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WO2017033880A1 - Composé ester d'oxime et initiateur de polymérisation contenant ledit composé - Google Patents

Composé ester d'oxime et initiateur de polymérisation contenant ledit composé Download PDF

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Publication number
WO2017033880A1
WO2017033880A1 PCT/JP2016/074349 JP2016074349W WO2017033880A1 WO 2017033880 A1 WO2017033880 A1 WO 2017033880A1 JP 2016074349 W JP2016074349 W JP 2016074349W WO 2017033880 A1 WO2017033880 A1 WO 2017033880A1
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group
carbon atoms
represented
general formula
cycloalkylalkyl
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PCT/JP2016/074349
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English (en)
Japanese (ja)
Inventor
柳澤　智史
貴之 伊香賀
良智 竹内
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株式会社Adeka
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Application filed by 株式会社Adeka filed Critical 株式会社Adeka
Priority to JP2017536415A priority Critical patent/JP6775508B2/ja
Priority to KR1020177032791A priority patent/KR20180044227A/ko
Priority to CN201680030952.5A priority patent/CN107614485A/zh
Publication of WO2017033880A1 publication Critical patent/WO2017033880A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/56—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by doubly-bound oxygen atoms
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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

Definitions

  • the present invention relates to a novel oxime ester compound useful as a polymerization initiator for use in a polymerizable composition, a polymerization initiator containing the oxime ester compound, and a polymerization comprising the ethylenic unsaturated compound in the polymerization initiator.
  • the present invention relates to a polymerizable composition, a colored polymerizable composition obtained by further adding a coloring material to the polymerizable composition, and a cured product obtained from the polymerizable composition or the colored polymerizable composition.
  • the polymerizable composition is obtained by adding a polymerization initiator to an ethylenically unsaturated compound and can be polymerized and cured by irradiating energy rays (light). Therefore, a photocurable ink, a photosensitive printing plate, Used in various photoresists.
  • Patent Documents 1 to 4 propose using an oxime ester compound as a polymerization initiator used in the polymerizable composition.
  • the oxime ester compound with satisfactory sensitivity has low solubility in general solvents and polymerizable compositions, and the polymerization initiator in the polymerizable composition has a low concentration.
  • the design of the polymerizable composition is limited, such as limiting the type and amount of the solvent and the polymerizable compound.
  • the oxime ester compound having high solubility in a general solvent or polymerizable composition has a problem that the sensitivity is not sufficiently satisfactory.
  • the problem to be solved by the present invention is that there has never been a polymerization initiator with high sensitivity and high solubility.
  • an object of the present invention is to provide a novel compound useful as a highly sensitive and highly soluble polymerization initiator, a polymerization initiator using the compound, and a polymerizable composition.
  • the present invention achieves the above object by providing a novel oxime ester compound represented by the following general formula (I) and a polymerization initiator containing the oxime ester compound.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently a group represented by the following general formula (II), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 13 , OR 13 , SR 13 , NR 14 R 15 , COR 13 , SOR 13 , SO 2 R 13 or CONR 14 R 15 , R 13 , R 14 and R 15 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, or the number of carbon atoms An aryl group having 6 to 20 carbon atoms, an ary
  • R 11 and R 11 may combine to form a ring.
  • R 12 and R 12 may In some cases, they may combine to form a ring.
  • R 17 and R 18 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a carbon atom.
  • a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, and a 6 to 20 carbon atom represented by R 17 and R 18
  • a hydrogen atom in an aryl group, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl Group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group
  • this invention provides the polymeric composition containing the said polymerization initiator and an ethylenically unsaturated compound.
  • the present invention also provides a colored polymerizable composition obtained by further adding a coloring material to the polymerizable composition.
  • the present invention provides a cured product obtained from the polymerizable composition or the colored polymerizable composition.
  • oxime ester compound of the present invention and the polymerization initiator containing the oxime ester compound will be described in detail based on preferred embodiments.
  • the oxime ester compound of the present invention is a novel compound represented by the above general formula (I).
  • the oxime ester compound has geometric isomers due to oxime double bonds, but these are not distinguished. That is, in the present specification, the compound represented by the above general formula (I) and the exemplified compound thereof represent a mixture of both or one of them, and are not limited to structures having isomers.
  • alkyl group having 1 to 20 carbon atoms represented by R 13 to R 19 in the general formulas (I) and (II) and the general formula (III) described later examples include, for example, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, Examples include tetradecyl, hexadecyl, octadecyl and icosyl.
  • the cycloalkyl group having 3 to 20 carbon atoms represented by R 13 to R 19 in the above general formulas (I) and (II) and the general formula (III) described later is a group having 3 to 20 carbon atoms.
  • the cycloalkylalkyl group having 4 to 20 carbon atoms represented by R 13 to R 19 in the general formulas (I) and (II) and the general formula (III) described later is a hydrogen atom of the alkyl group.
  • Examples of the aryl group having 6 to 20 carbon atoms represented by R 13 to R 19 in the general formulas (I) and (II) and the general formula (III) described later include, for example, phenyl, tolyl, xylyl, And ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups.
  • Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R 13 to R 19 in the general formulas (I) and (II) and the general formula (III) described later include, for example, benzyl, ⁇ -methyl Examples include benzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and naphthylpropyl.
  • the heterocyclic group having 2 to 20 carbon atoms represented by R 13 to R 15 , R 17 and R 18 in the above general formulas (I) and (II) and the following general formula (III) is as follows: For example, for example, pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl , Thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazo
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 may combine to form a ring
  • a plurality of R 11 may be bonded to form a ring
  • a plurality of R 12 may be bonded to form a ring
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 7 and R 8 , R 8 R 9 , R 9 and R 10 , R 20 and R 21 , R 22 and R 23 , R 23 and R 24 and R 24 and R 25 may combine to form a ring
  • Examples of such rings include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring
  • Ring A 1 and ring A 2 are condensed to form an aromatic ring having 30 or less carbon atoms.
  • Examples of the ring A 1 and the ring A 2 include a benzene ring, a non-benzene ring aromatic skeleton, a heterocyclic aromatic skeleton, and a skeleton in which the ring A 1 and the ring A 2 are condensed to form an aromatic ring.
  • Examples of the non-benzene aromatic skeleton represented by ring A 1 and ring A 2 in the general formula (I) include cyclobutadiene, cyclooctatetraene, and tropone.
  • heterocyclic aromatic skeleton represented by the ring A 1 and the ring A 2 in the general formula (I) examples include furan, thiophene, pyrrole, pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine, and pyrazine. Is mentioned.
  • Examples of the skeleton in which the ring A 1 and the ring A 2 in the general formula (I) are condensed to form an aromatic ring include azulene and the like.
  • condensed ring composed of the ring A 1 and the ring A 2 in the general formula (I) include the following condensed ring Nos. 1-No. 107, and since the oxime ester compound is excellent in stability and less colored, the condensed ring No. 1-No. 16 is more preferable.
  • the present invention is not limited by the following condensed ring.
  • Examples of the halogen atom that may replace the hydrogen atoms of R 13 to R 15 , R 17, and R 18 in III) include fluorine, chlorine, bromine, and iodine.
  • the oxime ester compound represented by the above general formula (I) containing two or more groups represented by the general formula (II) is preferable because it becomes highly sensitive when used as a polymerization initiator.
  • the oxime ester compound in which at least one of R 6 , R 7 , R 8 , R 9 and R 10 in the general formula (I) is COR 13 has high sensitivity when used as a polymerization initiator.
  • R 13 is phenyl
  • the absorption wavelength is good when used as a polymerization initiator, and the transparency of the resulting cured product is more preferable.
  • the oxime ester compound in which at least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 11 in the general formula (I) is represented by the general formula (II) is easy to produce and is an oxime ester. It is preferable because the compound has excellent stability.
  • R 1 to R 10 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 are each independently a group represented by the general formula (II), a hydrogen atom, a halogen atom, A nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 13 , OR 13 , SR 13 , NR 14 R 15 , COR 13 , SOR 13 , SO 2 R 13 or CONR 14 R 15 ;
  • R 13 , R 14 and R 15 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, or the number of carbon atoms
  • a hydrogen atom in an aryl group, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl Group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group, carboxyl group or heterocycl
  • the sensitivity becomes high.
  • the oxime ester compound in which R 13 is phenyl is more preferable because it has a good absorption wavelength when used as a polymerization initiator, and the resulting cured product has high transparency.
  • An oxime ester compound in which R 3 in the general formula (III) is a group represented by the general formula (II) is preferable because it is easy to synthesize and has good stability.
  • Preferred examples of the oxime ester compound of the present invention represented by the above general formula (I) include the following compound No. 1-No. 181. More preferably, the synthesis is easy, the stability is high, the sensitivity is high when used as a polymerization initiator of the polymerizable composition, the absorption wavelength is good, and the resulting cured product has high transparency.
  • the present invention is not limited by the following compounds.
  • a method of synthesizing by the following method is exemplified. That is, a known and commercially available secondary amine compound and an aryl halide are reacted to obtain a tertiary amine compound, and a tertiary amine compound and an acid chloride are reacted to obtain a ketone compound 1; Oxime compound 1 is obtained by reacting 1 with hydroxylamine hydrochloride.
  • the oxime compound 1 of the present invention represented by the above general formula (I) is obtained by reacting the oxime compound 1 with an acid anhydride or acid chloride.
  • the oxime ester compound of the present invention represented by the general formula (I) in the formula, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11
  • a compound in which R 12 is represented by the general formula (II) can also be synthesized according to the above method.
  • the oxime compound and the oxime ester compound can also be produced by the method described in Japanese Patent No. 4223071.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 17 , R 18 , A 1 and A 2 are (It is the same as the above general formulas (I) and (II).)
  • a method of producing by the following method may be mentioned. That is, a known and commercially available secondary amine compound and an aryl halide are reacted to obtain a tertiary amine compound, and a tertiary amine compound and an acid chloride are reacted to obtain a ketone compound 2;
  • the oxime compound 2 is obtained by reacting 2 with isobutyl nitrite.
  • the oxime ester compound 2 of the present invention represented by the above general formula (I) is obtained.
  • the oxime ester compound of the present invention represented by the general formula (I) in the formula, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 And a compound in which R 12 is represented by the general formula (II) can also be synthesized according to the above method.
  • the oxime compound and the oxime ester compound can also be produced by the method described in Japanese Patent No. 4223071.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 17 , R 18 , A 1 and A 2 are (It is the same as the above general formulas (I) and (II).)
  • novel oxime ester compound of the present invention described above is useful as a radical polymerization initiator, particularly a photopolymerization initiator or a thermal polymerization initiator.
  • novel oxime ester compound of the present invention can also be suitably used as a base generator and a sensitizer.
  • the polymerization initiator of the present invention can be used in combination with other polymerization initiators together with the oxime ester compound of the present invention.
  • other polymerization initiators that can be used in combination conventionally known compounds can be used.
  • the content of the oxime ester compound of the present invention in the polymerization initiator of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.
  • the polymerizable composition of the present invention contains the polymerization initiator and an ethylenically unsaturated compound as essential components.
  • the ethylenically unsaturated compound is not particularly limited, and those conventionally used in polymerizable compositions can be used. Examples thereof include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, and fluorine.
  • Unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid Allylic acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ⁇ -carboxypolycaprolactone mono ( Mono (meth) of a polymer having a carboxy group and a hydroxyl group at both ends, such as (meth) acrylate ) Acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopenta
  • A1-No. A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxy
  • a mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends a polyfunctional (meth) acrylate having one carboxy group and two or more (meth) acryloyl groups, an unsaturated one
  • a polymerization initiator containing the oxime ester compound of the present invention in an ester of a basic acid and a polyhydric alcohol or polyhydric phenol is suitable.
  • These ethylenically unsaturated compounds can be used alone or in admixture of two or more, and when used in admixture of two or more, they are copolymerized in advance as a copolymer. May be used.
  • an ethylenically unsaturated compound having an acid group such as a carboxyl group (hereinafter also referred to as a compound having alkali developability) can be used for the purpose of imparting alkali developability to the polymerizable composition of the present invention.
  • the compound having alkali developability is not particularly limited as long as it is soluble in an aqueous alkali solution.
  • copolymers of acrylic acid esters, phenols, cresol novolac epoxy resins examples thereof include resins obtained by further allowing polybasic acid anhydrides to act on polyphenylmethane type epoxy resins having polyfunctional epoxy groups, epoxy acrylate resins and epoxy acrylate resins.
  • ethylenically unsaturated compound such as Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Kayaku), SPC-1000, SPC. -3000 (manufactured by Showa Denko), Aronix M-140, M-215, M-350, M-450 (manufactured by Toagosei), NK ester A-DPHA-TMPT, A-DCP, A-HD-N, A- 9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the content of the polymerization initiator used in the polymerizable composition of the present invention is not particularly limited, but is preferably 0.5 to 70 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound. More preferably, it is 0.5 to 50 parts by mass, and most preferably 0.5 to 30 parts by mass.
  • the colored polymerizable composition of the present invention further contains a coloring material in the polymerizable composition.
  • coloring material examples include pigments, dyes, and natural pigments. These color materials can be used alone or in admixture of two or more.
  • the pigment examples include a nitroso compound; a nitro compound; an azo compound; a diazo compound; a xanthene compound; a quinoline compound; an anthraquinone compound; a coumarin compound; a phthalocyanine compound; an isoindolinone compound; an isoindolinone compound; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; furnace method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with epoxy resin, carbon black previously dispersed in a resin in a solvent and adsorbed with 20 to 200 mg / g of resin, carbon black treated with an acidic or
  • Graphite Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series , Ferrocyanide Organic or inorganic such as phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber Pigments can be used. These pigments can be used alone or in combination.
  • pigments can also be used as the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 9 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148,
  • dyes As the above dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.
  • the content of the coloring material is preferably 50 to 350 parts by mass, more preferably 100 to 250 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound.
  • a solvent capable of dissolving or dispersing the polymerization initiator, the ethylenically unsaturated compound, and the coloring material can be added to the colored polymerizable composition.
  • ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-di Ether solvents such as ethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lac
  • solvents can be used as one or a mixture of two or more.
  • ketones, ether ester solvents, etc. particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc., have good compatibility between the ethylenically unsaturated compound and the polymerization initiator in the polymerizable composition. Therefore, it is preferable.
  • the polymerizable composition and the colored polymerizable composition of the present invention include, if necessary, a polymer excluding an ethylenically unsaturated compound (hereinafter also referred to as a polymer), an inorganic compound, and a dispersant.
  • a polymer excluding an ethylenically unsaturated compound (hereinafter also referred to as a polymer), an inorganic compound, and a dispersant.
  • sensitizer excluding oxime ester compound of the present invention
  • surfactant silane coupling agent
  • melamine leveling agent
  • latent additive ethylenically unsaturated compound
  • ethylenically unsaturated compound Monomers to be removed, antifoaming agents, thickeners, thixotropic agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, organic fillers, antioxidants, antistatic agents, flow regulators and adhesion promoters
  • resin additives such as can be added.
  • the characteristics of the cured product can be improved by using the above polymer together with the ethylenically unsaturated compound.
  • the 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.
  • Polymer ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester,
  • Examples include phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin.
  • polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred.
  • the content of the polymer is preferably 0 to 500 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound.
  • the inorganic compound examples include nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, alumina, and other metal oxides; layered clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Gold, silver, copper, etc. are mentioned. Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable.
  • inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.
  • the content of the inorganic compound is preferably 0 to 1000 parts by mass, more preferably 0 to 800 parts per 100 parts by mass of the ethylenically unsaturated compound. Part by mass.
  • These inorganic compounds can be used alone or in combination of two or more.
  • the dispersing agent is not limited as long as it can disperse and stabilize a coloring material or an inorganic compound, and a commercially available dispersing agent, for example, BYK series manufactured by BYK Chemie can be used.
  • a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as the basic functional group, and the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof.
  • those having an amine value of 1 to 100 mgKOH / g are preferably used.
  • a sulfur atom-containing compound is generally used.
  • Alkyl compounds trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropyl
  • the surfactant examples include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; higher amines Cationic surfactants such as halogenates and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
  • fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
  • anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates
  • silane coupling agent for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, silanes having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403. A coupling agent is preferably used.
  • Examples of the melamine compound include all or part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea.
  • nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea.
  • Examples include compounds in which (at least two) are alkyl etherified.
  • examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other, and are methylol groups that are not alkyl etherified.
  • hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
  • alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
  • leveling agent Commercially available products can be used as the leveling agent.
  • leveling agents include BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK- 349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-340, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720, BYK-DYNET Tsu-made click Chemie Japan
  • the latent additive is inactive at room temperature, in the light exposure step and in the pre-bake step, and is protected at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Is activated by desorption. Examples of the effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability and adhesion.
  • the latent additive those described in the pamphlet of WO2014 / 021023 can be preferably used.
  • latent additive commercially available products can be used, and examples thereof include Adeka Arcles GPA-5001.
  • optional components other than the ethylenically unsaturated compound, the oxime ester compound of the present invention and the color material are included in the polymerizable composition and colored polymerizable composition of the present invention.
  • the amount of (excluding) is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the ethylenically unsaturated compound.
  • the polymerizable composition and colored polymerizable composition of the present invention include a photocurable paint or varnish; a photocurable adhesive; a printing ink; a dental composition; an electronic photoresist; an electroplating resist; Solder resists; and resists for forming structures in LCD manufacturing processes; compositions for encapsulating electrical and electronic components; solder resists; magnetic recording materials; plating masks; etching masks; three-dimensional objects by stereolithography Decolorizing materials for image recording materials; Decolorizing materials for image recording materials using microcapsules; Photoresist materials for printed wiring boards; Photoresist materials for UV and visible laser direct imaging systems; Photoresist material used for dielectric layer formation in sequential lamination of printed circuit boards or Can be used in various applications such as Mamorumaku, there is no particular limitation on the application.
  • the polymerizable composition and the colored polymerizable composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for forming protrusions for vertical alignment type liquid crystal display elements.
  • it is useful as a polymerizable composition and a colored polymerizable composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element.
  • the spacer for a liquid crystal display panel includes (1) a step of forming a coating film of the polymerizable composition of the present invention on a substrate, and (2) irradiation of the coating film with radiation through a mask having a predetermined pattern shape. (3) a baking step after exposure, (4) a step of developing the coating after exposure, and (5) a step of heating the coating after development.
  • the polymerizable composition and colored polymerizable composition of the present invention to which an ink repellent agent is added are useful as a partition-forming resin composition for an ink jet system, and the composition is used for a color filter, and particularly has a profile angle of 50. It is preferably used for a partition for an ink jet type color filter having a temperature equal to or higher than 0 °.
  • the ink repellent agent a composition comprising a fluorosurfactant and a fluorosurfactant is preferably used.
  • the polymerizable composition and colored polymerizable composition of the present invention can be used as a photosensitive paste composition by containing an inorganic material (inorganic compound).
  • the photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
  • a method for producing a cured product obtained from the polymerizable composition or the colored polymerizable composition of the present invention is described below.
  • the polymerizable composition or colored polymerizable composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, and semiconductor substrate. It can be applied on a supporting substrate such as metal, paper, and plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
  • an ultrahigh pressure mercury lamp As a light source for energy rays used for curing the polymerizable composition or colored polymerizable composition of the present invention, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, Xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc.
  • high energy rays such as radiation
  • an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp and the like that emit light having a wavelength of 300 to 450 nm are exemplified.
  • the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy.
  • the laser light light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser.
  • lasers that emit light in the visible to infrared region such as various semiconductor lasers and YAG lasers, are also used. When these lasers are used, a sensitizing dye that absorbs the visible to infrared region is added to the polymerizable composition or colored polymerizable composition of the present invention.
  • the cured product obtained from the polymerizable composition or colored polymerizable composition of the present invention is a printed circuit board; a color filter in a color display liquid crystal display element such as a color television, a PC monitor, a portable information terminal, a digital camera; a CCD image sensor Color filter; electrode material for plasma display panel; powder coating; printing plate; magnetic recording material; micromechanical component; waveguide; optical switch; color test system; glass fiber cable coating; It can be used for various applications such as materials, protective films, insulating films, optical elements, etc. There are no particular restrictions on the applications.
  • Line width sensitivity 2 ml of a resist solution was dropped on a glass substrate, and a coating film was applied using a spin coater under conditions of 500 rpm ⁇ 2 seconds ⁇ 900 rpm ⁇ 5 seconds ⁇ 1 second, and air-dried for 5 minutes. After air drying, the substrate was placed on a hot plate, prebaked at 90 ° C. for 90 seconds, and then cooled at 23 ° C. for 40 seconds. And pattern exposure at 10 mJ / cm 2 intervals until 10mJ / cm 2 ⁇ 80mJ / cm 2 using an exposure system with a gap 20 ⁇ m through a mask (line & space) to the cooled substrate. Development was performed for 27 to 28 seconds using a basic developer. Thereafter, the line width and film thickness before and after post-baking (230 ° C. ⁇ 30 minutes) were measured. The exposure amount at which the line width is 20 ⁇ m at the mask opening of 20 ⁇ m was defined as the line width sensitivity.
  • the oxime ester compound of the present invention has higher solubility in PGMEA and exposure than the existing oxime ester compound (Comparative Compound No. 1). It is clear that the amount is small, that is, the line width sensitivity is excellent.
  • the oxime ester compound of the present invention is useful because it has a high degree of freedom in blending and is excellent in photolithography when used as a polymerization initiator of a polymerizable composition.
  • the oxime ester compound of the present invention is useful as a highly sensitive and highly soluble polymerization initiator used in a polymerizable composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Photolithography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Indole Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un composé ester d'oxime représenté par la formule générale (I). Dans la formule générale (I), au moins l'un de R1, R2, R3, R4, R5, R6, R7, R8, R9 et R10 est un groupe représenté par la formule générale (II). Le composé ester d'oxime contient, de préférence, deux groupes ou plus représentés par la formule générale (II). Au moins l'un de R6, R7, R8, R9 et R10 dans la formule générale (I) est, de préférence, COR13.
PCT/JP2016/074349 2015-08-24 2016-08-22 Composé ester d'oxime et initiateur de polymérisation contenant ledit composé WO2017033880A1 (fr)

Priority Applications (3)

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JP2017536415A JP6775508B2 (ja) 2015-08-24 2016-08-22 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
KR1020177032791A KR20180044227A (ko) 2015-08-24 2016-08-22 옥심에스테르 화합물 및 그 화합물을 함유하는 중합 개시제
CN201680030952.5A CN107614485A (zh) 2015-08-24 2016-08-22 肟酯化合物及含有该化合物的聚合引发剂

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WO2017170465A1 (fr) * 2016-03-29 2017-10-05 株式会社Adeka Composition photosensible
WO2019013112A1 (fr) * 2017-07-13 2019-01-17 株式会社Adeka Composé ester d'oxime et initiateur de photopolymérisation le contenant
WO2020004601A1 (fr) 2018-06-29 2020-01-02 株式会社Adeka Composé ester d'oxime et initiateur de photopolymérisation le contenant
JP2020200272A (ja) * 2019-06-11 2020-12-17 株式会社Adeka カルバモイルオキシム化合物並びに該化合物を含有する重合開始剤及び重合性組成物
KR20230084120A (ko) 2020-10-08 2023-06-12 가부시키가이샤 아데카 화합물, 중합 개시제, 중합성 조성물, 경화물, 컬러 필터 및 경화물의 제조 방법

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WO2002100903A1 (fr) * 2001-06-11 2002-12-19 Ciba Specialty Chemicals Holding Inc. Photoamorceurs d'oxime ester possedant une structure combinee
WO2007080947A1 (fr) * 2006-01-13 2007-07-19 Toyo Ink Mfg. Co., Ltd. Compose de type ester de dicetoxime et son utilisation
WO2009147031A2 (fr) * 2008-06-06 2009-12-10 Basf Se Photoinitiateurs esters d'oximes
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JP4874659B2 (ja) * 2006-01-24 2012-02-15 富士フイルム株式会社 アニリン化合物及びその製造方法、並びに、感光性組成物
JP5978593B2 (ja) * 2010-10-28 2016-08-24 三菱化学株式会社 ホログラム記録媒体用組成物

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WO2002100903A1 (fr) * 2001-06-11 2002-12-19 Ciba Specialty Chemicals Holding Inc. Photoamorceurs d'oxime ester possedant une structure combinee
WO2007080947A1 (fr) * 2006-01-13 2007-07-19 Toyo Ink Mfg. Co., Ltd. Compose de type ester de dicetoxime et son utilisation
WO2009147031A2 (fr) * 2008-06-06 2009-12-10 Basf Se Photoinitiateurs esters d'oximes
WO2009147033A1 (fr) * 2008-06-06 2009-12-10 Basf Se Mélanges de photo-initiateurs
WO2010060702A1 (fr) * 2008-11-03 2010-06-03 Basf Se Mélanges de photo-initiateurs

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017170465A1 (fr) * 2016-03-29 2017-10-05 株式会社Adeka Composition photosensible
WO2019013112A1 (fr) * 2017-07-13 2019-01-17 株式会社Adeka Composé ester d'oxime et initiateur de photopolymérisation le contenant
KR20200029379A (ko) 2017-07-13 2020-03-18 가부시키가이샤 아데카 옥심에스테르 화합물 및 상기 화합물을 함유하는 광중합 개시제
TWI772456B (zh) * 2017-07-13 2022-08-01 日商艾迪科股份有限公司 肟酯化合物及含有該化合物之光聚合起始劑
WO2020004601A1 (fr) 2018-06-29 2020-01-02 株式会社Adeka Composé ester d'oxime et initiateur de photopolymérisation le contenant
KR20210027433A (ko) 2018-06-29 2021-03-10 가부시키가이샤 아데카 옥심에스테르 화합물 및 이것을 함유하는 광중합개시제
US12013637B2 (en) 2018-06-29 2024-06-18 Adeka Corporation Oxime ester compound and photopolymerization initiator containing same
JP2020200272A (ja) * 2019-06-11 2020-12-17 株式会社Adeka カルバモイルオキシム化合物並びに該化合物を含有する重合開始剤及び重合性組成物
KR20230084120A (ko) 2020-10-08 2023-06-12 가부시키가이샤 아데카 화합물, 중합 개시제, 중합성 조성물, 경화물, 컬러 필터 및 경화물의 제조 방법

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TW201713615A (zh) 2017-04-16
JP6775508B2 (ja) 2020-10-28
KR20180044227A (ko) 2018-05-02
CN107614485A (zh) 2018-01-19
JPWO2017033880A1 (ja) 2018-06-07

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