JP2010215575A - New oxime ester compound, radical polymerization initiator containing the same, polymerizable composition, negative type resist by using the same and method for forming image pattern by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new oxime ester compound functioning as a highly sensitive radical polymerization initiator polymerizing a radically polymerizable compound in a short time by the irradiation of an energy beam, and a curable composition by using the same. <P>SOLUTION: This radical polymerization initiator consists of a compound etc., obtained by esterifying a compound expressed by the formula. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel oxime ester compound, a radical polymerization initiator comprising the same, and a polymerizable composition using the same. More specifically, free radicals are efficiently generated by irradiation with energy rays, particularly light, and radically polymerizable compounds are reliably polymerized in a short time. For example, molding resins, casting resins, optical modeling resins, sealants, Dental polymerization resin, printing ink, paint, photosensitive resin for printing plate, color proof for printing, resist for color filter, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, rib material for plasma display , Dry film resist, printed circuit board resist, solder resist, semiconductor photoresist, microelectronic resist, micromachine component resist, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide Materials, overcoat agents, powder coatings, adhesives, adhesives, release agents, optical recording media, adhesives, release coating agents, compositions for image recording materials using microcapsules, various devices, etc. The present invention relates to a novel radical polymerization initiator for obtaining a polymer having good physical properties in the field and a polymerizable composition using the same.

  Conventionally, it is known that certain oxime ester compounds function as radical polymerization initiators (see Non-Patent Document 1, Patent Documents 1 and 2). Further, α-ketoxime ester compounds are disclosed as photo radical polymerization initiators for positive or negative photosensitive polyimide precursor compositions (see Patent Documents 3 and 4). In addition, certain α, α'-diketooxime ester compounds are disclosed (see Patent Documents 5 to 9). Moreover, a certain kind of o-acyl oxime ester compound is disclosed (refer patent documents 10-12). In recent years, high sensitivity of polymerization initiators has been universally demanded and active research has been done to improve productivity and various newly proposed processes. It should be noted that the impact of further sensitivity improvements on productivity and process response is immeasurable.

  Furthermore, in recent years, a photoresist method using a photosensitive resin has been used in various fields. In this photoresist method, for example, a photosensitive resin layer is formed on a substrate surface on which a desired image is to be provided by coating or transfer from another base material, and then an original image is formed on the photosensitive resin layer. In general, a method of forming an image corresponding to the original image by removing an unexposed portion by a developing treatment with a solvent or an aqueous alkaline solution after exposure by irradiating with an energy ray is generally used. As an example using such a photoresist method, for example, a certain type of negative resist is disclosed as a material for forming a display panel spacer (see Patent Documents 13 to 15). Also, certain types of negative resists have been disclosed as materials for manufacturing electrical / electronic components and printed circuit boards (see Patent Documents 16 to 18). Recently, a resist composition using a certain O-acyl oxime ester as a radical polymerization initiator is known as a more sensitive resist composition, and a certain kind of material for forming a spacer for a display panel is known. Negative resists are disclosed (see Patent Document 19). In addition, a certain type of negative resist is disclosed as a material for manufacturing electric / electronic parts and printed circuit boards (see Patent Document 20). Any of these can function as a resist composition, but in recent years, in order to improve productivity and respond to various newly proposed processes, the resist composition is added with higher and new functions, especially higher The development of various resist compositions has been actively promoted as a sensitive resist composition has been required.

US Pat. No. 3,558,309 US Pat. No. 4,255,513 JP-A-7-140,658 International Patent Publication No. 2008/078678 US Pat. No. 5,019,482 Japanese Patent Laid-Open No. 62-184,056 JP-A-62-273,259 JP 62-286,961 A JP-A-62-201,859 JP 2001-233842 A JP 2000-80,068 JP-T-2004-534,797 JP-A-11-174464 JP 2001-226449 A JP 2002-341931 A Japanese Patent Laid-Open No. 10-198033 JP 2002-236362 A JP 2002-249644 A JP 2001-261761 A JP 2001-302871 A

European polymer Journal, 1970, 6, 933−943

  An object of the present invention is to provide a novel oxime ester compound capable of efficiently generating active radicals by irradiation of energy rays, particularly light, and functioning as a highly sensitive radical polymerization initiator capable of polymerizing a radical polymerizable compound in a short time, and The object is to provide a curable composition using the same. A further object of the present invention is that the curing rate is extremely fast, and it can be suitably used for very clear pattern exposure or direct drawing by energy rays, and also has excellent adhesion to the substrate. In particular, the present invention is to provide a negative resist material having alkali developability that is preferably used for a photoresist material, and an image pattern forming method using the negative resist.

  As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have reached the present invention. That is, the present invention relates to a compound represented by the following general formula (1).

General formula (1)

Wherein R ¹ is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted amino group, substituted or unsubstituted Substituted phosphinoyl group, substituted or unsubstituted It represents a carbamoyl group or a substituted or unsubstituted sulfamoyl group,.
R ² represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group Represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.
R ³ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted acyl group.
R ^{4 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group. Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted Arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, or substituted or unsubstituted amino group To express. Provided that at least one of R ⁷ to R ¹⁰ is a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl A sulfonyl group or a substituted or unsubstituted arylsulfonyl group. )

The present invention also relates to the above compound, wherein at least one of R ^{7 to} R ¹⁰ is a nitro group.

The present invention also relates to the above compound, wherein R ⁸ is a nitro group.

  The present invention also relates to a radical polymerization initiator (A) comprising the compound described above.

  The present invention also relates to a polymerizable composition comprising the radical polymerization initiator (A) and the radical polymerizable compound (B).

  Moreover, this invention relates to the said polymeric composition which further contains a sensitizer (C).

  Moreover, this invention relates to the said polymeric composition which further contains a coloring component (D).

  Moreover, this invention relates to the said polymeric composition which further contains alkali-soluble resin (E).

  The present invention further relates to a negative resist comprising the polymerizable composition.

  The present invention further relates to a method for producing a polymer, wherein the polymerizable composition is polymerized by irradiation with energy rays.

  In addition, the present invention further forms an image pattern characterized by laminating the negative resist on a substrate, partially irradiating with energy rays and polymerizing, and removing unirradiated portions with an alkali developer. Regarding the method.

  The present invention further relates to an image pattern formed by the above image pattern forming method.

  The compound of the present invention is an α-ketoxime ester compound in which an electron-withdrawing substituent is substituted on carbazole, and efficiently generates active radicals by irradiation with energy rays, particularly light. Therefore, the compound which has a remarkably favorable effect as a radical polymerization initiator was able to be provided. Further, by using the compound of the present invention as the radical polymerization initiator (A), it is possible to provide a curable composition having good characteristics, for example, a molding resin, a casting resin, a resin for optical modeling, Sealant, dental polymerization resin, printing ink, inkjet ink, paint, photosensitive resin for printing plate, color proof for printing, resist for color filter, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, Optical fibers, ribs for plasma displays, dry film resists, resists for printed circuit boards, solder resists, photoresists for semiconductors, resists for microelectronics, resists for manufacturing micromachine parts, etching resists, microlens arrays, insulating materials, hologram materials, Optical Industrial-use oligomers and polymers that are practical in the fields of coatings, waveguide materials, overcoat agents, powder coatings, adhesives, adhesives, mold release agents, optical recording media, adhesives, release coating agents, etc. It was possible to provide a radical polymerization initiator and a polymerizable composition using the same to obtain a cured product having good characteristics. In particular, the polymerizable composition of the present invention is a polymerizable composition that can be suitably used for very clear pattern exposure or direct drawing, and has excellent adhesion to a substrate. High-sensitivity negative resist that can be suitably used in the present invention, and an image pattern forming method using the negative resist.

  Hereinafter, embodiments of the present invention will be described in detail.

  First, the compound of the present invention will be described. The compound of the present invention is characterized in that an electron-withdrawing substituent is substituted on the carbazole skeleton as represented by the general formula (1). In addition, by having this structure, the compound of the present invention decomposes very efficiently without using a sensitizer in combination with light irradiation in the wavelength region, and as a result, a large amount of radicals can be efficiently decomposed. It can function as a highly sensitive material that occurs in

General formula (1)

In the general formula, R ¹ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted amino group, substituted or unsubstituted Substituted phosphinoyl group, substituted or unsubstituted A carbamoyl group or a substituted or unsubstituted sulfamoyl group, a conversion.

Examples of the substituted or unsubstituted alkenyl group for R ¹ include straight-chain, branched-chain, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. Specific examples include a vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2- Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3- Examples thereof include butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

The substituted or unsubstituted alkyl group in R ¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally one or more Examples thereof include a linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by -O-. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. Examples thereof include, but are not limited to, CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _{2 and the} like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

The substituted or unsubstituted alkyloxy group in R ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally 1 Examples include a linear, branched, monocyclic or condensed polycyclic alkyloxy group interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

Examples of the substituted or unsubstituted aryl group in R ¹ include monocyclic or condensed polycyclic aryl groups having 6 to 24 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 1 -Anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2 -Fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group P-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromopheny Group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, and the like, but are not limited thereto. It is not a thing.

Examples of the substituted or unsubstituted aryloxy group in R ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9- Although a fluorenyloxy group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted heterocyclic group for R ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl Group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2- Indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquino Group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, - quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted heterocyclic oxy group in R ¹ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group , 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted alkylsulfanyl group in R ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group and an ethylthio group. Propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the substituted or unsubstituted arylsulfanyl group in R ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, Examples thereof include, but are not limited to, a 9-anthrylthio group and a 9-phenanthrylthio group.

The substituted or unsubstituted alkylsulfinyl group in R ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, and a butylsulfinyl group. Group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. However, it is not limited to these.

  As the substituted or unsubstituted arylsulfinyl group, an arylsulfinyl group having 6 to 30 carbon atoms is preferable, and specific examples include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group Group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfinyl group § sulfonyl phenylsulfinyl group, 4-dimethylaminophenyl sulfinyl but Le group and the like, but is not limited thereto.

The substituted or unsubstituted alkylsulfonyl group for R ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and a butylsulfonyl group. Hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group and the like. It is not limited to these.

The substituted or unsubstituted arylsulfonyl group for R ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, and 2-chlorophenyl. Sulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3- Nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfo Group, 4-but-dimethylaminophenyl sulfonyl group and the like, but is not limited thereto.

Examples of the substituted or unsubstituted acyl group for R ¹ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or 2 to 20 carbon atoms. A carbonyl group substituted with an alkyloxy group, a carbonyl group bonded with a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, or a carbonyl group substituted with a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms A carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is bonded. Specific examples include a formyl group, an acetyl group Group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxy Carbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthryl Carbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyl Oxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, Although an isonicotinoyl group etc. can be mentioned, it is not limited to these.

Examples of the substituted or unsubstituted acyloxy group in R ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, A fluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, a 2-naphthylcarbonyloxy group, and the like can be given.

Examples of the substituted or unsubstituted amino group in R ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

Examples of the substituted or unsubstituted phosphinoyl group in R ¹ include phosphinoyl groups having 2 to 50 carbon atoms. Specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenyl. Examples include, but are not limited to, phosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group. is not.

Examples of the substituted or unsubstituted carbamoyl group in R ¹ include a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N- Butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N 2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3 -Cyanoff Nylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, and the like, but are not limited thereto.

Examples of the substituted or unsubstituted sulfamoyl group in R ¹ include sulfamoyl groups having 0 to 30 carbon atoms, and specific examples thereof include sulfamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, N N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

R ² represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group A substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.

R ² is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, the amino group of the substituted or unsubstituted, substituted or unsubstituted alkenyl group in R ¹ described above, a substituted or unsubstituted alkyl group, a substituted Or unsubstituted alkyloxy Group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted A substituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, Or it is synonymous with a substituted or unsubstituted amino group.

R ³ is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted acyl group.

A substituted or unsubstituted alkenyl group in R ^3, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted acyl group, is a substituted or unsubstituted in R ¹ described above alkenyl group A substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted acyl group.

R ^{4 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group. Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted An arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or A substituted or unsubstituted amino group Provided that at least one of R ⁷ to R ¹⁰ is a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl A sulfonyl group or a substituted or unsubstituted arylsulfonyl group.

Examples of the halogen atom in R ^{4 to} R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the haloalkyl group in R ^{4 to} R ¹⁰ include an alkyl group having 1 to 15 carbon atoms in which all the hydrogen atoms are substituted with the halogen atoms described above, and specific examples include a trifluoromethyl group and a trichloromethyl group. , Tribromomethyl group, triiodomethyl group, pentafluoroethyl group, pentapentachloroethyl group, pentabromoethyl group, pentaiodoethyl group, trifluorodibromoethyl group, tribromodiiodoethyl group, heptafluoropropyl group, Heptachloropropyl group, heptabromopropyl group, nonafluorobutyl group, nonachlorobutyl group, nonabromobutyl group, undecafluoropentyl group, undecachloropentyl group, undecabromopentyl group, tridecafluorohexyl group, tridecachloro group Hexyl group, pentadecuff Examples thereof include, but are not limited to, oloheptyl group, heptadecafluorooctyl group, nonadecafluorononyl group, henicosafluorodecyl group, tricosafluoroundecyl group, pentacosafluorododecyl group, and the like. .

A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted in R ^{4 to} R ¹⁰ Unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted aryl As the sulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, or substituted or unsubstituted amino group, a substituted or non-substituted in R ¹ Lucenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group A substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.

Here, at least one of R ^{7 to} R ¹⁰ is a halogen atom, nitro group, cyano group, haloalkyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted. An alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group;

From the viewpoint of the characteristics when used as a synthetic surface or a radical polymerization initiator (A), the above substituent is more preferably substituted with R ⁸ .

Furthermore, it is preferable that at least one of R ^{7 to} R ¹⁰ is a nitro group.

More preferably, R ⁸ is more preferably a nitro group from the viewpoint of synthesis and characteristics when used as a radical polymerization initiator (A).

The hydrogen atom of the substituent in R ^{1 to} R ¹⁰ described above may be further substituted with another substituent.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyla Alkyl groups such as alkyl groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups and other dialkylamino groups, phenylamino groups, p-tolylamino groups and other arylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and other heterocyclic groups such as furyl groups and thienyl groups, hydroxy groups Group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, Trimethylammonium, dimethylsulfonium, trif Cycloalkenyl phenacyl phosphonium Niu mill group, and the like.

  Specific examples of the compound of the present invention described above are shown below, but the structure of the compound of the present invention is not limited thereto.

  The compound represented by the general formula (1) uses a ketone compound represented by the following general formula (2) as an intermediate. Hereinafter, unless otherwise specified, the “intermediate” refers to a ketone compound.

General formula (2)

(In the formula, R ^{2 to} R ¹⁰ have the same meaning as in the general formula (1).)

  In general, ketone compounds are readily available as raw materials. Moreover, it can obtain easily by the conventionally well-known synthetic | combination methods, for example, the various methods described in the Chemical Society of Japan edition, 4th edition, a new experimental chemistry course, the 14th volume, 751 (Maruzen).

  In particular, a ketone body of a carbazole compound as represented by the general formula (2) can be easily obtained by Friedel-Crafts acylation reaction, for example, obtained by a method similar to the method described in Japanese Patent No. 3993725. be able to.

  The precursor for synthesizing the compound represented by the general formula (1) is an oxime represented by the following general formula (3). Hereinafter, unless otherwise specified, the “precursor” refers to an oxime compound.

General formula (3)

(In the formula, R ^{2 to} R ¹⁰ have the same meaning as in the general formula (1).)

  The oxime represented by the general formula (3) can be obtained by using, for example, the Org. React., 7, <1953>, 327, and the 4th edition of the Chemical Society of Japan, with the ketone compound represented by the general formula (2) as an intermediate. Versions can be obtained by various methods described in Experimental Chemistry, Vol. 14, page 1316 (Maruzen). Furthermore, it can also be obtained from a method for synthesizing oximes described in commercially available chemistry texts (for example, J. March, Advanced Organic Organic Chemistry, 4th Edition, Wiley Interscience, 1992).

  One of the most convenient methods of synthesizing oximes is nitrosation of active methylene groups with nitrous acid or alkyl nitrites. The reaction conditions are, for example, Organic Syntheses Coll. Vol. VI, pp 840, Organic Syntheses Coll. Vol. III, pp 191 and 513, Organic Syntheses Coll. Vol. II, pp 202, 204 and 363, J. Am. Chem. Soc., 47, <1925>, 2033, J. Chem. Soc., 117, <1920>, 590, J. Am. Chem. Soc., 51, <1929>, 2264. Suitable for manufacturing. Nitrous acid is usually produced from sodium nitrite. The nitrite alkyl ester is, for example, methyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite.

  The compound represented by the general formula (1) is prepared by using the oxime compound represented by the general formula (3) as a precursor in the method described in the literature, for example, the oxime and acyl chloride or acid anhydride obtained by the method described above. With an inert solvent such as tetrahydrofuran, benzene or dimethylformamide, in the presence of a base, for example a tertiary amine such as triethylamine, or in a basic solvent such as pyridine. .

  Such reactions are known to those skilled in the art and are generally carried out at -15 ° C to + 50 ° C, preferably 0-30 ° C.

  All oxime ester groups exist in two configurations, (Z) or (E). The isomers can be separated by conventional methods, but mixtures of isomers can also be used as photoinitiating species. The invention therefore also relates to a mixture of configurational isomers of the compound of general formula (1).

The radical polymerization initiator (A) represented by the general formula (1) of the present invention can be easily identified using mass spectrometry, elemental analysis, and conventionally known analysis methods such as ¹ H-NMR. it can.

  Next, the case where the compound of this invention is used as a radical polymerization initiator (A) is demonstrated.

  Many of the conventionally known α-ketoxime ester compounds usually do not exhibit absorption at wavelengths longer than the ultraviolet region, and thus are poor in activity from near ultraviolet to near infrared light. However, the general formula (1 The radical polymerization initiator (A) represented by) has an absorption band from the near ultraviolet to the visible region by introducing an electron-withdrawing substituent into the carbazole group. It is possible to give activity to a region.

  Further, as described above, the radical polymerization initiator (A) of the present invention has a keto oxime ester structure as represented by the general formula (1). The reason why the radical polymerization initiator (A) of the present invention can function with higher sensitivity than conventionally known radical polymerization initiators can be considered for the following three reasons (possibility), but the details are not clear. Absent.

  The first reason is that the radical polymerization initiator (A) of the present invention has a very good energy due to a given energy beam because the carbazole chromophore represented by the general formula (1) has a good absorption. Can be absorbed into. Furthermore, it is conceivable that the obtained energy is efficiently used for the decomposition of the oxime ester moiety, so that the decomposition by the energy beam irradiation is fast and a large amount of radicals can be generated instantaneously.

  The second reason is that the radical polymerization initiator (A) of the present invention has a keto oxime ester structure, so that an inactive iminyl radical as an active species is rapidly decomposed as shown below. It is conceivable to further generate a decomposition product (carbazolyl radical) that can function as an active species. A keto-type oxime ester does not necessarily produce a large amount of radicals, and if the iminyl radical produced is metastable, the decomposition will be slow, and the amount of radicals produced will be less than the theoretical amount. This is greatly affected by the chromophore that it has. The radical polymerization initiator of the present invention has the structure shown in the general formula (1), so that the iminyl radical generated by the decomposition by light irradiation for some reason is very quickly decomposed, and a large amount of radicals are generated. It is thought that it has brought.

  Further, as described above, the radical polymerization initiator (A) of the present invention is considered to suppress recombination because the decomposition of the iminyl radical is very fast. When the number of recombination is large, the active species generated by the decomposition is reduced, so that the function as a radical polymerization initiator is lowered.

  As the third reason, as described above, there is a synergistic effect between the effect of the carbazole substituted with the electron-withdrawing substituent capable of functioning as an excellent chromophore and the effect of the keto oxime ester.

  Since the radical polymerization initiator (A) of the present invention functions as a very sensitive radical polymerization initiator by irradiation with energy rays, a polymerization reaction and a crosslinking reaction using a conventionally known radical polymerization initiator can be performed in a shorter time. As a result, it is possible to achieve a significant increase in sensitivity and improvement in characteristics of various applications using these reactions. Below, the utilization method of the radical polymerization initiator (A) of this invention is described.

  The composition comprising the radical polymerization initiator (A) and the radical polymerizable compound (B) of the present invention can be cured rapidly and reliably by irradiation with energy rays, and a cured product having good characteristics can be obtained. It can be used as a sex composition.

  The radically polymerizable compound (B) of the present invention will be described. The radical polymerizable compound (B) of the present invention is a compound having an ethylenically unsaturated bond capable of radical polymerization, and the compound having an ethylenically unsaturated bond capable of radical polymerization is ethylene capable of radical polymerization in the molecule. Any compound having at least one ionic unsaturated bond may be used, and it may have a chemical form such as a monomer, an oligomer or a polymer.

  Examples of such a compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, Examples include urethane, amides and anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, and other radical polymerizable compounds, but the present invention is not limited thereto. It is not something. Specific examples of the radically polymerizable compound (B) in the present invention are given below.

Examples of acrylates:
Examples of monofunctional alkyl acrylates:
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxy acrylates:
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated acrylates:
2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, p Nonyl phenoxyethyl acrylate, p- nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl acrylates:
β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2- Acryloyloxypropyltetrahydrophthalate.

Examples of other monofunctional acrylates:
N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified-2-acryloyl Oxyethyl acid phosphate.

Examples of bifunctional acrylates:
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 Diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neo Pentyl glycol diacrylate, ne Pentyl glycol PO modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A diacrylate, tricyclodecandi Methylol diacrylate, isocyanuric acid EO-modified diacrylate.

Examples of trifunctional acrylates:
Glycerin PO modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane PO modified triacrylate, isocyanuric acid EO modified triacrylate, isocyanuric acid EO modified ε-caprolactone modified triacrylate, 1,3 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetra- or higher functional acrylates:
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate.

Examples of methacrylates:
Examples of monofunctional alkyl methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate , Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxymethacrylates:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated methacrylates:
2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates:
2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, Ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, cresyl polyethylene glycol methacrylate, p- Cycloalkenyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates:
β-carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2- Methacryloyloxypropyl tetrahydrophthalate.

Examples of other monofunctional methacrylates:
Dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone Modified-2-methacryloyloxyethyl acid phosphate.

Examples of bifunctional methacrylates:
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopenty Glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct dimethacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3- (Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane Bisphenol A dimethacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A-dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A dimethacrylate, PO-modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO-modified bisphenol F dimethacrylate, PO-modified bisphenol F dimethacrylate, EO-modified tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate.

Examples of trifunctional methacrylates:
Glycerin PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate.

Examples of arylates:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

Examples of acid amides:
Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

Examples of styrenes:
Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene 2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds:
Vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone Such.

  Said radically polymerizable compound (B) can be easily obtained as a commercial item of the manufacturer shown below. For example, “Light acrylate”, “Light ester”, “Epoxy ester”, “Urethane acrylate” and “Highly functional oligomer” series manufactured by Kyoeisha Yushi Chemical Co., Ltd., Shin Nakamura Chemical Co., Ltd. "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Co., Ltd., manufactured by Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamar" series manufactured by KK, "Acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Shokubai Co., Ltd. "NICHIGO-UV purple light urethane acrylate oligomer" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. "Carboxylic acid vinyl ester monomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd. "Function" manufactured by Kojin Co., Ltd. Monomer "series and the like.

  Furthermore, examples of the radical polymerizable compound (B) include those described in the following literature. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyomi Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Meeting, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), edited by Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

  The radically polymerizable compound (B) of the present invention may be used alone or in a mixture of two or more at any ratio in order to improve desired properties.

  The amount of the radical polymerization initiator (A) of the present invention used in the polymerizable composition is 0.1 to 100 parts by weight, preferably 3 to 60 parts by weight, based on 100 parts by weight of the radical polymerizable compound (B). Part.

The polymerizable composition of the present invention can be used by mixing with a binder such as an organic polymer and applying it to a polymer film such as a glass plate, an aluminum plate, another metal plate, or polyethylene terephthalate.
Examples of binders that can be used by mixing with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, Examples thereof include polymers and copolymers such as polyvinyl esters, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol resin, Epoxy resin, alkyd resin, etc., supervised by Kiyoshi Akamatsu, “New Photosensitive Resin Technology” (1987, CMC) and “10188 Chemical Products”, pages 657-767 (1988, Chemical Industries Day) Inc.) industry known organic polymer according the like.

The polymerizable composition of the present invention can be used in combination with other polymerization initiators for the purpose of further improving sensitivity.
Examples of other polymerization initiators that can be used in combination with the polymerizable composition of the present invention include triazine derivatives described in JP-B-59-1281, JP-B-61-9621, and JP-A-60-60104. Organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and USP No. 3567453, diazonium compound gazette, USP 2,848,328, USP 2,852,379 and USP 2,940,853, organic azide compounds, JP-B 36-22062, JP-B 37-13109 Disclosed in Japanese Patent Publication No. SHO 38-18015 and SHO 45-9610. Luto-quinonediazides, including iodonium compounds described in JP-B-55-39162, JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977) Various onium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 1099851, European Patent No. 126712, “Journal of Imaging Science” (J.IMAG.SCI.) ”, Vol. 30, page 174 (1986), titanocenes described in JP-A No. 61-151197,“ COORDINATION CHEMISTRY REVIEW 84), 85-277 (1988) and special Transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701, aluminate complexes described in JP-A-3-209477, borate compounds described in JP-A-2-157760, No. 55-127550 and JP-A-60-202437, 2,4,5-triarylimidazole dimer, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, A sulfonium complex or an oxosulfonium complex described in JP-A-5-255347, an aminoketone compound described in JP-A-54-99185 and JP-A-63-264560, JP-A-2001-264530, JP-A-2001-261661. JP, JP 2000-80068, JP 2001-233842 A No. 2004-534797, USP 3558309 specification (1971), USP4202697 specification (1980) and Japanese Patent Application Laid-Open No. 61-24558, etc. The agent is preferably contained in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization.

  In addition, a thermal polymerization inhibitor can be added to the polymerizable composition of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the thermal polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The polymerization inhibitor is preferably added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization.

  The polymerizable composition of the present invention can further contain a polymerization accelerator represented by amine, thiol, disulfide and the like, a chain transfer catalyst, etc. for the purpose of further promoting the polymerization.

  Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the polymerizable composition of the present invention include, for example, amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP No. 4414312 Thiols described in the specification, JP-A No. 64-13144, disulfides described in JP-A No. 2-291561, thiones described in USP No. 3558322 and JP-A No. 64-17048, Examples include O-acylthiohydroxamate and N-alkyloxypyridinethiones described in JP-A-2-291560.

  Further, the polymerizable composition of the present invention can be used depending on the purpose, such as dyes, organic and inorganic pigments, phosphine, phosphonate, phosphite and other oxygen scavengers and reducing agents, antifoggants, antifading agents, antihalation agents, fluorescent enhancers. Whitening agents, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, UV absorbers, foaming agents, fungicides, antistatic agents, magnetic substances and other additives that impart various properties Alternatively, it may be mixed with a diluting solvent or the like.

  In the polymerizable composition of the present invention, a sensitizer (C) can be added for the purpose of further promoting polymerization. A sensitizer increases the activity with respect to light from the ultraviolet to the near infrared region, and therefore it is preferable to add a sensitizer when it is necessary to promote polymerization.

  Specific examples of such sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, and fluorene derivatives. , Naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, Oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzopo Filin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives , Spirooxazine derivatives, thiospiropyran derivatives, carbazole derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives, etc. Other specific examples include Ogahara Shin et al., “Dye Handbook” (1986, Kodansha), Okawara Sensitizers described in Shin et al., "Chemicals of Functional Dyes" (1981, CMC), edited by Tadasaburo Ikemori et al., "Special Functional Materials" (1986, CMC) However, the present invention is not limited to these, and other sensitizers that absorb light from the ultraviolet to the near-infrared region can be used, and these may be used in an arbitrary ratio as needed. . Among the sensitizers, examples of the sensitizer capable of particularly suitably sensitizing the radical polymerization initiator of the present invention include thioxanthone derivatives and Michler ketone derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis Examples thereof include (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, but are not limited thereto.

  The amount used in the case of using the radical polymerization initiator (C) of the present invention is 0.01 to 60 parts by weight, preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B). Parts, more preferably 0.1 to 10 parts by weight.

  A coloring component (D) can be added to the polymerization composition of the present invention depending on the purpose of coloring. A conventionally known pigment can be used as the coloring component (D). Further, for the purpose of obtaining a desired hue, a dye may be contained within a range in which heat resistance and weather resistance are not lowered. These may be used alone or in combination of two or more in order to obtain a desired color density and hue.

  As the pigment, for example, an organic pigment, an inorganic pigment, or carbon black (for example, acetylene black, channel black, furnace black, etc.) can be used, and two or more kinds of pigments can be mixed and used.

  Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments (eg, azo, disazo, polyazo, etc.), phthalocyanine pigments (eg, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, etc.), anthraquinone type Pigment (for example, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantrone, violanthrone, etc.), quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, iso Examples thereof include indoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, carbon black, cadmium red, Bengara, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, bitumen, cobalt Examples include blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

  Examples of the carbon black include “Special Black 350, 250, 100, 550, 5, 4, 4A, 6” manufactured by Degussa, Inc., “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, 45. , 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ”,“ REGAL 400R, 660R, 330R, 250R ”,“ MOGUL E, L ”, manufactured by Mitsubishi Chemical Corporation,“ MA7, 8, 11, 77, 100, 100R, 100S, 220, 230 "" # 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 4 5L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, # 260 ”and the like.

  Hereinafter, pigments that can be used in the polymerization composition of the present invention are indicated by color index (CI) numbers.

  Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272 or the like can be used, but is not limited thereto.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 , But the invention is not limited to the like can be used 177,179,180,181,182,185,187,188,193,194,199.

  Examples of orange pigments include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61 and the like can be used, but are not limited thereto.

  Examples of the green pigment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, and 37 can be used, but are not limited thereto.

  Examples of the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be used, but are not limited thereto.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like can be used, but are not limited thereto.

  Examples of the black pigment include C.I. I. Pigment Violet 1, 6, 7, 12, 20, 31 etc. can be used, but it is not limited to these.

  These pigments can be used by mixing two or more kinds at an arbitrary ratio.

When the pigment as the coloring component (D) is added, the amount used is 0.01 to 100 parts by weight, preferably 1 to 60 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B). The particle diameter of a certain pigment is preferably sufficiently small with respect to the wavelength of visible light from the viewpoint of absorption coefficient of visible light (spectrum appropriateness) and transparency. That is, the pigment preferably has an average primary particle size of 0.01 μm or more and 0.3 μm or less, particularly 0.01 μm or more and 0.1 μm or less. The primary particle diameter refers to the diameter of the smallest unit pigment particle, and is measured with an electron microscope.

  The primary particle diameter of the pigment can be controlled within an appropriate range using a known dispersing device such as a sand mill, a kneader, or a two roll.

  Moreover, when adding a pigment to the polymerization composition of the present invention, a pigment derivative or a pigment dispersant can be used for the purpose of improving the dispersibility of the pigment and the storage stability of the polymerization composition.

  Here, the pigment derivative is a compound in which a substituent is introduced into an organic dye. Organic dyes include light yellow aromatic polycyclic compounds such as phthalimide, naphthalene, naphthoquinone, anthracene, and anthraquinone that are not generally called dyes.

  Examples of pigment derivatives include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-06-06. What is described in 306301 gazette, Unexamined-Japanese-Patent No. 2001-220520, Unexamined-Japanese-Patent No. 2003-238842 etc. can be used, These can be used individually or in mixture of 2 or more types.

Examples of the pigment dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene Nonylphenyl ether, stearylamine acetate, etc. can be used.
Specific examples of the pigment dispersant include "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-203 / 204 (high molecular weight polycarboxylate)" manufactured by BYK Chemie, "Disperbyk-101 ( (Polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 ( Polymer copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated acid ester),“ BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ”,“ P104S, 240S (high molecular weight unsaturated) Saturated acid polycarboxylic acid and silicon system "," Lactimon (long chain amine and unsaturated acid poly) Recarboxylic acid and silicon) ”.

  Also, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) "," Floren TG-710 (urethane oligomer) "," Flownon "manufactured by Kyoeisha Chemical Co., Ltd. “SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (manufactured by Enomoto Kasei Co., Ltd.) Aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ” That.

  Further, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18 (poly) Carboxylic acid type polymer), “Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, “Abisia” Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 39000, 41000, 53000, “Nikkor T106 (polyoxy) manufactured by Nikko Chemical Co., Ltd. Ethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), "Ajisper PB821, 822, 824" manufactured by Ajinomoto Fine Techno Co., etc.

  The addition amount of the pigment derivative and the pigment dispersant is not particularly limited, but is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment. is there.

  Examples of the dye that may be contained to obtain a desired hue include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. It is done.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include, but are not limited to, Mordant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Examples include, but are not limited to, Disperse Blue 60.

  Other examples of the phthalocyanine dye include C.I. I. Examples of quinoneimine dyes such as Pad Blue 5 include C.I. I. Basic Blue 3, C.I. I. Examples of quinoline dyes such as Basic Blue 9 include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include, but are not limited to, Disperse Yellow 42.

  The amount used in the case of adding these dyes is 0.01 to 100 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the radical polymerizable compound (B). From the viewpoint of heat resistance and weather resistance, it is not preferable that the amount used is excessive.

  The polymerizable composition of the present invention may be used in combination with an alkali-soluble resin (E) for the purpose of being used for image formation as a so-called alkali development type photoresist material. The alkali-soluble resin (E) of the present invention acts as a binder and has a solubility in a developer used in the development processing step, particularly preferably an alkali developer, when forming an image pattern. If there is, it will not be specifically limited. Among them, an alkali-soluble resin which is a carboxyl group-containing copolymer is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”). ) And other copolymerizable ethylenically unsaturated monomers (hereinafter simply referred to as “copolymerizable unsaturated monomers”) (hereinafter simply referred to as “carboxyl group-containing copolymers”). Is preferred).

  Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacone Unsaturated dicarboxylic acids such as acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acrylic acid) Divalent or higher polyvalent carboxylic acids such as leuoxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) Mono [(meth) acryloyloxyalkyl] esters; ω-carboxypolycaprolactone monoacrylate, ω-carboxypoly It can be mentioned mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as caprolactone monomethacrylate. Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name. The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

  Examples of the copolymerizable unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxy. Styrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. Aromatic vinyl compounds, indenes such as indene and 1-methylindene,

  Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate , 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate , Toxipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, Unsaturated carboxylic acid esters such as 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate,

  2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated carboxylic acid aminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate,

  Unsaturated glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, vinyl carboxylic acid esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate, vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether Saturated ethers, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacryl Unsaturated amides such as amide, unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 1,3-butadiene, isoprene, chloroprene Aliphatic conjugated dienes such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, etc., at the end of the polymer molecular chain, a monoacryloyl group or a monomethacryloyl group And macromonomers having These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  As the carboxyl group-containing copolymer in the present invention, (P) acrylic acid and / or methacrylic acid are essential components, and in some cases, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyl). (Roxyethyl), a carboxyl group-containing unsaturated monomer component further containing at least one compound selected from the group consisting of ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate, and (Q) styrene, methyl Acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol mono A copolymer with at least one selected from the group of methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter referred to as “carboxyl group-containing copolymer (R)”) is preferred.

  Specific examples of the carboxyl group-containing copolymer (R) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid. / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / Polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, ( (Meth) acrylic acid / 2-hydroxyethyl (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / Styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,

  (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono [2- ( (Meth) acryloyloxyethyl] / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer And (meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer.

  In the carboxyl group-containing copolymer, the substituent present in the molecule may be further modified with another material. For example, a part of the carboxyl group present in the polymer is modified by reacting with a monomer having a functional group reactive with a carboxyl group, such as a known glycidyl group, and crosslinking that can participate in radical polymerization in the molecule. It is also possible to provide points. As such a monomer, glycidyl (meth) acrylic acid alkyl ester can be used, for example, glycidyl (meth) acrylic acid, glycidyl (meth) methyl acrylate, glycidyl (meth) ethyl acrylate, glycidyl (meth). Examples thereof include butyl acrylate and 2-ethylhexyl glycidyl (meth) acrylate. In addition, a hydroxyl group present in the polymer is condensed with 2-acryloyloxyethyl isocyanate, 2-methacryloylethyl isocyanate (“Karenz MOI” manufactured by Showa Denko KK), etc., to provide a similar polymerization crosslinking point. Is also possible.

  The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight. In this case, if the copolymerization ratio is less than 5% by weight, the solubility of the resulting resist composition in an alkaline developer tends to decrease, whereas if it exceeds 50% by weight, the solubility in an alkaline developer becomes excessive. When developing with an alkali developer, the resist film tends to drop off from the substrate and the image surface tends to become rough. The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 3,000 to 300,000, Preferably it is 5,000-100,000. Further, the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 3,000-60, 000, preferably 5,000 to 25,000. In the present invention, by using such an alkali-soluble resin having specific Mw and Mn, a radiation-sensitive composition having excellent developability can be obtained, whereby an image pattern having sharp pattern edges can be obtained. In addition to being able to be formed, residues, background stains, film residues and the like are less likely to occur on the unirradiated substrate and the light shielding layer during development. Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin in the present invention is preferably 1 to 5, particularly preferably 1 to 4.

  Examples of the alkali-soluble resin (E) other than the carboxyl group-containing copolymer include novolac resins and resins having a phenolic hydroxyl group such as polyhydroxystyrene. E).

  In this invention, alkali-soluble resin (E) can be used individually or in mixture of 2 or more types.

  The usage-amount when using alkali-soluble resin (E) in this invention is 10-600 weight part with respect to 100 weight part of radically polymerizable compounds (B).

  In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by application of energy such as ultraviolet rays, visible light, near infrared rays, electron beams, etc. to obtain a desired polymer, As the light source, a light source having a main wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable. Examples of light sources having a main wavelength of light emission in the wavelength region of 250 nm to 450 nm include ultrahigh pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulsed light emission. Various light sources such as a xenon lamp, a deuterium lamp, a fluorescent lamp, an Nd-YAG triple wave laser, a He-Cd laser, a nitrogen laser, an Xe-Cl excimer laser, an Xe-F excimer laser, and a semiconductor-excited solid laser can be used. The definitions of ultraviolet rays, visible light, near-infrared rays and the like in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, various inks, ink-jet inks, overcoat varnishes, various printing plate materials, photoresists, electrophotography, direct printing plate materials, optical fibers, hologram materials, and other photosensitive materials, microcapsules, etc. It can be applied to various recording media, as well as adhesives, pressure-sensitive adhesives, adhesives, release coating agents, sealants, and various paints.

[Image pattern formation method]
The polymerizable composition of the present invention comprising an alkali resin (E) is applied on a substrate, partially exposed to an energy ray and cured, and an image pattern in which an unexposed portion is removed with an alkali developer. It can be used as a negative resist used in forming.

  An image pattern forming method using the polymerizable composition or negative resist of the present invention comprising an alkaline resin (E) will be described. First, after applying a polymerizable composition or a negative resist liquid composition on the surface of a substrate, pre-baking is performed to evaporate the solvent to form a coating film. Next, this coating film is partially exposed to a pattern according to the mask through a photomask, then developed using an alkali developer, and the unexposed part of the coating film is dissolved and removed, and then as necessary. The target image pattern can be formed by post baking.

  When a polymerizable composition or a negative resist liquid composition is applied to a substrate, a known application method such as spray coating, spin coating, slit coating, or roll coating can be employed. The coating thickness can be appropriately changed depending on the application, but is usually 0.1 to 200 μm, preferably 0.2 to 100 μm, as the film thickness after drying.

  In addition, the polymerizable composition layer or the negative resist layer of the present invention is provided on a base film mainly composed of polyester, polypropylene, polyethylene and the like typified by polyethylene terephthalate, and the negative resist layer is formed with a protective film as necessary. It is also possible to use the polysynthetic composition or the negative resist of the present invention in the form of a so-called dry film known in the industry sandwiched. The dry film is usually used by laminating the protective film and adhering it to a substrate on which a resist pattern is to be formed, and laminating the substrate on a substrate under heating and pressure conditions as necessary. To do. Pattern exposure in the case of using the polysynthetic composition or negative resist of the present invention in the form of a dry film may be carried out without peeling off the base film, in which case the base film is removed after exposure. Then, alkali development is performed.

  Polymerizing the polymerizable composition or negative resist of the present invention comprising an alkaline resin (E). The energy irradiated for obtaining the polymer is the same as that for obtaining the polymer from the above-described polymerization composition of the present invention.

  Therefore, the polymerizable composition or negative resist of the present invention comprising the alkali resin (E) is a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a pulsed emission xenon lamp, a carbon arc lamp, Metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser By applying energy from various light sources such as KrF excimer laser and F2 laser, the desired polymer or cured product can be obtained.

Therefore, in the image pattern forming method of the present invention, it is possible to use energy rays from the light source during exposure. In particular, energy rays having a wavelength in the range of 190 to 450 nm are preferable. The amount of exposure depends on the film thickness and cannot be determined uniquely, but is usually 0.5 to 100,000 J / m ² .

  Examples of the base material used in the image pattern forming method of the present invention include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, glass epoxy film or substrate, but are not limited thereto. Is not to be done. In addition, these base materials may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  As a developing method used in the image pattern forming method of the present invention, for example, any of a liquid filling method, a dipping method, a shower method, a spray method and the like may be used, and the developing time is 20 to 30 ° C., preferably 5 to 300 seconds. Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and the like. Secondary amines such as di-n-propylamine, tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine and triethylamine, tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine, pyrrole , Piperidine, N-methylpiperidine, N-methylpyrrolidine, tertiary amines such as 30-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene Tetramethylammonium Rokishido, aqueous solution of an alkaline compound such as quaternary ammonium salts such as tetraethylammonium hydroxide can be used. In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound.

  Since the compound of the present invention efficiently generates active radicals by irradiation with energy rays, particularly light, it can function as a highly sensitive radical polymerization initiator. Therefore, the radically polymerizable composition comprising the radical polymerization initiator (A) of the present invention is also a highly sensitive polymerizable composition in which the radically polymerizable compound can be polymerized in a short time. Therefore, by using the polymerizable composition of the present invention, it is possible to provide a negative resist having alkali developability suitably used for a photoresist material and an image pattern forming method using the negative resist. Furthermore, a suitable image pattern can be provided by using this image pattern forming method.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all. In addition, unless otherwise indicated, a part shows a weight part in an example. First, a synthesis example is shown about the compound which is the radical polymerization initiator of this invention used for the Example.

Example 1
Radical polymerization initiator: Synthesis of compound (1) Intermediate of compound (1): Synthesis of compound (A)

  A solution prepared by dissolving 100.0 g of N-ethyl-3-nitrocarbazole in 1000 ml of chloroform, adding 122.1 g of aluminum chloride and stirring at 0 ° C., and dissolving 47.7 g of propionyl chloride in 200 ml of chloroform for 2 hours. It was dripped over. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was poured into 2000 g of ice water and extracted with 2000 mL of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 101.7 g of Compound (A) (yield 82.5%). .

Compound (1) Precursor: Synthesis of Compound (B)

  To a solution of 100.0 g of Compound (A), 800 ml of tetrahydrofuran and 400 ml of concentrated hydrochloric acid, 43.5 g of tert-butyl nitrite was added dropwise over 1 hour with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to obtain 116.0 g of compound (B). (Yield 96.0%)

Synthesis of Compound (1) When 20.0 g of Compound (B) was stirred in 200 ml of benzene, 7.5 g of acetic anhydride and 5.3 g of sodium acetate were added and heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 400 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, The residue was recrystallized from ethyl acetate-hexane to obtain 21.0 g of Compound (1) (yield 93.0%).

Example 2
Radical polymerization initiator: Synthesis of compound (2) 20.0 g of compound (B), 9.3 g of triethylamine, 6.8 g of propionyl chloride and 200 ml of tetrahydrofuran were mixed while cooling in an ice bath, and then stirred at room temperature for 1 hour. The mixture was further stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution is poured into 600 ml of ice water, the composition organism is extracted with 200 ml of ethyl acetate, the organic layer is washed with water (200 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered and the solvent is distilled off. The residue was recrystallized from dichloroethane-hexane to obtain 18.8 g of compound (2) (yield 83.3%).

Examples 3-60
By applying the methods of Synthesis Examples 1 and 2 described above to the intermediates shown in Table 1, the compounds which are the radical polymerization initiators of the present invention shown in Table 1 could be obtained.

Table 1

  For the obtained compounds (1) to (60), the results of elemental analysis (C, H, N) (Perkin Elmer 2400 CHN) and the mass analysis results by EI-MS (Thermo PolarisQ) are combined. The structure was confirmed. The results are shown in Tables 2 and 3.

  Next, it shows in Table 4 about the compound and sensitizer which were used for the comparative example.

Table 4

  Next, the case where the compound of this invention represented by General formula (1) is used as a radical polymerization initiator (A) is shown. First, the acrylic resin solution used for the Example and the comparative example is demonstrated. This acrylic resin solution is a solution containing the alkali-soluble resin (E) of the present invention.

(Preparation of acrylic resin solution (1))
Add 800 parts by weight of cyclohexanone to the reaction solution, heat to 100 ° C. while injecting nitrogen gas into the container, and drop the mixture of the following monomers and thermal polymerization initiator at the same temperature over 1 hour to conduct the polymerization reaction. It was.
Styrene 60.0 parts by weight Methacrylic acid 60.0 parts by weight Methyl methacrylate 65.0 parts by weight Butyl methacrylate 65.0 parts by weight Azobisisobutyronitrile 10.0 parts by weight

  After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then 2.0 parts by weight of azobisisobutyronitrile dissolved in 50.0 parts by weight of cyclohexanone was added, and the reaction was further continued at 100 ° C for 1 hour. Thus, an acrylic resin solution having a weight average molecular weight of about 40,000 was obtained. After cooling to room temperature, sample about 2 g of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. Thus, an acrylic resin solution (1) was prepared.

(Preparation of acrylic resin solution (2))
Add 370 parts by weight of cyclohexanone to the reaction solution, heat to 80 ° C. while injecting nitrogen gas into the container, and drop the mixture of the following monomer and thermal polymerization initiator at the same temperature over 1 hour to conduct the polymerization reaction. It was.
Methacrylic acid 20.0 parts by weight Methyl methacrylate 10.0 parts by weight n-butyl methacrylate 55.0 parts by weight 2-hydroxyethyl methacrylate 15.0 parts by weight 2,2′-azobisisobutyronitrile 4.0 parts by weight

  After cooling to room temperature, about 2 g of acrylic resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized acrylic resin solution so that the nonvolatile content was 20% by weight. The acrylic resin solution (2) was adjusted by adding. The weight average molecular weight of the obtained acrylic resin was 40000.

(1) Curability test 1: Examples 61-150, Comparative Examples 1-14
4 parts by weight of radical polymerization initiator (A), 0 or 1 part by weight of sensitizer, 10 parts by weight of Daptot DT170 (diallyl phthalate resin manufactured by Tohto Kasei Co., Ltd.) as radical polymerizable compound (B), ditrimethylolpropane tetraacrylate 85 parts by weight was blended and melted by heating to prepare a coating solution. Table 5 shows the radical polymerization initiator (A) and sensitizer (C) used. This coating solution was applied onto a pet film using a bar coater (# 3). This coated product was irradiated with ultraviolet rays at a compare speed of 40 m / min, 40 m / min, or 50 m / min (after high pressure mercury lamp 130 W / cm1 was lit, and then rubbed with a cotton cloth to confirm the presence or absence of scratches on the film. The results are shown in Table 3. In addition, it can be judged that after the ultraviolet irradiation, the cotton cloth is not damaged, and the larger the number at the conveyor speed (m / min) of the ultraviolet irradiation apparatus, the better the curability.
○: No scratch was observed on the film. Δ: Scratch was slightly observed on the film. ×: Scratch was confirmed on the film.

Table 5

The photopolymerizable composition (Examples 61 to 120) using the radical polymerization initiator (A) of the present invention is the same as the photopolymerizable composition (Comparative Examples 1 to 6) using a conventionally known radical polymerization initiator. It became clear that it has high curability compared with. Furthermore, the photopolymerizable composition (Examples 61 to 120) using the radical polymerization initiator (A) of the present invention is a case where a conventionally known radical polymerization initiator and a sensitizer are used in combination (comparison). It also became clear that it has higher curability than Examples 7-14). Although the detailed reason is not clear, the electronic effect of substituting at least one electron-withdrawing substituent among R ^{7 to} R ¹⁰ is due to the light absorption of the compound and the efficiency of photolysis after light absorption. This is presumed to have had a positive effect on the

  Moreover, although the photopolymerizable composition using the radical polymerization initiator (A) of the present invention exhibits sufficiently high curability as it is (Examples 61 to 120), it can be further increased by using the sensitizer (C) in combination. It became clear that it was possible to improve sclerosis | hardenability (Examples 121-150).

Furthermore, the photopolymerizable composition (Examples 61 to 82) using the radical polymerization initiator (A) of the present invention in which at least one of R ^{7 to} R ¹⁰ is a nitro group includes R ^{7 to} R ¹⁰ . It became clear that it has high curability compared with the case where the radical polymerization initiator (A) of the present invention in which at least one is a substituent other than a nitro group is used (Examples 83 to 120). .

Furthermore, in particular, the photopolymerizable compositions (Examples 61 to 68, 70, 71, 73 to 82) using the radical polymerization initiator (A) of the present invention in which R ⁸ is a nitro group are used in other cases (implementation). It was revealed that the curability is superior to Examples 15 and 18). Although the detailed reason is not clear, the position where the nitro group works most effectively is likely R ⁸ , and the same tendency is shown in other substituents.

(2) Curability test 2: Examples 151-176, Comparative Examples 15-20
100 parts by weight of dipentaerythritol pentaacrylate (Sartomer, SR399) as the radical polymerizable compound (B), 500 parts by weight of the acrylic resin solution (1) as the solution containing the alkali-soluble resin (E), and 400 of cyclohexanone as the solvent 6 parts by weight of a compound shown in Table 6 as a part by weight and a radical polymerization initiator (A) was added and mixed to prepare a uniform polymerizable composition solution.

The polymerizable composition solution is filtered through a 0.2 μm pore size disk filter, coated on a stainless steel plate (# 600 polishing) using a spin coater, and heated and dried in an oven at 80 ° C. for 3 minutes. The solvent was removed. After drying, the film thickness of the polymerizable composition formed on the stainless steel plate was 2 μm. The polymerizable composition film is irradiated with light (4.5 mW / cm ² ) of a high-pressure mercury lamp through a bandpass filter that selectively transmits light of 350 nm to 380 nm. The IR spectrum was measured, and the consumption rate of the acrylic group after 10 seconds of light irradiation was calculated from the change in absorption intensity at 810 cm ⁻¹ , which is the characteristic absorption of the acrylic group, after 10 seconds of light irradiation. The results are shown in Table 6.

Table 6

  The polymerizable composition (Examples 151 to 176) using the radical polymerization initiator (A) of the present invention is compared with the case where a known oxime ester is used as a radical polymerization initiator (Comparative Examples 15 to 20). The radicals are efficiently generated by light irradiation, and the acrylic group is polymerized. Even the slightest polymerization of acrylic has a significant impact on the improvement in productivity that has been demanded in recent years. By using the radical polymerization initiator (A) of the present invention, it is possible to cope with a more sensitive process. Is possible.

Moreover, when the polymerizable composition before light irradiation formed on the stainless steel plates of Examples 151 to 174 was immersed in an aqueous tetramethylammonium hydroxide solution having a concentration of 0.2% by weight at 20 ° C. for about 1 minute, an appropriate rate was obtained. It was confirmed that the polymerizable composition of the present invention was developed with an alkaline developer.
(3) Curability test 3: Examples 177 to 197, Comparative examples 21 to 29
100 parts by weight of dipentaerythritol pentaacrylate (Sartomer, SR399) as the radical polymerizable compound (B), 500 parts by weight of the acrylic resin solution (2) as the solution containing the alkali-soluble resin (E), and propylene glycol monomethyl as the solvent 200 parts by weight of ether acetate, each of the compounds shown in Table 7 as radical polymerization initiator (A) and sensitizer (C) were added in the amount of parts by weight described in the same table, and mixed to obtain a uniform polymerizable composition. The solution was adjusted.

  The polymerizable composition solution is filtered through a 0.2 μm pore size disk filter, coated on a 1 mm thick glass plate using a spin coater, and heated and dried in an oven at 80 ° C. for 3 minutes to remove the solvent. Removed. After drying, the film thickness of the polymerizable composition film formed on the glass plate was 5 μm. This polymerizable composition film was exposed using a JA-25 SS-25CP type spectral irradiator by changing the irradiation energy amount of the high-pressure mercury lamp, that is, the irradiation time in 13 stages, and then 20 Development was carried out with a 1% aqueous sodium carbonate solution at 1 ° C. for 1 minute, and the minimum amount of energy required to insolubilize the polymerizable composition at an irradiation wavelength of 365 nm was defined as sensitivity, and the results are shown in Table 7.

Table 7

  The polymerizable compositions (Examples 177 to 197) using the radical polymerization initiator (A) of the present invention are the same as the polymerizable compositions (Comparative Examples 21 to 29) using known oxime esters as radical polymerization initiators. The sensitivity is clearly higher than that. In addition, the polymerizable composition of the present invention is sufficiently sensitive even when no sensitizer is used in combination, but can be further increased in sensitivity by using a sensitizer together.

(4) Pattern shape test: Examples 198 to 218, Comparative examples 30 to 38
The polymerizable composition films on the glass substrates prepared in Examples 177 to 197 and Comparative Examples 21 to 29 have an exposure gap of about 100 μm and an exposure energy of 365 nm with a predetermined pattern mask (20 μm × 20 μm resolution). Light from a high pressure mercury lamp of 4.5 mW / cm ² was irradiated for 10 seconds. Thereafter, development was performed at room temperature for 60 seconds with a 0.2% by weight tetramethylammonium hydroxide aqueous solution to remove unexposed portions, and after washing with pure water, the resulting cured product was placed in an oven at 230 ° C. Heated for 30 minutes. The pattern shape obtained on the glass substrate was evaluated by the following method. The results are shown in Table 8.
(Pattern shape evaluation method)
The pattern shape obtained on the glass substrate was observed with an optical microscope, and the linearity of the pattern was evaluated. The rank of evaluation is as follows.
○: Good linearity ×: Poor linearity −: Pattern cannot be observed due to insufficient curing

Table 8

  The polymerizable composition (Examples 198 to 218) using the radical polymerization initiator (A) of the present invention had good linearity of the pattern shape obtained on the glass substrate, whereas the known oxime In the polymerizable composition using the ester as a radical polymerization initiator (Comparative Examples 30 to 38), the pattern shape obtained on the glass substrate was poor or the pattern shape could not be observed due to insufficient curing.

(5) Pattern adhesion test: Examples 219 to 239, Comparative examples 39 to 47
The pattern-formed substrates prepared in Examples 198 to 218 and Comparative Examples 30 to 38 were subjected to a PCT (pressure cooker) test under the conditions of 121 ° C., 100% RH, 2 atm, and 24 hours. Pattern adhesion was evaluated by applying cellophane tape and performing a peeling test. The results are shown in Table 9.

  The rank of evaluation is as follows.

○: no peeling of 20 μm pattern was observed ×: peeling of 20 μm pattern was observed −: evaluation was not possible due to insufficient curing

Table 9

  When the polymerizable composition of the present invention was used (Examples 219 to 239), the adhesiveness of the pattern obtained on the glass substrate to the substrate was good, whereas the polymerizable composition of the present invention was used. In the case (Comparative Examples 39 to 47), sufficient pattern adhesion to the substrate was not obtained.

(6) Coloring resist film evaluation test: Examples 240 to 48 and Comparative examples 48 to
[Adjustment of red pigment dispersion]
A mixture having the following composition was stirred and mixed uniformly, then dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered with a 5 μm filter to prepare a red pigment dispersion.

11.0 parts by weight of diketopyrrolopyrrole pigment (CIPigment Red 254) (“Irga Four Red B-CF” manufactured by Ciba Specialty Chemicals)
Diketopyrrolopyrrole pigment derivative having the following structure 1.0 part by weight Acrylic resin solution 40.0 parts by weight Cyclohexanone 48.0 parts by weight

[Adjustment of green pigment dispersion]
A green pigment dispersion was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.

7.1 parts by weight of copper halide phthalocyanine pigment (CI Pigment Green 36) (“Rionol Green 6YK” manufactured by Toyo Ink Co., Ltd.)
3.9 parts by weight of monoazo pigment (CI Pigment Yellow 150) (“E4GN-GT” manufactured by LANXESS)
Triazine pigment derivative having the following structure 1.0 part by weight Acrylic resin solution 40.0 parts by weight Cyclohexanone 48.0 parts by weight

[Adjustment of blue pigment dispersion]
A blue pigment dispersion was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.

ε-type copper phthalocyanine pigment (CIPigment Blue 15: 6) 11.0 parts by weight (“Heliogen Blue L-6700F” manufactured by BASF)
Phthalocyanine pigment derivative having the following structure: 1.0 part by weight Acrylic resin solution: 40.0 parts by weight Cyclohexanone: 48.0 parts by weight

[Adjustment of black pigment dispersion]
A black pigment dispersion was prepared using a mixture having the following composition in the same manner as the red pigment dispersion.

Carbon black ("MA77" manufactured by Mitsubishi Chemical Corporation) 12.0 parts by weight Acrylic resin solution 40.0 parts by weight Cyclohexanone 48.0 parts by weight

<Preparation of coloring polymerization composition>
[Red polysynthetic composition]
Example 240
As a radical polymerization initiator (A), 58 parts by weight of the red pigment dispersion, 20 parts by weight of the acrylic resin solution (2), 3 parts by weight of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.) A mixture of 2 parts by weight of compound (1) and 17 parts by weight of cyclohexanone was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a red polymerizable composition of the present invention.

(Blue polysynthetic composition)
Example 241
As a radical polymerization initiator (A), 54 parts by weight of the blue pigment dispersion, 15 parts by weight of the acrylic resin solution (2), 4 parts by weight of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.) A mixture of 4 parts by weight of compound (1) and 25 parts by weight of cyclohexanone was stirred and mixed uniformly, and then filtered through a 1 μm filter to obtain the blue polymerizable composition of the present invention.

[Green polysynthesis composition]
Example 242
67 parts by weight of the green pigment dispersion, 11 parts by weight of the acrylic resin solution (2), 3 parts by weight of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), and radical polymerization initiator (A) A mixture of 2 parts by weight of compound (1) and 18 parts by weight of cyclohexanone was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green polymerizable composition of the present invention.

[Black composite composition]
Example 243
As a radical polymerization initiator (A), 75 parts by weight of the black pigment dispersion, 9 parts by weight of the acrylic resin solution (2), 3 parts by weight of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.) A mixture of 3 parts by weight of compound (1) and 13 parts by weight of cyclohexanone was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a green polymerizable composition of the present invention.

Examples 244 to 289, Comparative Examples 48 to 61
[Red polysynthetic composition]
A red polymerizable composition shown in Table 10 was obtained in the same manner as in Example 220 except that the compound (1) as the radical polymerization initiator was replaced with the compound shown in Table 10.

(Blue polysynthetic composition)
Blue polymerizable compositions shown in Table 10 were obtained in the same manner as in Example 221, except that the compound (1) as the radical polymerization initiator was replaced with the compounds shown in Table 10.

[Green polysynthesis composition]
Green polymerizable compositions shown in Table 10 were obtained in the same manner as in Example 222 except that the compound (1) as the radical polymerization initiator was replaced with the compounds shown in Table 10.

[Black composite composition]
A black polymerizable composition shown in Table 10 was obtained in the same manner as in Example 223 except that the compound (1) as a radical polymerization initiator was replaced with the compound shown in Table 10.

Table 10

[Filter segment and black matrix pattern formation]
The obtained colored polymerizable composition was applied to a 10 cm × 10 cm glass substrate by spin coating so that the film thickness after post-baking would be the film thickness shown in Table 4, and then in a clean oven at 70 ° C. Pre-baked for 15 minutes. Next, after cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form striped filter segments on the substrate.

[Evaluation]
The sensitivity of the obtained colored polymerizable composition and the pattern shape of the filter segment or black matrix formed by the above method were evaluated by the following methods. The results are shown in Table 11.

(sensitivity)
The sensitivity of the resist was determined by the irradiation exposure amount at which the formed filter segment or black matrix pattern was finished according to the image size of the photomask. The rank of evaluation is as follows.
A: Less than 40 mJ / cm ² ○: 40 mJ / cm ² or more and less than 80 mJ / cm ² Δ: 80 mJ / cm ² or more and less than 250 mJ / cm ² ×: 250 mJ / cm ² or more

(Pattern shape)
The shape of the formed filter segment or black matrix pattern was evaluated by (1) the linearity of the pattern and (2) the cross-sectional shape of the pattern.

(1) was evaluated by observing with an optical microscope. The rank of evaluation is as follows.
○: Good linearity △: Partially poor linearity ×: Poor linearity

(2) was evaluated by observing with a scanning electron microscope (SEM). The rank of evaluation is as follows.
○: Forward tapered shape.
Δ: Non-tapered shape.
X: Reverse taper shape.

(Residual film rate evaluation)
With respect to the film thickness measured after forming and drying the coating film of each colored composition, the remaining film has the ratio of the film thickness measured after going through exposure (100 mJ / cm ² ), development, and post-baking steps. Rate. The rank of evaluation is as follows.
○: 70% or more ×: less than 70%

Table 11

  As shown in Table 11, the colored polymerizable composition (Examples 244 to 289) using the radical polymerization initiator (A) represented by the general formula (1) was very sensitive and obtained. While the linearity and cross-sectional shape of the pattern were good, the colored polysynthetic compositions (Comparative Examples 48 to 61) using a known oxime ester compound as a radical polymerization initiator had poor sensitivity and had a pattern. -No improvement in linearity and cross-sectional shape was obtained.

  Furthermore, by using the colored polysynthetic composition (Examples 244 to 289) using the radical polymerization initiator (A) represented by the general formula (1), a high residual film ratio is obtained and production is stable in coating film formation. A product having excellent properties can be obtained. On the other hand, a colored polysynthetic composition (Comparative Examples 22 to 31) using a known oxime ester compound as a radical polymerization initiator has a poor residual film rate and does not reach a sufficient level in coating formation.

  The photopolymerizable composition using the compound of the present invention as a radical polymerization initiator may be excellent in curability as compared with a photopolymerizable composition using a combination of a conventionally known radical polymerization initiator and a sensitizer. It became clear. It became clear that this high curability contributes to a more sensitive process. In addition, the compound of the present invention that has brought about such high curability absorbs light well, and can significantly improve radical generation efficiency, and a carbazole chromophore represented by the general formula (1): This is probably because the keto-type oxime ester structure capable of generating a large amount of radicals by decomposition by light irradiation has a synergistic effect.

  The present invention relates to a novel oxime ester compound, a radical polymerization initiator (A) using the same, a polysynthetic composition using the same, a negative resist using the same, and an image pattern forming method using the same. . The compound of the present invention functions as a radical generator that is very sensitive to irradiation with energy rays. Therefore, the radical polymerization initiator (A) of the present invention using the compound of the present invention rapidly and surely proceeds with polymerization, crosslinking reaction, etc. using a radical generated by irradiation of energy rays as conventionally used as a catalyst. As a result, it can be expected to increase the sensitivity to energy rays for various applications, or to improve the characteristics of various applications by sufficiently proceeding the reaction. Examples of applications that can be expected to increase sensitivity and improve properties according to the present invention include molding resins, casting resins, photo-molding resins, sealants, dental polymerization resins, printing inks that utilize polymerization or crosslinking reactions, Ink-jet ink, paint, photosensitive resin for printing plates, color proof for printing, resist for color filters, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, rib material for plasma display, dry film resist, Resist for printed circuit boards, solder resist, photoresist for semiconductor, resist for microelectronics, resist for micromachine parts manufacturing, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat Agent, powder coatings, adhesives, pressure-sensitive adhesives, release agents, optical recording media, adhesive, release coat agent composition for image recording materials using microcapsules, and various devices and the like.

Claims (12)

A compound represented by the following general formula (1).
General formula (1)

Wherein R ¹ is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted amino group, substituted or unsubstituted Substituted phosphinoyl group, substituted or unsubstituted It represents a carbamoyl group or a substituted or unsubstituted sulfamoyl group,.
R ² represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group Represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.
R ³ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted acyl group.
R ^{4 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group. Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted Arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, or substituted or unsubstituted amino group To express. Provided that at least one of R ⁷ to R ¹⁰ is a halogen atom, a nitro group, a cyano group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkyl A sulfonyl group or a substituted or unsubstituted arylsulfonyl group. ) At least one of R ⁷ to R ¹⁰ is A compound according to claim 1, wherein the nitro group. R ⁸ is, according to claim 1 or 2 A compound according nitro group.   A radical polymerization initiator (A) comprising the compound according to claim 1.   A polymerizable composition comprising the radical polymerization initiator (A) according to claim 4 and a radical polymerizable compound (B).   The polymerizable composition according to claim 5, further comprising a sensitizer (C).   The polymerizable composition according to claim 5 or 6, further comprising a coloring component (D).   The polymerizable composition according to claim 5, further comprising an alkali-soluble resin (E).   A negative resist comprising the polymerizable composition according to claim 8.   The manufacturing method of the polymer which irradiates and polymerizes the polymerizable composition in any one of Claims 5-8 with an energy ray.   10. A method for forming an image pattern, comprising: laminating the negative resist according to claim 9 on a substrate, partially irradiating with energy rays and polymerizing, and removing an unirradiated portion with an alkali developer.   An image pattern formed by the image pattern forming method according to claim 11.