert-octyl, noninore, isonoel, decyl, isodecyl , Bulle, arryl, butur, ethur, propyninore, methoxyethinole, ethoxyethinole, propiroxychechinole, methoxyethoxyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluorochloromethyl, difluoromethyl, trifluoromethyl, Trifluoroethyl, perful Loetyl, 2- (benzoxazole-2′-yl) ethenyl and the like.
[0013] R及び R'で表されるアルキル基としては、例えば、メチル、ェチル、プロピル、イソプ 口ピル、ブチル、イソブチル、第二ブチル、第三ブチル、ァミル、イソァミル、第三アミ ノレ、へキシル、ヘプチル、ォクチル、イソォクチル、 2 _ェチルへキシル、第三ォクチ ノレ、ノニル、イソノニル、デシル、イソデシル、ビュル、ァリル、ブテュル、ェチュル、プ ロビニノレ、メトキシェチノレ、エトキシェチノレ、プロピロキシェチノレ、メトキシェトキシェチ ノレ、エトキシェトキシェチノレ、プロピロキシェトキシェチノレ、メトキシプロピノレ、モノフノレ ォロメチル、ジフルォロメチル、トリフルォロメチル、トリフルォロェチル、パーフルォロ ェチル、 2- (ベンゾォキサゾール— 2'—ィル）ェテュル等が挙げられ、 R及び R'で 表されるァリール基としては、例えば、フエニル、トリル、キシリル、ェチルフエニル、ク ロロフエ二ノレ、ナフチル、アンスリル、フエナンスレニル等が挙げられ、 R及び R'で表 されるァラルキル基としては、例えば、べンジル、クロ口べンジノレ、 ひ一メチルベンジ ノレ、 ひ、 α—ジメチルベンジル、フエニルェチル、フエニルェテニル等が挙げられ、 R 及び R'で表される複素環基としては、例えば、ピリジル、ピリミジル、フリル、チォフエ ニル等が挙げられ、また、 R及び R'が一緒になつて形成しうる環としては、例えば、ピ ペリジン環、モルホリン環等が挙げられる。 [0013] Examples of the alkyl group represented by R and R 'include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amino, Xylyl, heptyl, octyl, isooctyl, 2_ethylhexyl, tertiary octanol, nonyl, isononyl, decyl, isodecyl, bur, arryl, butul, echul, provininole, methoxyethynole, ethoxyethinole, propiroxychechinole, methoxyethoxy Shetinore, ethoxycetochetinole, propyloxetechinochinole, methoxypropinole, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazole-2 ' -Il) Etul, etc., and R and R ' Examples of the aryl group include phenyl, tolyl, xylyl, ethenyl phenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like. Examples of the aralkyl group represented by R and R ′ include benzyl, Examples of the heterocyclic group represented by R 1 and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl, and the like. Examples of the ring that can be formed by combining R and R ′ include a piperidine ring and a morpholine ring.
[0014] Αで表されるシクロアルキルアルキル基としては、シクロプロピノレメチノレ、 2—シクロ プロピルェチル、 3—シクロプロピルプロピル、シクロブチルメチル、 2—シクロブチル ェチル、 3—シクロブチルプロピル、シクロペンチルメチル、 2—シクロペンチルェチ ノレ、 3—シクロペンチルプロピル、シクロへキシルメチル、 3—シクロへキシルプロピル 、 2—クロロー 3—シクロへキシルプロピル等が挙げられる。 [0014] Examples of the cycloalkylalkyl group represented by Α include cyclopropinoremethinole, 2-cyclopropylethyl, 3-cyclopropylpropyl, cyclobutylmethyl, 2-cyclobutylethyl, 3-cyclobutylpropyl, cyclopentylmethyl, Examples include 2-cyclopentylethanol, 3-cyclopentylpropyl, cyclohexylmethyl, 3-cyclohexylpropyl, 2-chloro-3-cyclohexylpropyl, and the like.
[0015] 本発明のォキシムエステル化合物の中でも、上記一般式（I)において、 Xがアルキ ル基、特にメチル基であるもの； Rがアルキル基、特にメチル基であるもの； Rがァノレ [0015] Among the oxime ester compounds of the present invention, in the above general formula (I), those in which X is an alkyl group, particularly a methyl group; those in which R is an alkyl group, particularly a methyl group;
1 2 キル基、特にメチル基であるもの； Rがアルキル基、特にェチル基であるもの； Aがシ  1 2 Kill group, especially methyl group; R is alkyl group, especially ethyl group;
3  Three
クロアルキルアルキル基、特にシクロへキシルメチル基であるもの； mが 1であるもの が好ましい。  Those having a chloroalkyl group, particularly a cyclohexylmethyl group; those in which m is 1 are preferred.
[0016] 従って、上記一般式 (I)で表される本発明のォキシムエステル化合物の好ましい具 体例としては、以下の化合物 No.：!〜 No. 3の化合物が挙げられる。ただし、本発明 は以下の化合物により何ら制限を受けるものではなレ' Accordingly, preferred specific examples of the oxime ester compound of the present invention represented by the above general formula (I) include the following compounds No .:! To No. 3. However, the present invention Is not limited by the following compounds.
[0017] [化 2] 化合物 Να  [0017] [Chemical 2] Compound Να
Figure imgf000006_0001
Figure imgf000006_0001
[0018] [化 3] 化合物 No. 2  [0018] [Chemical 3] Compound No. 2
Figure imgf000006_0002
Figure imgf000006_0002
[0019] [化 4] 化合物 No. 3  [0019] [Chemical 4] Compound No. 3
Figure imgf000006_0003
Figure imgf000006_0003
[0020] 上記一般式 (I)で表される本発明のォキシムエステル化合物は、一般的に以下の 方法により製造することができる。まず、カルバゾールイ匕合物 1とカルボン酸クロリド 2 及び Xの 1つがハロゲン原子であるカルボン酸クロリド 3を同時又は順次に塩化亜鉛 の存在下に反応させてァシル化合物 4を得る。次いで、ァシル化合物 4とアルコール 化合物 5とをカリウム —ブトキシドの存在下に反応させてァシル体 6を得る。アルコ ール化合物は、アシノレ化反応を行う前にカルボン酸クロリドに付加させてもよレ、。次 いで、ァシル体 6と塩酸ヒドロキシルァミンとを DMFの存在下に反応させてォキシム 化合物 7を得る。次いで、ォキシム化合物 7と酸無水物 8あるいは酸クロライド 8'を反 応させて上記一般式 (I)で表される本発明のォキシムエステル化合物を得る。例えば 、化合物 No. 1は、下記 [化 5]の反応式で示される方法によって製造することができる [0020] The oxime ester compound of the present invention represented by the general formula (I) can be generally produced by the following method. First, carbazole compound 1 and carboxylic acid chloride 3 in which one of carboxylic acid chlorides 2 and X is a halogen atom are reacted simultaneously or sequentially in the presence of zinc chloride to obtain acyl compound 4. Next, the acyl compound 4 and alcohol Compound 5 is reacted in the presence of potassium butoxide to give acyl 6 The alcohol compound may be added to the carboxylic acid chloride before the acylation reaction. Next, the acyl compound 6 and hydroxylamine hydrochloride are reacted in the presence of DMF to obtain the oxime compound 7. Next, the oxime compound 7 and the acid anhydride 8 or the acid chloride 8 ′ are reacted to obtain the oxime ester compound of the present invention represented by the above general formula (I). For example, Compound No. 1 can be produced by a method represented by the following reaction formula [Chemical Formula 5]
[0021] [化 5]
Figure imgf000007_0001
[0021] [Chemical 5]
Figure imgf000007_0001
力ル 化合物 1 カルボン酸 カルボン酸  Compound 1 Carboxylic acid Carboxylic acid
ク□ Uド 2 クロリド 3 ァシル化合物 4 ァシル化合物 4 A-0H  U U 2 Chloride 3 Casyl compound 4 Casyl compound 4 A-0H
アルコール ァシル体 6 Alcohol body 6
Figure imgf000007_0002
Figure imgf000007_0002
才キシ厶化合物 7  Talented Ki Compound 7
» 才キシ厶化合物 7 酸
Figure imgf000007_0003
»Tasty Xi compounds 7 acids
Figure imgf000007_0003
睃クロライド 8 ' —般式  睃 Chloride 8 '— General formula
(才キシムエステル化合物）  (A talented oxime ester compound)
[0022] 本発明のォキシムエステル化合物は、エチレン性不飽和結合を有する重合性化合 物の光重合開始剤として有用である。 [0022] The oxime ester compound of the present invention is useful as a photopolymerization initiator for a polymerizable compound having an ethylenically unsaturated bond.
[0023] 次に、本発明の感光性組成物について説明する。 Next, the photosensitive composition of the present invention will be described.
[0024] エチレン性不飽和結合を有する上記重合性化合物としては、従来、感光性組成物 に用いられているものを用いることができる。即ち、エチレン性不飽和結合を有する 上記重合性化合物としては、例えば、スチレン、 ひ一メチルスチレン、クロロスチレン 等のスチレン系化合物；メチル (メタ）アタリレート、ェチル (メタ）アタリレート、 n—プロ ピル (メタ）アタリレート、イソプロピル (メタ）アタリレート、 n—ブチル (メタ）アタリレート、 イソブチル (メタ）アタリレート、第二ブチル (メタ）アタリレート、第三ブチル (メタ）アタリ レート、テトラヒドロフリル（メタ）アタリレート、 2—ェチルへキシル（メタ）アタリレート、ラ ゥリノレ（メタ）アタリレート、ステアリノレ（メタ）アタリレート、シクロへキシル（メタ）アタリレー チル (メタ）アタリレート、エトキシェチル (メタ）アタリレート、ポリ（エトキシ）ェチル (メタ） アタリレート、プロピルォキシェチル（メタ）アタリレート、ブトキシェチル（メタ）アタリレ ート、ブトキシエトキシェチル (メタ）アタリレート、ポリ（プロピルォキシ）プロピル (メタ） アタリレート、ビュル（メタ）アタリレート、エチレングリコールジ（メタ）アタリレート、ジェ チレングリコールジ（メタ）アタリレート、トリエチレングリコールジ（メタ）アタリレート、ポリ エチレングリコールジ（メタ）アタリレート、プロピレングリコールジ（メタ）アタリレート、ポ リプロピレングリコールジ（メタ）アタリレート、 1， 4_ブタンジオールジ（メタ）アタリレー ト、ネオペンチルグリコールジ（メタ）アタリレート、 1, 6—へキサンジオールジ（メタ）ァ タリレート、トリメチロールプロパントリ（メタ）アタリレート、トリメチロールェタントリ（メタ） アタリレート、トリス（2—アタリロイルェチル）イソシァヌラート、ペンタエリスリトールペン タ（メタ）アタリレート、ペンタエリスリトールテトラ（メタ）アタリレート等の多価アルコール を α , 不飽和カルボン酸でエステル化して得られる化合物；アクリロニトリル、 （メ タ）アクリルアミド、 N—置換（メタ）アタリレート；酢酸ビエル、イソブチルビニルエーテ ノレ、 N ビュルピロリドン、ビニルクロリド、ビニリデンク口リド、ジビニルベンゼン、ジビ ニルスクシナート、ジァリルフタラート、トリアリルホスフアート、トリアリルイソシァヌラー ト等が挙げられる。これらの中でも、スチレン、メチル (メタ）アタリレート、 n—ブチル (メ タ）アタリレート、ヒドロキシェチル（メタ）アタリレートに、本発明のォキシムエステル化 合物を有効成分とする光重合開始剤は好適である。 [0024] As the polymerizable compound having an ethylenically unsaturated bond, those conventionally used in photosensitive compositions can be used. That is, examples of the polymerizable compound having an ethylenically unsaturated bond include styrene compounds such as styrene, monomethylstyrene, and chlorostyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-pro Pyr (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tetrahydrofuryl (Meth) Atarylate, 2-Ethylhexyl (Meth) Atylate, Laurinole (Meth) Atarylate, Stearinore (Meth) Atarylate, Cyclohexyl (Meth) Attalylyl (Meth) Atarylate, Ethoxyethyl (Meth) Atarylate, poly (ethoxy) ethyl (meth) acrylate, propyloxetyl (meth) acrylate, butoxychetil (meth) acrylate, butoxyethoxyethyl (meth) acrylate, poly (propyloxy) propyl (meth) Atallate, Bulle (Meta) Atrelay , Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, poly Ripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, tris (2- allyloylethyl) isocyanurate, pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate Alcohol Compound obtained by esterification of α with unsaturated carboxylic acid; acrylonitrile, (meth) acrylamide, N-substituted (meth) acrylate, vinyl acetate, isobutyl vinyl ether, N bull pyrrolidone, vinyl chloride, vinylidene mouth Lido, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate and the like. Among these, styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, hydroxyethyl (meth) acrylate, and photopolymerization starting with the oxime ester compound of the present invention as an active ingredient Agents are preferred.
また、エチレン性不飽和結合を有する上記重合性化合物とともに、熱可塑性有機 重合体を用いることによって、硬化物の特性を改善することもできる。該熱可塑性有 機重合体としては、例えば、ポリスチレン、ポリメチルメタタリレート、メチルメタクリレー ト—ェチルアタリレート共重合体、ポリ（メタ）アクリル酸、スチレン—（メタ）アクリル酸共 重合体、 （メタ）アクリル酸—メチルメタタリレート共重合体、ポリビュルブチラール、セ ルロースエステル、ポリアクリノレアミド、飽和ポリエステル、エポキシ樹脂等が挙げられ 、これらの中でも、ポリスチレン、（メタ）アクリル酸一メチルメタタリレート共重合体、ェ ポキシ樹脂が好ましい。 In addition, the properties of the cured product can be improved by using a thermoplastic organic polymer together with the polymerizable compound having an ethylenically unsaturated bond. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer. , (Meth) acrylic acid-methyl methacrylate copolymer, polybutyral, Examples include, but are not limited to, polystyrene, polyacrylolamide, saturated polyester, and epoxy resin. Among these, polystyrene, (meth) acrylic acid monomethyl methacrylate copolymer, and epoxy resin are preferable.
[0026] また、本発明の感光性組成物には、光重合開始剤として、本発明のォキシムエステ ル化合物の他に、必要に応じて他の光重合開始剤を併用することも可能であり、そ の他の光重合開始剤を併用することによって著しい相乗効果を奏する場合もある。  [0026] Further, in the photosensitive composition of the present invention, as the photopolymerization initiator, in addition to the oxime ester compound of the present invention, another photopolymerization initiator can be used in combination, if necessary. In some cases, other photopolymerization initiators may be used in combination to produce a remarkable synergistic effect.
[0027] 本発明のォキシムエステルイ匕合物と併用できる光重合開始剤としては、従来既知 の化合物を用いることが可能であり、例えば、ベンゾフエノン、フエ二ルビフエ二ルケト ン、 1—ヒドロキシ _ 1 _ベンゾィルシクロへキサン、ベンジル、ベンジルジメチルケタ ール、 1 _ベンジル一 1—ジメチルァミノ _ 1― (4' _モルホリノべンゾィノレ）プロパン、 2 _モルホリル _ 2 _ (4'—メチルメルカプト）ベンゾィルプロパン、チォキサントン、 1 —クロル _4 _プロポキシチォキサントン、イソプロピルチォキサントン、ジェチルチオ キサントン、ェチルアントラキノン、 4一べンゾィルー 4'ーメチルジフエニルスルフイド、 ベンゾインブチルエーテル、 2—ヒドロキシー2—ベンゾィルプロパン、 2—ヒドロキシ - 2 - (4 '—イソプロピル）ベンゾィルプロパン、 4 ブチルベンゾィルトリクロロメタン、 4 フエノキシベンゾィルジクロロメタン、ベンゾィル蟻酸メチル、 1 , 7—ビス（9'ーァク リジニノレ）ヘプタン、 9—n—ブチノレー 3, 6 ビス（2 '—モルホリノイソブチロイル）カル バゾール、 2—メチル 4, 6 ビス（トリクロロメチル） s トリアジン、 2 フエ二ノレ一 4, 6 ビス（トリクロロメチル） s トリァジン、 2 ナフチル一 4, 6 ビス（トリクロロメ チル） s トリアジン、 2, 2 ビス（2 クロ口フエ二ル）一 4, 5, 4 ' , 5 '—テトラフエ二 ルー 1 2 '—ビイミダゾール等が挙げられる。  As the photopolymerization initiator that can be used in combination with the oxime ester compound of the present invention, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl, 1-hydroxy_ 1_Benzylcyclohexane, benzyl, benzyldimethylketal, 1_benzyl mono 1-dimethylamino_ 1- (4'_morpholinobenzoinole) propane, 2_morpholyl_2_ (4'-methylmercapto) benzoyl Propane, thixanthone, 1-chloro _4 _propoxythixanthone, isopropyl thixanthone, jetylthioxanthone, ethylanthraquinone, 4-benzoyl 4'-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane , 2-hydroxy-2- (4'-isopropyl) benzoyl Lopan, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-alkylininole) heptane, 9-n-butynole 3,6bis (2'-morpholino) Isobutyroyl) carbazole, 2-methyl 4,6 bis (trichloromethyl) s triazine, 2 phenylol 4,6 bis (trichloromethyl) s triazine, 2 naphthyl 1,4,6 bis (trichloromethyl) s Examples include triazine, 2,2 bis (2-chlorophenyl) -1,4,5,4 ', 5'-tetraphenyl1,2'-biimidazole, and the like.
[0028] また、本発明の感光性組成物には、必要に応じて、 p _ァニソール、ハイドロキノン 、ピロカテコール、第三ブチルカテコール、フヱノチアジン等の熱重合抑制剤；可塑 剤；接着促進剤；充填剤等の慣用の添加物を加えることができる。  [0028] In addition, the photosensitive composition of the present invention includes, as necessary, thermal polymerization inhibitors such as p_anisole, hydroquinone, pyrocatechol, tert-butylcatechol, and funothiazine; plasticizer; adhesion promoter; filling Conventional additives such as agents can be added.
[0029] 本発明の感光性組成物には、通常、必要に応じて前記の各成分 (本発明のォキシ ムエステル化合物及びエチレン性不飽和結合を有する重合性化合物）を溶解または 分散しえる溶媒、例えば、アセトン、メチルェチルケトン、メチルイソプチルケトン、メチ ノレセロソルブ、ェチルセ口ソルブ、クロ口ホルム、塩化メチレン、へキサン、ヘプタン、 オクタン、シクロへキサン、ベンゼン、トルエン、キシレン、メタノーノレ、エタノール、イソ プロパノールを加えることができる。 [0029] The photosensitive composition of the present invention usually contains a solvent capable of dissolving or dispersing each of the above components (the oxime ester compound of the present invention and the polymerizable compound having an ethylenically unsaturated bond), if necessary. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methineless cellosolve, ethyl acetate sorb, black mouth form, methylene chloride, hexane, heptane, Octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol can be added.
[0030] 本発明の感光性組成物は、ロールコーター、カーテンコーター、各種の印刷、浸漬 等の公知の手段で、金属、紙、プラスチック等の支持基体上に適用される。また、一 旦フィルム等の支持基体上に施した後、他の支持基体上に転写することもでき、その 適用方法に制限はない。  [0030] The photosensitive composition of the present invention is applied onto a support substrate such as metal, paper, plastic, and the like by a known means such as a roll coater, a curtain coater, various types of printing and dipping. In addition, after application on a support substrate such as a film, it can be transferred onto another support substrate, and the application method is not limited.
[0031] 本発明の感光性組成物は、光硬化性塗料、光硬化性インキ、光硬化性接着剤、印 刷版、印刷配線板用フォトレジスト等の各種の用途に使用することができ、その用途 に特に制限はない。  [0031] The photosensitive composition of the present invention can be used for various applications such as a photocurable paint, a photocurable ink, a photocurable adhesive, a printing plate, a photoresist for a printed wiring board, and the like. There are no particular restrictions on its use.
[0032] また、本発明のォキシムエステル化合物を含有する感光性組成物を硬化させる際 に用いられる活性光の光源としては、波長 300〜450nmの光を発光するものを用い ること力 Sでき、例えば、超高圧水銀、水銀蒸気アーク、カーボンアーク、キセノンァー ク等を用いることができる。  [0032] In addition, as a light source of active light used when curing the photosensitive composition containing the oxime ester compound of the present invention, it is possible to use a light source that emits light having a wavelength of 300 to 450 nm. For example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be used.
[0033] 尚、本発明の感光性組成物において、光重合開始剤の添力卩量は特に限定されるも のではないが、本発明のォキシムエステルイ匕合物は、エチレン性不飽和結合を有す る上記重合性化合物 100重量部に対して、好ましくは 1〜50重量部、より好ましくは 5 〜 30重量部である。  [0033] In the photosensitive composition of the present invention, the additive amount of the photopolymerization initiator is not particularly limited, but the oxime ester compound of the present invention is an ethylenically unsaturated compound. The amount is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymerizable compound having a bond.
実施例  Example
[0034] 以下、実施例等を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実 施例に限定されるものではない。  Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples.
[0035] [実施例 1]化合物 No. 1の製造 [0035] [Example 1] Production of compound No. 1
<ステップ 1 > 4 _フルォロ― 2 _メチル安息香酸クロリドの製造  <Step 1> Production of 4_Fluoro-2_Methylbenzoic acid chloride
下記構造を持つ 4_フルオロー 2_メチル安息香酸クロリドを、以下のようにして製 造した。  4_Fluoro-2-methylbenzoic acid chloride having the following structure was prepared as follows.
[0036] [化 6] [0036] [Chemical 6]
Figure imgf000010_0001
[0037] 窒素雰囲気下で 4 フルオロー 2—メチル安息香酸 20· 0g (0. 13モノレ）、 N, N— ジメチルホルムアミド 0· 10g (l . 3ミリモル）及びトルエン 134gを仕込み、室温にて塩 化チォニル 23. 2g (0. 20モル）を滴下し、 60〜65°Cに昇温して 1時間攪拌した。溶 媒を留去し、減圧下、 50°Cで乾燥して褐色液体 19. 7g (収率 88%、 GC純度 99%) を得た。
Figure imgf000010_0001
[0037] Under a nitrogen atmosphere, 4 fluoro-2-methylbenzoic acid 20 · 0 g (0.13 monole), N, N-dimethylformamide 0 · 10 g (l.3 mmol) and toluene 134 g were charged and salified at room temperature. Thionyl 23.2g (0.20mol) was dripped, it heated up at 60-65 degreeC and stirred for 1 hour. The solvent was distilled off and dried under reduced pressure at 50 ° C. to obtain 19.7 g (yield 88%, GC purity 99%) of a brown liquid.
[0038] 得られた褐色液体の IR測定の結果は次の通りであり、該褐色液体は目的物である ことを確認した。  The results of IR measurement of the obtained brown liquid were as follows, and it was confirmed that the brown liquid was the target product.
IR測定：（cm 1) IR measurement: (cm 1 )
2985、 2931、 1766、 1606、 1579、 1486、 1450、 1384、 1240、 1189、 1105、 2985, 2931, 1766, 1606, 1579, 1486, 1450, 1384, 1240, 1189, 1105,
964、 869、 823 964, 869, 823
[0039] <ステップ 2 >ァシル体の製造 [0039] <Step 2> Production of asil
下記ァシル体を、以下のようにして製造した。  The following acyl compounds were produced as follows.
[0040] [化 7] [0040] [Chemical 7]
ァシル体
Figure imgf000011_0001
Ashiru
Figure imgf000011_0001
[0041] モノクロ口ベンゼン 33· lg、 N—ェチルカルバゾール 21 · 5g (0. 11モル）及び塩 化亜鉛 1 · 40g (10ミリモノレ）を混合して 80。Cまで昇温し、 4 フルォロ一 2—メチル安 息香酸クロリド 17. 3g (0. 10モル）を滴下した。 80〜85°Cで 1時間攪拌後、室温ま で冷却した。 n ヘプタン 33. lg及び水 16. 5gを加えて油層を分離し、 1%水酸化 ナトリウム水溶液 8. 30gをカ卩えて中和し、さらに水 40. Ogを 2回に分けて加えて油層 を洗浄した。油層を分離して n—ヘプタンを留去し、モノクロ口ベンゼン溶液 50. Ogを 得た。得られたモノクロ口ベンゼン溶液にモノクロ口ベンゼン 90. Ogを滴下し、塩ィ匕ァ ノレミニゥム 40. Ogをカロえて 10〜： 15。Cに冷去 Pした。塩ィ匕ァセチノレ 9. 90g (0. 13モノレ )を 10〜20°Cで滴下し、室温で 1時間攪拌した。反応液を、二塩ィ匕ェタン 224g及び 氷水 134gを混合したものに 25〜30°Cで滴下した。油層を分離し、 5%HC1水溶液 4 0g、水 40g、 2%Na〇H水溶液 40gの順に洗浄した。二塩化エタンを留去し、酢酸 n プロピル 74.6gから再結晶を行った。ろ過、酢酸 n—プロピル/ n—ヘプタン混合 溶媒による洗浄を経て、淡黄色固体 22.4g (収率 60%、 HPLC純度 98%)を得た。 [0041] Monoclonal benzene 33 · lg, N-ethylcarbazole 21 · 5 g (0.11 mol) and zinc chloride 1 · 40 g (10 millimonoles) were mixed 80. The temperature was raised to C, and 17.3 g (0.10 mol) of 4-fluoro-2-methylbenzoic acid chloride was added dropwise. After stirring at 80 to 85 ° C for 1 hour, the mixture was cooled to room temperature. n Add 33. lg of heptane and 16.5 g of water to separate the oil layer, neutralize 8.30 g of 1% aqueous sodium hydroxide solution, and add 40. Og of water in two portions to add the oil layer. Washed. The oil layer was separated and n-heptane was distilled off to obtain 50. 90. Og of black and white benzene was added dropwise to the resulting black and white benzene solution to give 40.Og of salt. Cooled to C. 9.90 g (0.13 monole) of salt acetylene was added dropwise at 10 to 20 ° C. and stirred at room temperature for 1 hour. The reaction solution was added dropwise to a mixture of 224 g of disodium ethane and 134 g of ice water at 25 to 30 ° C. The oil layer was separated and washed in the order of 40 g of 5% HC1 aqueous solution, 40 g of water, and 40 g of 2% NaOH aqueous solution. Dichloroethane is distilled off and acetic acid n Recrystallization was performed from 74.6 g of propyl. Filtration and washing with a mixed solvent of n-propyl acetate / n-heptane gave 22.4 g of a pale yellow solid (yield 60%, HPLC purity 98%).
[0042] 得られた淡黄色結晶は、融点 175°Cで、 NMRのケミカルシフト及び IRの測定 結果は次の通りであり、 目的物であるァシル体であることを確認した。 [0042] The obtained pale yellow crystal had a melting point of 175 ° C and the NMR chemical shift and IR measurement results were as follows, confirming that it was the target acyl compound.
iH NMR測定：（ppm)  iH NMR measurement: (ppm)
8.70(s:lH)、 8.52(s:lH)、 8.17(d:lH)、 8.09(d:lH)、 7.50(s:lH)、 7. 48(d:lH)、 7.39(d:lH)、 7.05(d:lH)、 7.00(d:lH)、 4.45(d:2H)、 2.7 3(s:3H)、 2.37(s:3H)、 1.49(t:3H)  8.70 (s: lH), 8.52 (s: lH), 8.17 (d: lH), 8.09 (d: lH), 7.50 (s: lH), 7.48 (d: lH), 7.39 (d: lH) 7.05 (d: lH), 7.00 (d: lH), 4.45 (d: 2H), 2.7 3 (s: 3H), 2.37 (s: 3H), 1.49 (t: 3H)
IR測定：（cm1) IR measurement: (cm 1 )
3448、 3054、 2064、 1662、 1625、 1589、 1567、 1484、 1386、 1305、 1245、 1153、 1124、 1022、 809  3448, 3054, 2064, 1662, 1625, 1589, 1567, 1484, 1386, 1305, 1245, 1153, 1124, 1022, 809
[0043] <ステップ 3 >化合物 No.1の製造  [0043] <Step 3> Production of Compound No. 1
窒素気流下、シクロへキサンメタノール 57. lg(0.5モル）及び 1, 3 ジメチルー 2 —イミダゾリジノン 66.0gを仕込み、 30〜40。Cでカリウム— t ブトキシド 8.4g(0.0 75モノレ）を加えて 73〜75°Cまで昇温した。続いてステップ 2で得られたァシル体の 1 8.7g(0.05モノレ）をカロ免て 1時間 禅した。塩酸ヒドロキシノレ了ミン 6.3g(0.09モ ノレ）を加えて 73〜75°Cで 1時間攪拌後、室温まで冷却した。酢酸 n プロピル 48.2 g及び 4%水酸化カリウム水溶液 24. lgをカ卩えて油層を分離し、水 75gを 2回に分け て加えて油層を洗浄した。油層を分離して脱水後、 60〜70°Cで無水酢酸 6. lg(0. 06モル）を加え、 80〜90°Cで 1時間攪拌した。室温まで冷却すると淡黄色固体が析 出した。ろ過、酢酸 n—プロピル/ n—ヘプタンによる洗浄を経て、淡黄色結晶 10g( 収率 38%、 HPLC純度 99%<)を得た。該淡黄色結晶について分析を行ったところ 、該淡黄色結晶は目的物である化合物 No.1であることが確認された。分析結果を 以下に示す。  Under nitrogen flow, cyclohexanemethanol 57. lg (0.5 mol) and 1,3 dimethyl 2 —imidazolidinone 66.0 g were charged, 30-40. With C, potassium-t butoxide (8.4 g, 0.075 monole) was added, and the temperature was raised to 73 to 75 ° C. Subsequently, 1 8.7 g (0.05 monole) of the isacyl obtained in step 2 was calo-free and Zen for 1 hour. After adding 6.3 g (0.09 monole) of hydroxynore hydrochloride hydrochloride and stirring at 73-75 ° C. for 1 hour, the mixture was cooled to room temperature. 48.2 g of n-propyl acetate and 24. lg of 4% aqueous potassium hydroxide solution were added to separate the oil layer, and 75 g of water was added in two portions to wash the oil layer. After the oil layer was separated and dehydrated, 6. lg (0.06 mol) of acetic anhydride was added at 60 to 70 ° C, and the mixture was stirred at 80 to 90 ° C for 1 hour. A pale yellow solid was precipitated upon cooling to room temperature. Filtration and washing with n-propyl acetate / n-heptane gave 10 g of pale yellow crystals (yield 38%, HPLC purity 99% <). When the pale yellow crystal was analyzed, it was confirmed that the pale yellow crystal was the target compound No. 1. The analysis results are shown below.
[0044] (分析結果）  [0044] (Analysis results)
(1)融点： 148.2°C  (1) Melting point: 148.2 ° C
(S^H— NMR測定：（ppm)  (S ^ H—NMR measurement: (ppm)
8.50(d:lH)、 8.44(d:lH)、 8.08(dd:lH)、 7.98(dd:lH)、 7.47(d:lH)、 7.45(d:lH)、 7.37(d:lH)、 6.86(d:lH)、 6.78 (dd: 1H)、 4.43(q:2H)、 3 .84(d:2H)、 2.52(s:3H)、 2.40(s:3H)、 2.30(s:3H)、 1.92-1.71(m:6H )、 1.48(t:3H)l.38-1.04(m:5H) 8.50 (d: lH), 8.44 (d: lH), 8.08 (dd: lH), 7.98 (dd: lH), 7.47 (d: lH), 7.45 (d: lH), 7.37 (d: lH), 6.86 (d: lH), 6.78 (dd: 1H), 4.43 (q: 2H), 3.84 (d: 2H), 2.52 (s: 3H) 2.40 (s: 3H), 2.30 (s: 3H), 1.92-1.71 (m: 6H), 1.48 (t: 3H) l.38-1.04 (m: 5H)
(3) IR測定：（cm-1) (3) IR measurement: (cm- 1 )
2927、 2853、 1751、 1649、 1626、 1605、 1590、 1568、 1488、 1450、 1376、 1308、 1275、 1244、 1149、 1129、 1044、 1009、 983、 941、 894、 812、 772 2927, 2853, 1751, 1649, 1626, 1605, 1590, 1568, 1488, 1450, 1376, 1308, 1275, 1244, 1149, 1129, 1044, 1009, 983, 941, 894, 812, 772
(4) UVスペクトル測定（ァセトニトリル：水 = 9： 1)(4) UV spectrum measurement (acetonitrile: water = 9: 1)
max=273、 299、 341nm  max = 273, 299, 341nm
(5)分解温度測定 (窒素ガス雰囲気下、昇温速度 10°CZ分、 5%重量減少温度） 241.2°C  (5) Decomposition temperature measurement (in nitrogen gas atmosphere, heating rate 10 ° CZ min, 5% weight loss temperature) 241.2 ° C
[0045] [実施例 2]感光性組成物 No.1の製造  [0045] [Example 2] Production of photosensitive composition No. 1
アクリル系共重合体 14gに対し、トリメチロールプロパントリアタリレート 5.9g、実施 例 1で得られた化合物 No. 1の 2.7g及びェチルセ口ソルブ 79gを加えて良く攪拌し 、感光性組成物 No.1を得た。  To acrylic copolymer 14g, trimethylolpropane tritalylate 5.9g, 2.7g of compound No. 1 obtained in Example 1 and ethyl acetate sorb 79g were added and stirred well, photosensitive composition No. Got one.
尚、上記アクリル系共重合体は、メタクリル酸 20質量部、ヒドロキシェチルメタクリレ ート 15質量部、メチルメタタリレート 10質量部及びブチルメタタリレート 55質量部をェ チルセ口ソルブ 300質量部に溶解し、窒素雰囲気下でァゾビスイソブチル二トリル 0. 75質量部をカ卩えて 70°Cで 5時間反応させることにより得られたものである。  The acrylic copolymer is composed of 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate and 55 parts by mass of butyl methacrylate. It was obtained by dissolving 0.75 parts by mass of azobisisobutyl nitrile in a nitrogen atmosphere and reacting at 70 ° C for 5 hours.
[0046] [実施例 3]感光性組成物 No.2の製造 [0046] [Example 3] Production of photosensitive composition No. 2
アクリル系共重合体 7.2gに対し、トリメチロールプロパントリアタリレート 4.3g、実施 例 1で得られた化合物 No. 1の 2.0g及びェチルセ口ソルブ 87gを加えて良く攪拌し 、感光性組成物 No.2を得た。  To acrylic copolymer 7.2g, trimethylolpropane tritalylate 4.3g, 2.0g of compound No. 1 obtained in Example 1 and ethyl acetate mouthsolve 87g were added and stirred well. .2 was obtained.
[0047] [実施例 4]感光性組成物 No.3の製造 [0047] [Example 4] Production of photosensitive composition No. 3
スチレン—アクリル系感光性共重合体 14gに対し、ジペンタエリスリトールへキサァ タリレート 6.0g、実施例 1で得られた化合物 No.1の 1.3g、 2, 2_ビス（2—クロロフ ェニル）_4， 5, 4'， 5，一テトラフェニル _1_2，一ビイミダゾール 1.3g及びェチルセ 口ソルブ 83gを加えて良く攪拌し、感光性組成物 No.3を得た。  Dipentaerythritol hexaphthalate 6.0g with respect to 14g of styrene-acrylic photosensitive copolymer, 1.3g of compound No. 1 obtained in Example 1, 2, 2_bis (2-chlorophenyl) _4, Photosensitive composition No. 3 was obtained by adding 1.3 g of 5,4 ′, 5, monotetraphenyl_1_2, monobiimidazole and 83 g of ethyl acetate and stirring well.
尚、上記スチレン—アクリル系感光性共重合体は、スチレン 26.3質量部、 2—ヒド ロキシメタタリレート 43. 8質量部、メタクリル酸 35質量部及びメタクリル酸ェチル 70質 量部をェチルセ口ソルブ 175質量部に溶解し、窒素雰囲気下でァゾビスイソブチル 二トリル 0. 75質量部を加え 90°Cで 5時間反応させ、次いで、イソシァネートェチルメ タクリレート 23. 5質量部、ォクチル酸錫 0. 11質量部をェチルセ口ソルブ 20質量部 で溶解したものを約 10分かけて滴下し、滴下後 2時間反応させることにより得られた ものである。 The styrene-acrylic photosensitive copolymer is composed of 26.3 parts by mass of styrene and 2-hydride. Loxymetatalylate 43.8 parts by weight, 35 parts by weight of methacrylic acid and 70 parts by weight of ethyl acetate are dissolved in 175 parts by weight of ethyl acetate sorb, and 0.775 parts by weight of azobisisobutyl nitrile is dissolved in a nitrogen atmosphere. The mixture was reacted at 90 ° C for 5 hours, and then 23.5 parts by weight of isocyanatoethyl methacrylate and 0.11 part of tin octylate dissolved in 20 parts by weight of ethyl acetate sorb were added dropwise over about 10 minutes. Then, it was obtained by reacting for 2 hours after dropping.
[0048] [実施例 5]感光性組成物 No. 4の製造  [0048] [Example 5] Production of photosensitive composition No. 4
スチレン—アクリル系感光性共重合体 12gに対し、ジペンタエリスリトールペンタ及 びへキサアタリレート 8. lg、実施例 1で得られた化合物 No. 1の 2. 5g、ェチルセ口 ソルブ 47g及びシクロへキサノン 30gを加えて良く攪拌し、感光性組成物 No. 4を得 た。  12 g of styrene-acrylic photosensitive copolymer, 8. lg of dipentaerythritol penta and hexaatalylate, 2.5 g of compound No. 1 obtained in Example 1, 47 g of ethyl acetate and 47 g of cyclohexane 30 g of xanone was added and stirred well to obtain photosensitive composition No. 4.
[0049] [実施例 6]感光性組成物 No. 5の製造  [0049] [Example 6] Production of photosensitive composition No. 5
アクリル系共重合体 20gに対し、トリメチロールプロパントリアタリレート 8. 7g、実施 例 1で得られた化合物 No. 1の 2. 2g、ビスフエノール A型エポキシ樹脂 4. 6g及びェ チルセ口ソルブ 65gをカ卩えて良く攪拌し、感光性組成物 No. 5を得た。  20 g of acrylic copolymer, 8.7 g of trimethylolpropane tritalylate, 2.2 g of compound No. 1 obtained in Example 1, 4.6 g of bisphenol A type epoxy resin and 65 g of ethyl acetate sorb The mixture was stirred well and photosensitive composition No. 5 was obtained.
[0050] [比較例 1]感光性組成物 No. 6の製造 [0050] [Comparative Example 1] Production of photosensitive composition No. 6
実施例 2で用いたアクリル系共重合体 14gに対して、ジペンタエリスリトールペンタ 及びへキサアタリレート 5. 9g、比較化合物 1 (下記 [化 8]) 2. lg及びェチルセ口カレ ブ 78gを加えてよく攪拌し、感光性組成物 Νο· 6を得た。  To 14 g of the acrylic copolymer used in Example 2, 5.9 g of dipentaerythritol penta and hexaatalylate, comparative compound 1 (the following [Chemical Formula 8]) 2. lg and 78 g of ethyl acetate are added. The mixture was thoroughly stirred to obtain a photosensitive composition Νο · 6.
[0051] [化 8] [0051] [Chemical 8]
Figure imgf000014_0001
Figure imgf000014_0001
分解温度測定 （窒素ガス雰囲気下、 昇温速度 1 0 Z分、 5 %重量減少温度) 1 9 1 . 2 V  Decomposition temperature measurement (in nitrogen gas atmosphere, heating rate 10 Z min, 5% weight loss temperature) 1 9 1.2 V
[比較例 2]感光性組成物 No. 7の製造 [Comparative Example 2] Production of photosensitive composition No. 7
アクリル系共重合体の代わりに実施例 4で用いたスチレン—アクリル系感光性共重 合体を用いた以外は、比較例 1と同一の条件で感光性組成物 No. 7を得た。 Styrene-acrylic photosensitive copolymer used in Example 4 instead of acrylic copolymer Photosensitive composition No. 7 was obtained under the same conditions as in Comparative Example 1 except that the coalescence was used.
[0053] [比較例 3]感光性組成物 No. 8の製造 [0053] [Comparative Example 3] Production of photosensitive composition No. 8
実施例 2で用いたアクリル系共重合体 7. 2gに対して、トリメチロールプロパントリア タリレート 4. 3g、比較化合物 2 (下記 [化 9]) 1. 5g及びェチルセ口ソルブ 87gを加え て良く攪拌し、感光性組成物 No. 8を得た。  Add 7.2 g of trimethylolpropane tritalylate, 1.5 g of comparative compound 2 (the following [Chemical Formula 9]) and 87 g of ethyl acetate mouthsolve to 7.2 g of the acrylic copolymer used in Example 2, and stir well. Photosensitive composition No. 8 was obtained.
[0054] [化 9] [0054] [Chemical 9]
Figure imgf000015_0001
Figure imgf000015_0001
分解温度測定 （窒素ガス雰囲気下、 昇温速度 1 0で 分、 5 %重量減少温度) 2 3 2 . 2で  Decomposition temperature measurement (in nitrogen gas atmosphere, heating rate 10 min, 5% weight loss temperature) 2 3 2.2
[0055] [比較例 4]感光性組成物 No. 9の製造 [0055] [Comparative Example 4] Production of photosensitive composition No. 9
アクリル系共重合体の代わりに、実施例 4で用いたスチレン アクリル系感光性共 重合体を用いた以外は、比較例 3と同一の条件で感光性組成物 No. 9を得た。  Photosensitive composition No. 9 was obtained under the same conditions as in Comparative Example 3 except that the styrene-acrylic photosensitive copolymer used in Example 4 was used instead of the acrylic copolymer.
[0056] 得られた感光性組成物の評価は以下のようにして行った。すなわち、基板上に r グリシドキシプロピルメチルエトキシシランをスピンコートして良くスピン乾燥させた後、 上記感光性組成物 No.：!〜 9をスピンコート（1300r. p. m、 50秒間）し乾燥させた。 70°Cで 20分間プリベータを行った後、ポリビニルアルコール 5質量％溶液をコートし て酸素遮断膜とした。 70°C20分間の乾燥後、所定のマスクを用い、光源として超高 圧水銀ランプを用いて露光後、 2. 5%炭酸ナトリウム溶液に 25°Cで 30秒間浸漬して 現像し、良く水洗した。水洗乾燥後、 230°Cで 1時間ベータしてパターンを定着させ た。尚、露光量は、 80mj/cm2であった。得られたパターンについて、以下の評価 を行った。各感光性組成物に用いた光重合開始剤とその分解温度および各種評価 結果を表 1に示す。 [0056] The obtained photosensitive composition was evaluated as follows. That is, after spin-coating r-glycidoxypropylmethylethoxysilane on a substrate and spin-drying it well, the above photosensitive composition No .:! ~ 9 was spin-coated (1300 rpm, 50 seconds). Dried. After pre-beta for 20 minutes at 70 ° C, a 5% by mass solution of polyvinyl alcohol was coated to form an oxygen barrier film. After drying at 70 ° C for 20 minutes, using a specified mask, using an ultra-high pressure mercury lamp as the light source, after exposure, immerse in 2.5% sodium carbonate solution at 25 ° C for 30 seconds, develop, and rinse thoroughly . After washing with water and drying, beta was fixed at 230 ° C for 1 hour to fix the pattern. The exposure amount was 80 mj / cm 2 . The obtained pattern was evaluated as follows. Table 1 shows the photopolymerization initiator used in each photosensitive composition, its decomposition temperature, and various evaluation results.
[0057] <密着性>  [0057] <Adhesion>
JIS D 0202の試験方法に従レ、、露光現像した後 200°Cで 30分間加熱した塗膜 に基盤目状にクロスカットを入れ、次レ、でセロハンテープによってピーリングテストを 行い、基盤目の剥離の状態を目視により評価した。全く剥離が認められなかったもの を〇、剥離が認められたものを Xとした。 Coating film heated to 200 ° C for 30 minutes after exposure and development according to JIS D 0202 test method A cross cut was made in the shape of the substrate, and a peeling test was conducted with cellophane tape at the next stage, and the state of peeling of the substrate was visually evaluated. The case where peeling was not recognized at all was marked as ◯, and the case where peeling was observed was marked as X.
<耐アルカリ性 >  <Alkali resistance>
現像露光した後、 200°Cで 30分間加熱処理を行った。加熱処理後の塗膜を a) 5% NaOHaq. 中 24時間、 b) 4%K〇Haq. 中 50°Cで 10分間、 c) l%Na〇Haq. 中 80 After development exposure, heat treatment was performed at 200 ° C. for 30 minutes. Medium after heat treatment a) 5% NaOHaq. Medium 24 hours, b) 4% K0Haq. Medium 10 minutes at 50 ° C c) l% NaOHaq. Medium 80
°Cで 5分間の条件で浸漬し、浸漬後の外観を目視により評価した。外観変化もなくレ ジストの剥離も全くなかったものを〇、レジストの浮きが見られたものを△、レジストの 剥離が認められたものを Xとした。 Immersion was carried out at 5 ° C for 5 minutes, and the appearance after immersion was visually evaluated. The case where there was no change in the appearance and the resist was not peeled at all was marked as ◯, the case where the resist was lifted was marked as △, and the case where the resist was peeled off was marked as X.
<感度 > <Sensitivity>
露光量を、 50mj/cm2で行った以外は、上記の現像性の試験と同様にして露光部 の形状がマスクの形状に一致するものを 5、マスクの形状に対して面積で 5%以下で はあるが欠落が認められるものを 4、面積で 5〜20%の欠落があるものを 3、面積で 2 0〜50%の欠落があるものを 2、面積で 50%より欠落が大きいものを 1として 5段階で 評価した。結果を表 1に示す。 Except that the exposure was performed at 50 mj / cm 2 , 5 in which the shape of the exposed area matched the shape of the mask in the same manner as in the above developability test, 5% or less in area with respect to the mask shape However, there are 4 missing areas, 3 with 5 to 20% missing areas, 2 with 20 to 50% missing areas, and larger than 50% missing areas. 1 was evaluated on a 5-point scale. The results are shown in Table 1.
[表 1] [table 1]
Figure imgf000016_0001
実施例 1〜6及び比較例 1〜4より明らかなように本発明のォキシムエステル化合物 を用いた感光性組成物の密着性は公知のォキシムエステルィヒ合物の場合よりも同等 又は優れて、耐アルカリ性では優れている。特に比較例 1及び 2より密着性、耐アル カリ性に優れており、比較化合物 1との基本的な性能差であるか、比較化合物 1の耐 熱性が低いために 230°Cでの熱硬化処理において比較化合物 1が分解したために 感光性組成物の性能が低下したと考えられる。本発明のォキシムエステルイヒ合物は 、分解温度が 240°C以上と公知のォキシムエステル化合物より 9〜50°C耐熱性に優 れ、熱硬化処理温度において安定である。
Figure imgf000016_0001
As is clear from Examples 1 to 6 and Comparative Examples 1 to 4, the adhesion of the photosensitive composition using the oxime ester compound of the present invention is equal to or better than that of the known oxime ester compound. The alkali resistance is excellent. In particular, better adhesion and better resistance than Comparative Examples 1 and 2. Photosensitivity composition due to decomposition of comparative compound 1 in heat curing treatment at 230 ° C due to excellent potency and basic performance difference from comparative compound 1 or low heat resistance of comparative compound 1 It is thought that the performance of the object has deteriorated. The oxime ester ich compound of the present invention has a decomposition temperature of 240 ° C. or higher, better heat resistance of 9 to 50 ° C. than known oxime ester compounds, and is stable at the thermosetting temperature.
[0060] [実施例 7]露光処理における昇華性評価  [0060] [Example 7] Sublimation evaluation in exposure processing
化合物 No. 1の開始剤 0. 5gをプロピレングリコールモノメチルエーテルアセテート 10gに溶解し、アクリル系重合体（実施例 2に同じ) 0. 5gを加え、混合したものを直径 70mmのシャーレに入れて 70。Cで 12時間で乾燥した。シャーレに 100 X 100mmの 石英板を蓋になるように乗せて 10mj/cm2で 2時間露光した。石英板への附着物の 多少により昇華性を評価した。附着物は認められなかった。露光処理前後の石英板 の写真を図 1及び図 2に示す。 Compound No. 1 initiator 0.5g was dissolved in propylene glycol monomethyl ether acetate 10g, acrylic polymer (same as in Example 2) 0.5g was added, and the mixture was placed in a petri dish with a diameter of 70mm. . Dry in C for 12 hours. A 100 × 100 mm quartz plate was placed on the petri dish so as to cover it, and exposed at 10 mj / cm 2 for 2 hours. The sublimation property was evaluated by the amount of attachments to the quartz plate. There were no attachments. Figures 1 and 2 show photographs of the quartz plate before and after the exposure process.
[0061] [比較例 5]比較化合物における昇華性評価  [0061] [Comparative Example 5] Sublimation evaluation of comparative compounds
化合物 No. 1を比較化合物 2にかえた以外は、実施例 7と同様にして附着物を評 価した。多数の附着物があった。露光処理前後の石英板の写真を図 3及び図 4に示 す。  The attachments were evaluated in the same manner as in Example 7 except that Compound No. 1 was changed to Comparative Compound 2. There were numerous attachments. Figures 3 and 4 show photographs of the quartz plate before and after the exposure process.
[0062] 図 1は実施例 7に用いた石英板の露光前の写真であり、図 2は実施例 7に用いた石 英板の露光後の写真である。図 3は比較例 5に用いた石英板の露光前の写真であり 、図 4は比較例 5に用いた石英板の露光後の写真である。図 1、図 2、図 3の石英板に は附着物は認められない。図 4では無数の結晶状の附着物が認められる。  FIG. 1 is a photograph before exposure of the quartz plate used in Example 7, and FIG. 2 is a photograph after exposure of the stone plate used in Example 7. FIG. 3 is a photograph of the quartz plate used in Comparative Example 5 before exposure, and FIG. 4 is a photograph of the quartz plate used in Comparative Example 5 after exposure. No attachments are observed on the quartz plates in Figs. 1, 2 and 3. In Fig. 4, countless crystalline attachments are observed.
[0063] 実施例 7および比較例 5から本発明の化合物は露光後の昇華物がなぐマスク汚れ カ¾いと推測できる。一方、公知の光開始剤では昇華物が多量にあり、マスク汚れを 起こすと推測できる。よって、本発明の光開始剤を用いた硬化性組成物は連続使用 可能であるが、従来の光開始剤を用いた場合はマスクなど装置の洗浄が必要になる ので、本発明の光開始剤を用いることにより生産性の向上が期待できる。  [0063] From Example 7 and Comparative Example 5, it can be inferred that the compound of the present invention is a mask stain that sublimates after exposure do not have. On the other hand, it can be inferred that the known photoinitiator has a large amount of sublimation and causes mask contamination. Therefore, the curable composition using the photoinitiator of the present invention can be used continuously. However, when a conventional photoinitiator is used, it is necessary to clean an apparatus such as a mask. The use of can be expected to improve productivity.
産業上の利用可能性  Industrial applicability
[0064] 本発明のォキシムエステルイヒ合物は、高感度であり、且つ熱分解温度が高く感光 性組成物の密着性、耐アルカリ性を損なうことがなぐ更に光照射で発生する分解物 がマスクに付着することがない、光重合開始剤として有用なものである。 [0064] The oxime ester ricin compound of the present invention is highly sensitive and has a high thermal decomposition temperature and does not impair the adhesion and alkali resistance of the photosensitive composition. Is useful as a photopolymerization initiator that does not adhere to the mask.

Claims

請求の範囲 The scope of the claims
下記一般式 (I)で表されるォキシムエステル化合物。  An oxime ester compound represented by the following general formula (I):
Figure imgf000019_0001
Figure imgf000019_0001
(式中、 Xは水素原子、ハロゲン原子又はアルキル基を表し、 mが 2以上の場合、 複数の Xは各々異なる基でもよく、 Rい R 2及び R 3は R、 〇R、 C O R、 S R、 C O N R R ' 又は C Nを表し、 R及び R ' は、 アルキル基、 ァリール基、 ァラル キル基又は複素環基を表し、 これらはハロゲン原子及び Z又は複素環基で置換さ れていてもよく、これらのうちアルキル基及びァラルキル基のアルキレン部分は、 不飽和結合、 エーテル結合、 チォェ一テル結合、 エステル結合により中断されて いてもよく、 また、 R及び R ' は一緒になつて環を形成していてもよい。 Aはシ クロアルキルアルキル基を表し、 mは 1 ~ 4の正数を表す。） (In the formula, X represents a hydrogen atom, a halogen atom or an alkyl group, and when m is 2 or more, a plurality of Xs may be different from each other, R and R 2 and R 3 are R, 〇R, COR, SR , CONRR ′ or CN, R and R ′ represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom and Z or a heterocyclic group. Among them, the alkyl group and the alkylene part of the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioter bond, or an ester bond, and R and R ′ are joined together to form a ring. A represents a cycloalkylalkyl group, and m represents a positive number of 1 to 4.)
Xがアルキル基であることを特徴とする請求の範囲第 1項記載のォキシムエステル 化合物。 2. The oxime ester compound according to claim 1, wherein X is an alkyl group.
Rがアルキル基であることを特徴とする請求の範囲第 1又は 2項記載のォキシムェ The oxime according to claim 1 or 2, wherein R is an alkyl group.
1 1
ステル化合物。 Stealth compound.
Rがアルキル基であることを特徴とする請求の範囲第 1〜3項のいずれかに記載の The R according to any one of claims 1 to 3, wherein R is an alkyl group.
2 2
ォキシムエステル化合物。 Oxime ester compounds.
Rがアルキル基であることを特徴とする請求の範囲第 1〜4項のいずれかに記載の The R according to any one of claims 1 to 4, wherein R is an alkyl group.
3 Three
ォキシムエステル化合物。 Oxime ester compounds.
請求の範囲第 1〜5項のいずれかに記載のォキシムエステル化合物を有効成分と する光重合開始剤。  A photopolymerization initiator comprising the oxime ester compound according to any one of claims 1 to 5 as an active ingredient.
エチレン性不飽和結合を有する重合性化合物に、請求の範囲第 6項記載の光重 合開始剤を含有させてなる感光性組成物。  A photosensitive composition comprising a polymerizable compound having an ethylenically unsaturated bond and the photopolymerization initiator according to claim 6.
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CN117616337A (en) 2021-07-20 2024-02-27 株式会社艾迪科 Film forming material for semiconductor, member forming material for semiconductor, process member forming material for semiconductor, underlayer film forming material, underlayer film, and semiconductor device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004534797A (en) * 2001-06-11 2004-11-18 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド Oxime ester photoinitiators with combined structures
JP2005054012A (en) * 2003-08-01 2005-03-03 Toyo Ink Mfg Co Ltd Radical photopolymerization initiator and radical photopolymerizable composition using same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4590145A (en) * 1985-06-28 1986-05-20 Daicel Chemical Industries, Ltd. Photopolymerization initiator comprised of thioxanthones and oxime esters
SG77689A1 (en) * 1998-06-26 2001-01-16 Ciba Sc Holding Ag New o-acyloxime photoinitiators
NL1016815C2 (en) * 1999-12-15 2002-05-14 Ciba Sc Holding Ag Oximester photo initiators.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004534797A (en) * 2001-06-11 2004-11-18 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド Oxime ester photoinitiators with combined structures
JP2005054012A (en) * 2003-08-01 2005-03-03 Toyo Ink Mfg Co Ltd Radical photopolymerization initiator and radical photopolymerizable composition using same

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101687794B (en) * 2007-05-11 2013-09-11 巴斯夫欧洲公司 Oxime ester photoinitiators
WO2008138724A1 (en) * 2007-05-11 2008-11-20 Basf Se Oxime ester photoinitiators
US8911921B2 (en) 2007-05-11 2014-12-16 Ciba Corporation Oxime ester photoinitiators
EP2402315A1 (en) * 2007-05-11 2012-01-04 Basf Se Oxime ester photoinitiators
EP2037323A3 (en) * 2007-07-17 2009-12-02 FUJIFILM Corporation Photosensitive compositions, curable compositions, novel compounds, photopolymerizable compositions, color filters, and planographic printing plate precursors
EP2207062A3 (en) * 2007-07-17 2011-04-06 FUJIFILM Corporation Photosensitive compositions, curable compositions, novel compounds, photopolymerizable compositions, color filters, and planographic printing plate precursors
US8728686B2 (en) 2007-07-17 2014-05-20 Fujifilm Corporation Photosensitive compositions, curable compositions, novel compounds, photopolymerizable compositions, color filters, and planographic printing plate precursors
CN102617445A (en) * 2007-07-17 2012-08-01 富士胶片株式会社 Photosensitive compositions, curable compositions, novel compounds, photopolymerizable compositions, color filters, and planographic printing plate precursors
JP2009191061A (en) * 2007-08-27 2009-08-27 Fujifilm Corp New compound, photopolymerizable composition, photopolymerizable composition for color filter, color filter, and method for producing the same, solid-state imaging device, and planographic printing plate original
US8361681B2 (en) 2008-03-28 2013-01-29 Fujifilm Corporation Polymerizable compositions, color filters, production methods thereof, and solid-state imaging devices
US8569393B2 (en) 2009-12-07 2013-10-29 Agfa-Gevaert N.V. UV-LED curable compositions and inks
WO2011069943A1 (en) 2009-12-07 2011-06-16 Agfa-Gevaert Uv-led curable compositions and inks
WO2011069947A1 (en) 2009-12-07 2011-06-16 Agfa-Gevaert Photoinitiators for uv-led curable compositions and inks
US8957224B2 (en) 2009-12-07 2015-02-17 Agfa Graphics Nv Photoinitiators for UV-LED curable compositions and inks

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