JP2010091753A - Polymerizable composition, negative resist using the same, and image pattern forming method using the resist - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-sensitivity polymerizable composition which efficiently generates active radicals upon irradiation with an energy ray, and to further provide a negative resist material which cures at a very high rate, is suitably used for very clear pattern exposure or direct drawing, has excellent adhesion to a substrate, and is suitably used as a photoresist material. <P>SOLUTION: The polymerizable composition includes a specific oxime ester-based radical polymerization initiator (A), a radical-polymerizable compound (B), and an alkali-soluble resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymerizable composition, a negative resist using the same, and an image pattern forming method using the same. More specifically, active radicals are efficiently generated by irradiation of energy rays, particularly light, radically polymerizable compounds are polymerized in a short time, and exposure is performed through a mask film in which a pattern is recorded in advance or direct drawing by a laser light source. For example, spacers for liquid crystal displays, solder resists, resists for circuit board preparation, photoresists for semiconductors, resists for microelectronics, hologram materials, rib materials for plasma displays, resists for manufacturing parts for micromachines, etching resists, waveguides Materials, compositions for image recording materials using microcapsules, polymerizable compositions for obtaining cured products having good physical properties in the fields of various devices, negative resists using the same, and Image pattern formation using Law on.

  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 1 to 3). Also, certain types of negative resists have been disclosed as materials for manufacturing electrical / electronic components and printed circuit boards (see Patent Documents 4 to 6). Recently, a resist composition using a certain O-acyloxime ester as a photopolymerization 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 7). 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 8). 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.

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

  An object of the present invention is to provide a highly sensitive polymerizable composition capable of efficiently generating active radicals upon irradiation with energy rays, particularly light, and capable of polymerizing a radical polymerizable compound in an extremely short time. A further object of the present invention is that the curing speed is extremely high, and it can be suitably used for very clear pattern exposure or direct drawing by an energy beam, and has excellent adhesion to a substrate, in particular. An object of the present invention is to provide a negative resist material having alkali developability suitably 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, the present inventors have reached the present invention. That is, the present invention relates to a polymerizable composition comprising a radical polymerization initiator (A) represented by the following general formula (1), a radical polymerizable compound (B), and an alkali-soluble resin (C).

General formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, substituted or unsubstituted aryl group, substituted or unsubstituted complex, A cyclic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted complex A ring 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 amino group, or a substituted or unsubstituted acyl group. ^{However, R 1, R 2, R} 3, R 4 and R ⁵ Any one is a substituted or unsubstituted heterocyclic group.
X represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Substituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted Or not yet It represents conversion sulfamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphinoyl group, or a substituted or unsubstituted heterocyclic group.
A represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Substituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, or substituted or unsubstituted amino group Represents. )

The present invention also relates to the above polymerizable group wherein the heterocyclic group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a polycyclic heterocyclic group having at least one ring containing a hetero atom as a constituent element. Relates to the composition.

The present invention also relates to the above polymerizable composition, wherein the heterocyclic group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a tricyclic heterocyclic group having at least one ring containing a hetero atom as a constituent element.

In the present invention, the heterocyclic group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ is selected from the substituents represented by the following general formulas (2) to (9), which are substituted or unsubstituted. It is related with the said polymeric composition which is the heterocyclic group formed.

General formula (2)

General formula (3)

General formula (4)

General formula (5)

General formula (6)

General formula (7)

General formula (8)

General formula (9)

(Wherein X ′ has the same meaning as X in formula (1)).

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

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

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

  The present invention also provides a method for forming an image pattern, comprising: laminating the negative resist on a substrate, partially irradiating and curing an energy ray, and removing an unirradiated portion with an alkali developer. About.

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

  The polymerizable composition of the present invention efficiently generates active radicals when irradiated with energy rays, particularly light, and is highly sensitive and capable of polymerizing radically polymerizable compounds in a short time. It is a polymerizable composition that can be suitably used for pattern exposure or direct drawing, and has very good adhesion to a substrate. Therefore, it was possible to provide a highly sensitive negative resist suitably used for a photoresist material and an image pattern forming method using the negative resist.

[Radical polymerization initiator (A)]
First, the radical polymerization initiator (A) of the present invention will be described. The radical polymerization initiator (A) of the present invention is characterized in that a heterocyclic group is substituted on the 3-position phenyl group as represented by the general formula (1).

  Here, the heterocyclic group in the present invention includes both aromatic and aliphatic groups, and is a monocyclic heterocyclic group containing a hetero atom, or a polycyclic ring containing at least one ring containing a hetero atom as a constituent element. Sex heterocyclic group. Hereinafter, unless otherwise specified, the heterocyclic ring is defined as described above.

  Furthermore, in the present invention, polycyclic means a compound in which a plurality of rings are condensed, and tricyclic means a compound in which three rings are condensed.

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Substituted heterocyclic group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Substituted 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 amino group Or a substituted or unsubstituted acyl group. However, ^one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a substituted or unsubstituted heterocyclic group.

  Examples of the substituted or unsubstituted aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group. , 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like, but are not limited thereto.

  Specific examples of the substituted or unsubstituted heterocyclic group include the following heterocyclic groups, but are not limited thereto.

  The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl 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, Examples thereof include, but are not limited to, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

  The substituted or unsubstituted alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples include, but are not limited to, vinyl group, allyl group, styryl group and the like.

  The substituted or unsubstituted alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples include ethynyl group, propynyl group, propargyl group, phenylethynyl group, trimethylsilylethynyl group and the like. It is not limited.

  As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 18 carbon atoms is preferable. Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, Octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy, isopropoxy, isobutoxy, isopentyloxy, sec-butoxy, t-butoxy, sec-pentyloxy, t-pentyloxy Group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyloxy group, 2 Tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like but not limited thereto.

  The substituted or unsubstituted aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. However, it is not limited to these.

  The substituted or unsubstituted heterocyclic oxy group is preferably a heterocyclic oxy group having 3 to 18 carbon atoms. Specific 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 However, it is not limited to these.

  The substituted or unsubstituted alkylsulfanyl group is preferably an alkylsulfanyl group having 1 to 18 carbon atoms, and specific examples include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, a pentylsulfanyl group, and a hexylsulfanyl group. Groups, octylsulfanyl groups, decylsulfanyl groups, dodecylsulfanyl groups, octadecylsulfanyl groups, and the like, but are not limited thereto.

  The substituted or unsubstituted arylsulfanyl group is preferably an arylsulfanyl group having 6 to 18 carbon atoms, and specific examples thereof include a phenylsulfanyl group, a 1-naphthylsulfanyl group, a 2-naphthylsulfanyl group, and a 9-anthrylsulfanyl group. , 9-phenanthrylsulfanyl group and the like, but are not limited thereto.

  The substituted or unsubstituted alkylsulfinyl group is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexyl group. Examples thereof include a sulfinyl group, a cyclohexylsulfinyl group, an octylsulfinyl group, a 2-ethylhexylsulfinyl group, a decanoylsulfinyl group, a dodecanoylsulfinyl group, an octadecanoylsulfinyl group, a cyanomethylsulfinyl group, and a methoxymethylsulfinyl group.

  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-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenol Rusurufiniru group, 4-dimethylaminophenyl sulfinyl group and the like.

The substituted or unsubstituted amino group is preferably an amino group having 0 to 50 carbon atoms, and specific examples thereof include —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N -4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, etc. Not intended to be.

  As the substituted or unsubstituted acyl group, an acyl group having 1 to 18 carbon atoms is preferable, and specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, Myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1- Examples thereof include, but are not limited to, naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-anthroyl group, and 5-naphthacenoyl group.

  Further, the above-mentioned substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted Alternatively, the hydrogen atom of the unsubstituted arylsulfinyl group, the substituted or unsubstituted amino group, and the substituted or unsubstituted acyl group 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.

  The substituent X in the general formula (1) is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy Group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted A substituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, Substituted or unsubstituted carbamo It represents group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphinoyl group, or a substituted or unsubstituted heterocyclic group.

  As the substituted or unsubstituted alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable, and specific examples include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3- Torofenashiru group, and the like.

  As the substituted or unsubstituted aryl group, an aryl group having 6 to 30 carbon atoms is preferable. Specific examples include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl. Group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl Group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl Teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenyl group Examples include a rhenyl group, a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The substituted or unsubstituted alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a styryl group.

  The substituted or unsubstituted alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples include an ethynyl group, a propynyl group, and a propargyl group.

  As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Specific examples include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, and a sec-butoxy group. T-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethoxy group, aminocarbonylmethoxy group, N, N-dibutylaminocarbonylmethoxy group, N-methylaminocarbonylmethoxy group, N-ethylaminocarbonylmethoxy group, N-octylaminocarbonylmethoxy group, - methyl -N- benzyl aminocarbonyl methoxy, benzyloxy group, and a cyano methoxy group.

  The substituted or unsubstituted aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, and specific examples include a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, and the like.

  Examples of the substituted or unsubstituted heterocyclic oxy group include a heterocyclic oxy group having 3 to 18 carbon atoms. Specific examples include a 2-furanyloxy group, a 2-thienyloxy group, a 2-indolyloxy group, 3 -Indolyloxy group, 2-carbazolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy Groups and the like.

  As the substituted or unsubstituted acyloxy group, an acyloxy group having 2 to 20 carbon atoms is preferable. Specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, and trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

  The substituted or unsubstituted alkylsulfanyl group is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, cyclohexyl Examples thereof include a sulfanyl group, an octylsulfanyl group, a 2-ethylhexylsulfanyl group, a decanoylsulfanyl group, a dodecanoylsulfanyl group, an octadecanoylsulfanyl group, a cyanomethylsulfanyl group, and a methoxymethylsulfanyl group.

  The substituted or unsubstituted arylsulfanyl group is preferably an arylsulfanyl group having 6 to 30 carbon atoms, and specific examples thereof include a phenylsulfanyl group, a 1-naphthylsulfanyl group, a 2-naphthylsulfanyl group, a 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenol Rusurufaniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The substituted or unsubstituted alkylsulfinyl group is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  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-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenol Rusurufiniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The substituted or unsubstituted alkylsulfonyl group 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, a butylsulfonyl group, and a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  As the substituted or unsubstituted arylsulfonyl group, an arylsulfonyl group having 6 to 30 carbon atoms is preferable. Specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylamino Etc. phenylsulfonyl group.

  As the substituted or unsubstituted acyl group, an acyl group having 2 to 20 carbon atoms is preferable. Specific examples include an acetyl group, a propanoyl group, a butanoyl group, a trifluoromethylcarbonyl group, a pentanoyl group, a benzoyl group, and 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The substituted or unsubstituted alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, and an octyl group. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenyl Sulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycal Nyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl Group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  As the substituted or unsubstituted carbamoyl group, a carbamoyl group having 1 to 30 carbon atoms is preferable. Specific examples include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an 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-chlorophenyl Carbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarba Mo 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.

  The substituted or unsubstituted sulfamoyl group is preferably a sulfamoyl group having 0 to 30 carbon atoms, and specific examples include a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, and an N, N-dialkyl. A sulfamoyl group, an N, N-diarylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group and the like can be mentioned. 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.

As the substituted or unsubstituted amino group, an amino group having 0 to 50 carbon atoms is preferable, and specific examples include —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N-sulfonyl. Amino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like can be mentioned. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N -4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like can be mentioned.

  The substituted or unsubstituted phosphinoyl group is preferably a phosphinoyl group having 2 to 50 carbon atoms, and specific examples include a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, and a diphenylphosphinoyl group. , Dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  As the substituted or unsubstituted heterocyclic group, a heterocyclic ring having 3 to 18 carbon atoms is preferable. Specific examples include a thienyl group, a benzo [b] thienyl group, a naphtho [2,3-b] thienyl group, and a thiantenyl group. , Furyl 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, indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group Group, 4aH-carbazolyl group, Rubazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl 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 and the like.

  Further, the above-mentioned substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl Oxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy 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 alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, Replace Properly is unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, and a hydrogen atom or a substituted or unsubstituted heterocyclic group may be further substituted with other substituents.

  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 Alkylamino group such as mino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl group 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 Sulfonyl phenacyl phosphonium Niu mill group, and the like.

  The substituent A in the general formula (1) is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy Group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted A substituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, Or substituted or unsubstituted It represents an amino group.

  Here, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Substituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, and substituted or unsubstituted amino group Mentioned above A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl in the substituent X Oxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy 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 alkoxycarbonyl group, and substituted or unsubstituted amino Same as group It is.

Here, the heterocyclic group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ is preferably a polycyclic heterocyclic group, more preferably a tricyclic heterocyclic group.

  Further, particularly preferred tricyclic heterocyclic groups include the heterocyclic groups shown below.

  X ′ is synonymous with the substituent represented by the substituent X in the general formula (1), and preferably includes a methyl group, an ethyl group, a butyl group, a phenyl group, a naphthyl group, and the like, but is not limited thereto. It is not a thing.

  Among the substituents that the heterocyclic group may have, particularly preferred is a substituted or unsubstituted acyl group, specifically, an acetyl group, an ethynyl group, a furanyl group, a tenoyl group, a benzoyl group, Examples include, but are not limited to, a toluoyl group.

When the heterocyclic groups in R ¹ , R ² , R ³ , R ⁴ and R ⁵ are substituted by these heterocyclic groups, the compound is decomposed with a smaller amount of light irradiation so that radicals are efficiently generated. In addition, it is preferable because of its excellent absorption characteristics, compatibility with resins / solvents, and stability over time. However, the detailed reason is not clear at present.

  The substituent X is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted phosphinyl group, or a substituted or unsubstituted heterocyclic group. And more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Group, t-butyl group, trifluoromethyl group, phenyl group, benzyl group, furanyl group, thienyl group and the like are mentioned, but the present invention is not limited to these examples.

The substituent A is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a methoxy group. Examples thereof include a phenyl group, a methylsulfanylphenyl group, a dimethylaminophenyl group, a naphthyl group, and a 4-methoxynaphthyl group, but the present invention is not limited to these.
Specific examples of the compound of the present invention described above are shown in Table 1, but the structure of the compound of the present invention is not limited thereto.

Table 1

  The starting material for the synthesis of the radical polymerization initiator (A) represented by the general formula (1) is an oxime represented by the following general formula (10).

General formula (10)

(In formula, R < ¹ > -R < ⁵ > and A are synonymous with General formula (1).)

  The oxime represented by the general formula (10) is described in, for example, Org. React., 7, <1953>, 327, edited by The Chemical Society of Japan, 4th edition, Experimental Chemistry Course, Vol. 14, page 1316 (Maruzen). It can be obtained by various methods. Furthermore, it can also be obtained from a method for synthesizing oximes described in commercially available chemistry texts (for example, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992). The β-diketone that is a starting material for oxime synthesis is, for example, Tetrahedron: Asymmetry, 14, <2003>, 2739, Chem. Ber., 113, <1980>, 1507, Helvetica Chimica Acta, 84, <2001 >, 2316, Organic Syntheses, Coll. Vol. III, pp 251; Bull. Chem. Soc. Jpn., 71, <1998>, 2253.

  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 radical polymerization initiator (A) represented by the general formula (1) is a method described in the literature, for example, an oxime and an acyl obtained by the method described above, using the oxime represented by the general formula (10) as a starting material. Reacting with chloride or anhydride in 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 It is manufactured by.

  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 identified by elemental analysis values and ¹ H-NMR.

  Many of the conventionally known α, α′-diketooxime ester compounds generally do not exhibit absorption at wavelengths longer than the ultraviolet region, and thus are less active against near ultraviolet to near infrared light. The radical polymerization initiator (A) represented by the general formula (1) has an absorption band from the near ultraviolet to the visible region by introducing a heterocyclic group on the phenyl group. It is possible to have activity up to the wavelength region.

  Furthermore, as described above, the radical polymerization initiator (A) of the present invention is any of the substituents represented by the general formulas (2) to (9) on the 3-position phenyl group in the general formula (1). In addition to the above-described absorption characteristics and sensitivity, the solubility and developability are also improved. Although the detailed reason is not clear at present, it is thought that the electronic contribution of the heterocyclic group has a good effect on the compound.

[Radically polymerizable compound (B)]
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. ”Monomers” series.

  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 usage-amount of the radical polymerization initiator (A) of this invention is 0.1-100 weight part with respect to 100 weight part of radically polymerizable compounds (B), Preferably it is 3-60 weight part.

[Alkali-soluble resin (C)]
The alkali-soluble resin (C) of the present invention will be described. The alkali-soluble resin (C) 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 (C) other than the carboxyl group-containing copolymer include novolac resins and resins having a phenolic hydroxyl group such as polyhydroxystyrene, and their modified products are also alkali-soluble resins ( C).

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

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

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

  Specific examples of such a sensitizer (D) include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, and benzoin derivatives. , 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, tetrabenzenes Zoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran Derivatives, spirooxazine derivatives, thiospiropyran derivatives, carbazole derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives, and the like. Other specific examples include Ogahara Nobu et al. Sensitizers described in Okawara Nobu et al., “Functional dye chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special functional materials” (1986, CMC) However, it is not limited to these, and other examples include sensitizers that absorb light from the ultraviolet to the near-infrared region, and these may be used in two or more at any ratio as necessary. It doesn't matter. 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 ratio of the radical polymerization initiator (A) and the sensitizer (D) represented by the general formula (1) is arbitrary, but is preferably 1 to 10,000 parts by weight with respect to 100 parts by weight of the radical polymerization initiator. More preferably, it is 20 to 5000 parts by weight, and particularly preferably 30 to 2000 parts by weight.

[Chain transfer agent]
In the polymerizable composition of the present invention, a chain transfer agent can be added for the purpose of further promoting polymerization. The addition of a chain transfer agent suppresses the inhibition of polymerization by oxygen and promotes a uniform photocuring reaction even under high light shielding. Therefore, the addition of a chain transfer agent is preferred when it is necessary to promote polymerization. The chain transfer agent is not particularly limited as long as it has such a function, but a thiol compound is preferable, and a polyfunctional thiol compound is particularly preferable.

  The compound having a thiol group used as a chain transfer agent is not particularly limited as long as it has at least one or more thiol groups in the molecule, and is arbitrarily selected from those conventionally used for polymerizable compositions. Can be selected and used. Examples of the compound having such a thiol group include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 5-chloro-2-mercaptobenzothiazole, 2-mercapto-5-methoxybenzothiazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 5-mercapto-1-methyltetrazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 2-mercapto-1-methyl Examples thereof include, but are not limited to, imidazole, 2-mercaptothiazoline, and octanethiol.

  Particularly preferred polyfunctional thiol compounds include compounds having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, 1,4-butanediolbis (3-mercaptopropio 1, 4-butanediol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylol Propanetris (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), 2,5-hexanedithiol, 2,9-decandici 1,4-bis (1-mercaptoethylbenzene), bis (1-mercaptoethyl ester) phthalate, bis (2-mercaptopropyl ester) phthalate, bis (3-mercaptobutyl ester) phthalate, phthalic acid Bis (3-mercaptoisobutyl ester), ethylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), 1,4-butanediol bis (3 -Mercaptobutyrate), 1,3-butanediol bis (3-mercaptobutyrate), 1,2-butanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol Tetrakis (3- Lucaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoiso) Butyrate), 1,4-butanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol tetrakis ( 2-mercaptoisobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoiso) Butyrate), 1,4-butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexakis ( 3-mercaptoisobutyrate), 1,8-octanediol bis (3-mercaptobutyrate), 1,8-octanediol bis (2-mercaptopropionate), 1,8-octanediol bis (3-mercapto) Isobutyrate), 2,4,6-trimercapto-S-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-S-triazine, and the like. is not.

  In the present invention, these chain transfer agents can be used alone or in combination of two or more.

  The amount of the chain transfer agent used is preferably 5 to 3000 parts by weight, more preferably 20 to 1000 parts by weight with respect to 100 parts by weight of the radical polymerization initiator (A) of the present invention.

[Other photopolymerization initiators]
The polymerizable composition of the present invention is sufficiently sensitive only with the radical polymerization initiator (A), but for other purposes such as improving the surface curability of the polymerizable composition and improving the adhesion to the substrate, etc. The polymerization initiator can be used in combination.

  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 38-30015 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. 109851, European Patent No. 126712, “Journal of Imaging Science” (J.IMAG.SCI.) ", Volume 30, page 174 (1986), titanocenes described in JP-A-61-1151197," COORDINATION CHEMISTRY REVIEW " 84), 85-277 (1988) and special A transition metal complex containing a transition metal such as ruthenium described in JP-A-2-302701, an aluminate complex described in JP-A-3-209477, a borate compound 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, JP-A-5-213861, JP-A-5-255347, JP-A-5-255421, JP-A-6-157623, JP-A-2000-344812, JP-A-2002-265512, and Japanese Patent Application No. 2004. No. 053009 and the sulfonium complex or oxosulfo described in Japanese Patent Application No. 2004-263413 Ni complexes, JP-A Nos. 2001-264530, 2001-261661, 2000-80068, 2001-233842, USP 3558309 (1971), USP 4202697 (1980) Oxime ester compounds described in JP-A-61-24558, JP-A-2004-534797, and JP-A-2004-359639, bifunctional photoinitiators described in JP-A-2002-530372, etc. However, it is not limited to these.

  These polymerization initiators are preferably contained in an amount of 10 parts by weight or less based on 100 parts by weight of the radical polymerization initiator (A) of the present invention.

[binder]
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 resins, alkyd resins, etc., supervised by Kiyoshi Akamatsu, “New Photosensitive Resin Technology” (1987, CMC) and “10308 Chemical Products”, pages 657-767 (1988, Chemical Industries Day) Company) industry known organic polymer described, and the like.

[Coloring component (E)]
A coloring component 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. 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.

  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.

The amount used in the case of adding these pigments 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 the absorption coefficient of visible light (spectrum appropriateness) and transparency, it is preferable that it is sufficiently small with respect to the wavelength of visible light. 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 this invention, a pigment derivative can be used in order to improve the dispersibility of a pigment.

  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 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, methine dyes, and the like. 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.

[Additive]
In addition, the polymerizable composition of the present invention further comprises an oxygen scavenger such as phosphine, phosphonate, phosphite, a reducing agent, a polymerization accelerator, an antifoggant, an antifading agent, an antihalation agent, a fluorescent whitening, depending on the purpose. Agents, surfactants, extenders, plasticizers, flame retardants, antioxidants, UV absorbers, foaming agents, fungicides, thermal polymerization inhibitors, antistatic agents, magnetic substances and other additives that impart various properties You may mix and use an agent.

[solvent]
The polymerizable composition of the present invention can be used by adding a solvent for the purpose of improving workability during coating and film formation. The added solvent can be substantially removed by heat drying or vacuum drying after coating. Specific examples of the solvent that can be added to the polymerizable composition of the present invention include, for example, ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol (Poly) alkylene glycol monoalkyl ether acetates such as monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-n -Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoe Ether, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

  Ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, ethyl butyrate, isopropyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxy Esters such as methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Chill, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methyl propionate, ethyl 2-methoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. Esters;

  Aromatic hydrocarbons such as toluene and xylene, and amides such as N-methylpyrrolidone and N, N-dimethylacetamide can be exemplified.

  These solvents can be used alone or in admixture of two or more.

[Image pattern formation method]
The polymerizable composition of the present invention is applied on a substrate, partially exposed to an energy ray and cured, and used to form an image pattern in which an unexposed portion is removed with an alkaline developer. It can be used as a resist. An image pattern forming method using the polymerizable composition of the present invention will be described. First, after apply | coating the liquid composition of a polymeric composition on the surface of a base material, it prebakes and a solvent is evaporated and a coating film is formed. 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 the liquid composition of the polymerizable composition is applied to the substrate, a known application method such as spray coating, spin coating, slit coating, roll coating or the like 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.

  Also, a polymerizable composition layer of the present invention is provided on a base film mainly composed of polyester typified by polyethylene terephthalate, polypropylene, polyethylene, etc., and the polymerizable composition layer is sandwiched between protective films as necessary, so-called It is also possible to use the polymerizable composition of the present invention in a form known as a dry film known in the industry. 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. When the polymerizable composition of the present invention is used in the form of a dry film, pattern exposure may be carried out without peeling off the base film. To implement.

  In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by application of energy such as ultraviolet rays, visible rays, near infrared rays, electron beams, etc. to obtain a desired polymer. The definitions of ultraviolet rays, near-ultraviolet rays, visible light, near-infrared rays, infrared rays, and the like referred to in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, the polymerizable composition of the present invention includes 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, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, Energy from various light sources such as 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, KrF excimer laser, F2 laser The objective polymer and hardened | cured material can be obtained by provision of this.

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.

  The polymerizable composition of the present invention is a highly sensitive polymerizable composition capable of efficiently generating active radicals upon irradiation with energy rays, particularly light, and capable of polymerizing a radical polymerizable compound 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 and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited only to the following. 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 (C) 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.

  The compounds used in Examples and Comparative Examples are shown in Table 2.

Table 2

Examples 1 to 23 and Comparative Examples 1 to 3
100 parts by weight of dipentaerythritol pentaacrylate (Sartomer, SR399) as a radical polymerizable compound (B), 500 parts by weight of an acrylic resin solution (1) as a solution containing an alkali-soluble resin (C), and 400 of cyclohexanone as a solvent 6 parts by weight of the compounds shown in Table 3 as parts by weight and radical polymerization initiator (A) were 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 (9 mW / cm ² ) of a high-pressure mercury lamp through a bandpass filter that selectively transmits light of 350 to 380 nm, and the IR spectrum of the polymerizable composition film Was measured, and the consumption rate of the acrylic group after 15 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. The results are shown in Table 3.

Table 3

  The polymerizable composition (Examples 1 to 23) using the radical polymerization initiator (A) of the present invention is a case where a known α, α'-diketooxime ester is used as a radical polymerization initiator (Comparative Example 1). Rather than ~ 3), radicals are more efficiently generated by light irradiation to polymerize acrylic groups. That is, by using an α, α′-diketooxime ester compound having a heterocyclic group on the 3-position phenyl group in the general formula (1) as a radical polymerization initiator, high sensitivity can be achieved. It is possible.

  Furthermore, the radical polymerization initiator (A) of the present invention in which a substituent selected from any one of the general formulas (2) to (9) is introduced onto the 3-position phenyl group in the general formula (1). The polysynthetic compositions (Examples 1, 3, 5-11, and 13) using a radical polymerization initiator in which a heterocyclic group other than the general formulas (2) to (9) is substituted on the 3-position phenyl group It is superior in sensitivity to the polymerizable composition using Examples (Examples 2, 4, 12, 14 to 23). That is, the polymerization initiator of the present invention represented by the general formula (1) is further substituted by substitution of the heterocyclic group represented by the general formulas (2) to (9) on the 3-position phenyl group. It became clear that it functions as a highly sensitive initiator.

  Moreover, when the polymerizable composition before light irradiation formed on the stainless steel plates of Examples 1 to 8 was immersed in a 0.2% by weight aqueous tetramethylammonium hydroxide solution 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.

Examples 23-71 and Comparative Examples 4-9
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 (C), and propylene glycol monomethyl as the solvent 200 parts by weight of ether acetate, each of the compounds shown in Table 4 as radical polymerization initiator (A) and sensitizer (D) were added in parts by weight listed 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 for insolubilization of the polymerizable composition at an irradiation wavelength of 365 nm was defined as sensitivity, and the results are shown in Table 4.

Table 4

  The polymerizable composition (Examples 24-71) using the radical polymerization initiator (A) of the present invention is a polymerizable composition using a known α, α'-diketooxime ester as a radical polymerization initiator ( Compared with Comparative Examples 4 to 9), the sensitivity is clearly higher. 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.

Examples 72-98 and Comparative Examples 10-15
The polymerizable composition films on the glass substrates prepared in Examples 24-29, 33-38, 48-53, 60-68, and Comparative Examples 4-9 were applied with a predetermined pattern mask (20 μm × 20 μm resolution). The exposure gap was about 100 μm and the exposure energy of 365 nm was irradiated with light from a high pressure mercury lamp having an exposure energy of 10 mW / cm ² for 15 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 5.

(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 5

  The polymerizable compositions (Examples 72 to 98) 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 α , Α′-diketooxime ester as a radical polymerization initiator (Comparative Examples 10 to 15), the linearity of the pattern shape obtained on the glass substrate was poor or insufficiently cured, resulting in a pattern shape. Could not be observed.

Examples 99-125 and Comparative Examples 16-21
The pattern-formed substrates prepared in Examples 72 to 98 and Comparative Examples 10 to 15 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 6.

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 6

  When the polymerizable composition of the present invention was used (Examples 99 to 125), the adhesion 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 16 to 21), sufficient adhesion of the pattern to the substrate was not obtained.

Examples 126 to 161, Comparative Examples 22 to 31
[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 126
As a photopolymerization initiator (A), 58 parts by weight of a red pigment dispersion, 20 parts by weight of an 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 127
As a photopolymerization 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 128
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.), as a photopolymerization 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 129
As a photopolymerization 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.

Example 130
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (2).

Example 131
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as the photopolymerization initiator was replaced with the compound (2).

Example 132
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (2).

Example 133
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (5).

Example 134
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as the photopolymerization initiator was replaced with the compound (5).

Example 135
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (5).

Example 136
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (7).

Example 137
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as the photopolymerization initiator was replaced with the compound (7).

Example 138
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (7).

Example 139
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (10).

Example 140
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as a photopolymerization initiator was replaced with the compound (10).

Example 141
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (10).

Example 142
A black polymerizable composition was obtained in the same manner as in Example 129 except that the compound (1) as the photopolymerization initiator was replaced with the compound (10).

Example 143
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (11).

Example 144
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as a photopolymerization initiator was replaced with the compound (11).

Example 145
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (11).

Example 146
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (12).

Example 147
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as a photopolymerization initiator was replaced with the compound (12).

Example 148
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (12).

Example 149
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (13).

Example 150
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as a photopolymerization initiator was replaced with the compound (13).

Example 151
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (13).

Example 152
A black polymerizable composition was obtained in the same manner as in Example 129 except that the compound (1) as the photopolymerization initiator was replaced with the compound (13).

Example 153
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (15).

Example 154
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as the photopolymerization initiator was replaced with the compound (15).

Example 155
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (15).

Example 156
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (19).

Example 157
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as a photopolymerization initiator was replaced with the compound (19).

Example 158
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (19).

Example 159
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (21).

Example 160
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as a photopolymerization initiator was replaced with the compound (21).

Example 161
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (21).

Comparative Example 22
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (24).

Comparative Example 23
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as a photopolymerization initiator was replaced with the compound (24).

Comparative Example 24
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (24).

Comparative Example 25
A black polymerizable composition was obtained in the same manner as in Example 129 except that the compound (1) as the photopolymerization initiator was replaced with the compound (24).

Comparative Example 26
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (25).

Comparative Example 27
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as the photopolymerization initiator was replaced with the compound (25).

Comparative Example 28
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (25).

Comparative Example 29
A red polymerizable composition was obtained in the same manner as in Example 126 except that the compound (1) as the photopolymerization initiator was replaced with the compound (26).

Comparative Example 30
A blue polymerizable composition was obtained in the same manner as in Example 127 except that the compound (1) as a photopolymerization initiator was replaced with the compound (26).

Comparative Example 31
A green polymerizable composition was obtained in the same manner as in Example 128 except that the compound (1) as the photopolymerization initiator was replaced with the compound (26).

[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 7.

(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 50 mJ / cm ² O: 50 mJ / cm ² or more and less than 100 mJ / cm ² Δ: 100 mJ / cm ² or more and less than 300 mJ / cm ² ×: 300 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 Δ: 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 7

  As shown in Table 7, the colored polymerization compositions (Examples 126 to 161) using the photopolymerization initiator represented by the general formula (1) have high sensitivity, and the linearity of the obtained pattern. And the cross-sectional shape was also good, the colored polysynthetic compositions (Comparative Examples 22 to 31) using a known α, α′-diketooxime ester compound as a photopolymerization initiator had poor sensitivity, No good pattern linearity and cross-sectional shape were obtained.

  Furthermore, by using the colored polysynthetic composition (Examples 126 to 161) using the photopolymerization initiator represented by the general formula (1), it has a high residual film ratio and is excellent in production stability in coating film formation. You can get things. On the other hand, a colored polysynthetic composition (Comparative Examples 22 to 31) using a known α, α′-diketooxime ester compound as a photopolymerization initiator has a poor residual film ratio and is at a sufficient level in coating film formation. Not reached.

  The present invention relates to a high-sensitivity polymerizable composition, a negative resist using the same, and an image pattern forming method using the same. For example, a spacer for liquid crystal display, MVA (multiple division vertical alignment) system Ribs, solder resists, resists for circuit board creation, resists for semiconductors, resists for microelectronics, hologram materials, rib materials for plasma displays, resists for manufacturing parts for micromachines, etching resists, waveguide materials, micro It can be a material and method for quickly and reliably obtaining a patterned cured product having good physical properties in the field of compositions for image recording materials using capsules, various devices and the like.

Claims (9)

A polymerizable composition comprising a radical polymerization initiator (A) represented by the following general formula (1), a radical polymerizable compound (B), and an alkali-soluble resin (C).
General formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, substituted or unsubstituted aryl group, substituted or unsubstituted complex, A cyclic group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted complex A ring 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 amino group, or a substituted or unsubstituted acyl group. ^{However, R 1, R 2, R} 3, R 4 and R ⁵ Any one is a substituted or unsubstituted heterocyclic group.
X represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Substituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted Or not yet It represents conversion sulfamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphinoyl group, or a substituted or unsubstituted heterocyclic group.
A represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyloxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Substituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted alkoxycarbonyl group, or substituted or unsubstituted amino group Represents. ) ^2. The polymerizable composition according to claim 1, wherein the heterocyclic group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a polycyclic heterocyclic group having at least one ring containing a hetero atom as a constituent element. . The polymerizable group according to claim 1 or 2, wherein the heterocyclic group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a tricyclic heterocyclic group containing at least one ring containing a hetero atom as a constituent element. Composition. The heterocyclic group in R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a heterocyclic group selected from substituted or unsubstituted substituents represented by the following general formulas (2) to (9). The polymerizable composition according to any one of claims 1 to 3.
General formula (2)

General formula (3)

General formula (4)

General formula (5)

General formula (6)

General formula (7)

General formula (8)

General formula (9)

(In the formula, X ′ has the same meaning as X in formula (1).)   The polymerizable composition according to any one of claims 1 to 4, further comprising a sensitizer (D).   The polymerizable composition according to any one of claims 1 to 5, further comprising a coloring component (E).   A negative resist comprising the polymerizable composition according to claim 1.   A method of forming an image pattern, comprising: laminating the negative resist according to claim 7 on a substrate, partially irradiating and curing an energy ray, and removing an unirradiated portion with an alkali developer.   An image pattern formed by the image pattern forming method according to claim 8.