JP2017149661A - Oxime ester compound, and polymerization initiator containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound activated by absorbing efficiently near-ultraviolet light of 365 nm or the like, having high sensitivity and curability, and useful as a polymerization initiator; and to provide a polymerization initiator using the compound, and a polymerizable composition.SOLUTION: Provided is an oxime ester compound has a skeleton in which groups having condensed rings adjoin by spiro bond or direct bond, and have one or more groups shown by formula (1), respectively in each group having the condensed ring (n is 0 or 1; * shows a bonding position to an adjacent condensed ring; and Rand Reach independently show H, halogen, nitro, cyano, a C1-20 hydrocarbon group, or a C2-20 group containing a heterocycle).SELECTED DRAWING: None

Description

  The present invention relates to a novel oxime ester compound useful as a polymerization initiator for use in a polymerizable composition, a polymerization initiator containing the compound, and a polymerizable composition comprising the ethylenic unsaturated compound in the polymerization initiator. And a colored polymerizable resin composition further containing a coloring material in the polymerizable composition and the cured product obtained from the polymerizable composition.

  The polymerizable composition is obtained by adding a polymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by irradiation with energy rays (light). It is used for photosensitive printing plates and various photoresists.

As the polymerization initiator used in the polymerizable composition, Patent Documents 1 to 4 below propose using an oxime ester compound.
However, among the oxime ester compounds described in the above-mentioned patent documents, the oxime ester compound having satisfactory sensitivity has a problem that the transmittance in the visible light region is low and a desired color cannot be obtained with a color filter (particularly, a transparent insulating film). In the case of a transparent polymerizable composition such as the above, and a color filter resist using a blue pigment or dye, brightness, luminance and color purity are reduced when a compound having absorption at 380 to 450 nm is mixed. The oxime ester compound having a high transmittance in the visible light region has a problem that the sensitivity is not sufficiently satisfactory, and a polymerization initiator having both characteristics has been demanded.

  In addition, a colored polymerizable resin composition containing a color material such as a color filter is required to have high sensitivity, and the polymerization initiator in the resist needs to have a high concentration. However, a high concentration of the polymerization initiator causes generation of a residue due to deterioration of developability, contamination of a photomask or a heating furnace with a sublimation product, and the like.

JP 2000-80068 A JP-T-2006-516246 JP-T-2015-523318 WO2007 / 080947 pamphlet

  The problem to be solved by the present invention is that a cured product having high sensitivity and curability and high transparency is obtained, and there has been no oxime ester compound useful as a polymerization disclosure agent.

  Accordingly, an object of the present invention is to provide a novel oxime which is effective as a polymerization initiator by obtaining a cured product having high sensitivity and curability, which is activated by efficiently absorbing near ultraviolet light such as 365 nm and the like, and high transparency. An object of the present invention is to provide an ester compound, a polymerization initiator using the compound, and a polymerizable composition.

  The present invention relates to an oxime ester compound having a skeleton in which groups having a condensed ring are adjacent to each other by a spiro structure or a direct bond and a group represented by the following general formula (I), and a polymerization containing the compound The above object is achieved by providing an initiator.

（式中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
Ｒ^１及びＲ^２で表される炭素原子数１〜２０の炭化水素基又はＲ^１及びＲ^２で表される複素環を含有する炭素原子数２〜２０の基の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ＣＨ_２＝ＣＨ−Ｏ−、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、Ｒ^１及びＲ^２で表される炭素原子数１〜２０の炭化水素基又はＲ^１及びＲ^２で表される複素環を含有する炭素原子数２〜２０の基中のメチレン基は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^３−、−ＮＲ^３ＣＯ−、−Ｓ−、−ＣＳ−、−ＳＯ_２−、−ＳＣＯ−、−ＣＯＳ−、−ＯＣＳ−又はＣＳＯ−で置換される場合もあり、
Ｒ^３は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、
ｎは０又は１を表す。式中の＊は、＊部分で、隣接する基と結合することを意味する。）

(In the formula, each of R ¹ and R ² independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a C 2-20 carbon atom containing a heterocyclic ring. Represents a group,
Hydrogen atom of the group having 2 to 20 carbon atoms containing heterocyclic ring represented by hydrocarbon radicals or ^{R 1} and ^{R 2} having 1 to 20 carbon atoms represented by R ¹ and ^{R 2,} a halogen atom, It may be substituted with a nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, CH ₂ ═CH—O—, mercapto group, isocyanate group or heterocyclic group-containing group. There, a methylene group in the group having 2 to 20 carbon atoms containing heterocyclic ring represented by hydrocarbon group, or ^{R 1} and ^{R 2} having 1 to 20 carbon atoms represented by ^{R 1} and ^{R 2, -O -, - CO -, -} COO -, - OCO -, - NR 3 -, - NR 3 CO -, - S -, - CS -, - SO 2 -, - SCO -, - COS -, - OCS -Or CSO- may be substituted,
R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 0 or 1. * In the formula means bonding with an adjacent group at the * portion. )

Moreover, this invention provides the polymeric composition containing the said polymerization initiator and an ethylenically unsaturated compound.
Moreover, this invention provides the colored polymeric composition containing the said polymeric composition and a coloring material.

  Moreover, this invention forms the hardened | cured material characterized by including the process of preparing a base | substrate, the process of apply | coating the said polymeric composition or the said colored polymerizable composition to a base | substrate, and the process of irradiating an energy ray. A method is provided.

  Moreover, this invention provides the hardened | cured material of the said polymeric composition or the said colored polymeric composition.

  According to the present invention, a cured product having high sensitivity and curability and high transparency can be obtained, and an oxime ester compound useful as a polymerization initiator can be provided.

  Hereinafter, the oxime ester compound of the present invention and a polymerization initiator containing the compound will be described in detail based on preferred embodiments.

The oxime ester compound of the present invention is a novel compound having a skeleton in which groups having condensed rings are adjacent to each other and a group represented by the above general formula (I). The oxime ester compound has a geometric isomer and an optical isomer, but these are not distinguished.
That is, in the present specification, the compounds represented by the following general formulas (IIa), (IIb), (IVa) and (IVb) and their exemplified compounds represent one or a mixture of two or more of these isomers. It is not limited to the structure showing a specific isomer.

  The groups having the condensed ring are adjacent to each other by either a spiro structure or a direct bond. The groups having two condensed rings are bonded in a form sharing a spiro structure, or two condensed rings. Means that one atom in the condensed ring of the group having one condensed ring is bonded to one atom in the condensed ring of the group having the other condensed ring by a direct bond.

As the condensed ring, those having a conjugated ring structure are preferable because they have high sensitivity when used as a polymerization initiator, and adjacent atoms are atoms on the conjugated ring or atoms present in the same plane as the conjugated ring. Some cases are even more preferred.
When the groups having the condensed ring are adjacent to each other by a spiro structure, the adjacent atom has two condensed rings, for example, an atom surrounded by a circle in the group represented by [Chemical 1A] below. Means an atom shared by the fused rings of a group. A typical example of such an atom is carbon, but is not limited to this, and silicon and nitrogen can also be used. When the groups having the condensed ring are adjacent to each other by a direct bond, the atoms in the condensed ring of the group having two condensed rings, such as an atom surrounded by a circle in the group represented by [Chemical 1B] below, are represented. Among them, it means an atom bonded by a direct bond. A typical example of such an atom is carbon, but is not limited to this, and nitrogen can also be used.

  As a skeleton in which the groups having the condensed ring are adjacent to each other by either a spiro structure or a direct bond, when used as a polymerization initiator, the sensitivity is high and the cured product has excellent transparency. -1) to (a-12) or a structure shown by any of the following (b-1) to (b-12) is preferable.

  Since the sensitivity is good when the oxime ester compound of the present invention is used as a polymerization initiator, each of the groups having the condensed ring preferably has a group represented by the general formula (I). .

  As the oxime ester compound of the present invention, a compound represented by the following general formula (IIa) or (IIb) is preferable because of excellent transparency.

〔式中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ⁸、Ｒ^９、Ｒ^１０及びＲ^１１（以下、Ｒ^４〜Ｒ^１１とも記載）は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、トリフルオロメチル基、ホルミル基、スルホ基、上記一般式（Ｉ）で表される基、Ｒ^２０、ＯＲ^２０、ＳＲ^２０、ＮＲ^２１Ｒ^２２、ＣＯＲ^２０、ＳＯＲ^２０、ＳＯ_２Ｒ^２０、ＣＯＮＲ^２１Ｒ^２２、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
Ｒ^２０、Ｒ^２１及びＲ^２２は、それぞれ独立に、水素原子、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
Ｘ^１及びＸ^２は、それぞれ独立に−ＣＯ−、−ＣＲ^２３Ｒ^２４−、下記一般式（III）

（式中、Ｒ^２５は、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表す。式中の＊は、＊部分で、隣接する基と結合することを意味する。）
で表される基又は隣接するＹ^１若しくはＹ^２と結合して環を形成する基を表し、該隣接するＹ^１若しくはＹ^２と結合して環を形成する基中の水素原子は、上記一般式（Ｉ）で表される基により置換される場合もあり、
Ｒ^２３及びＲ^２４は、それぞれ独立に、水素原子、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、Ｒ^２３とＲ^２４は、結合して環を形成する場合もあり、
Ｙ^１及びＹ^２は、それぞれ独立に−ＣＲ^２６Ｒ^２７−又は隣接するＸ^１若しくはＸ^２と結合して環を形成する場合もあり、
Ｒ^２６及びＲ^２７は、それぞれ独立に、水素原子、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、Ｒ^２６とＲ^２７は、結合して環を形成する場合があり、
Ｒ^４〜Ｒ^１１、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６及びＲ^２７（以下、Ｒ^４〜Ｒ^１１及びＲ^２０〜Ｒ^２７とも記載）で表される炭素原子数１〜２０の炭化水素基又はＲ^４〜Ｒ^１１及びＲ^２０〜Ｒ^２７で表される複素環を含有する炭素原子数２〜２０の基の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、メルカプト基、イソシアネート基、カルボキシル基又は複素環含有基で置換される場合があり、Ｒ^４〜Ｒ^１１及びＲ^２０〜Ｒ^２７で表される複素環を含有する炭素原子数２〜２０の基又はＲ^４〜Ｒ^１１及びＲ^２０〜Ｒ^２７で表される複素環を含有する炭素原子数２〜２０の基中のメチレン基は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^２８−、−ＮＲ^２８ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＳＣＯ−又は−ＣＯＳ−で置換される場合もあり、
Ｒ^２８は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、
Ｒ^４とＲ^５、Ｒ^５とＲ^６、Ｒ^６とＲ^７、Ｒ^８とＲ^９、Ｒ^９とＲ^１０又はＲ^１０とＲ^１１は結合して環を形成する場合もあり、
Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ⁸、Ｒ^９、Ｒ^１０及びＲ^１１の少なくとも一つが上記一般式（Ｉ）で表される基であるか、Ｙ^１と結合して環を形成する基及びＹ^２と結合して環を形成する基中の水素原子の少なくとも一つが、上記一般式（Ｉ）で表される基により置換されている。〕

[Wherein, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ (hereinafter also referred to as R ^{4 to} R ¹¹ ) are each independently a hydrogen atom, a halogen atom, Nitro group, cyano group, hydroxyl group, carboxyl group, trifluoromethyl group, formyl group, sulfo group, group represented by the above general formula (I), R ²⁰ , OR ²⁰ , SR ²⁰ , NR ²¹ R ²² , COR ²⁰ , SOR ²⁰ , SO ₂ R ²⁰ , CONR ²¹ R ²² , a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
X ¹ and X ² are each independently —CO—, —CR ²³ R ²⁴ —, the following general formula (III)

(In the formula, R ²⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring. * Means that it is bonded to an adjacent group at the * part.)
A group represented by or combined with the adjacent Y ¹ or Y ² represents a group forming a ring, the hydrogen atom in the groups bound to Y ¹ or Y ² to the adjacent form a ring, the general In some cases, the group may be substituted by a group represented by the formula (I),
R ²³ and R ²⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R ²³ and R ²⁴ are bonded to each other. May form a ring,
Y ¹ and Y ² may each independently bond with —CR ²⁶ R ²⁷ — or adjacent X ¹ or X ² to form a ring,
R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R ²⁶ and R ²⁷ are bonded to each other. May form a ring,
R ^{4 to} R ¹¹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ (hereinafter also referred to as R ^{4 to} R ¹¹ and R ^{20 to} R ²⁷ ) The hydrogen atom of the group having 2 to 20 carbon atoms containing a heterocyclic group represented by a hydrocarbon group having 1 to 20 carbon atoms or R ^{4 to} R ¹¹ and R ^{20 to} R ²⁷ is a halogen atom, a nitro group, It may be substituted with a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group, a carboxyl group, or a heterocyclic group, and R ^{4 to} R ¹¹ and A group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ^{20 to} R ²⁷ or a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ^{4 to} R ¹¹ and R ^{20 to} R ²⁷ Group Tylene group is substituted with —O—, —CO—, —COO—, —OCO—, —NR ²⁸ —, —NR ²⁸ CO—, —S—, —SO ₂ —, —SCO— or —COS—. Sometimes
R ²⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ or R ¹⁰ and R ¹¹ may be combined to form a ring,
At least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is a group represented by the above general formula (I), or is bonded to Y ¹ to form a ring. At least one hydrogen atom in the group to be formed and the group that is bonded to Y ² to form a ring is substituted with the group represented by the above general formula (I). ]

〔式中、Ｒ^１２及びＲ^１６は、それぞれ独立に、Ｒ^３１、ＯＲ^３１、ＳＲ^３１、ＰＲ^３２Ｒ^３３、ＮＲ^３２Ｒ^３３又はＮＨＰＲ^３２Ｒ^３３を表し、
Ｒ^３１、Ｒ^３２及びＲ^３３は、それぞれ独立に、炭素原子数１〜２０の炭化水素基を表し、
Ｒ^３２とＲ^３３は、結合して環を形成する場合もあり、
Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１７、Ｒ^１８及びＲ^１９は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、上記一般式（Ｉ）で表される基、Ｒ^３４、ＯＲ^３４、ＳＲ^３４、ＮＲ^３５Ｒ^３６、ＣＯＲ^３４、ＳＯＲ^３４、ＳＯ_２Ｒ^３４、ＣＯＮＲ^３５Ｒ^３６、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
Ｒ^３４、Ｒ^３５及びＲ^３６は、それぞれ独立に、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
環Ａ^１及び環Ａ^２は、炭素原子数４〜２０の芳香環又は複素環を含有する炭素原子数２〜２０の基を表し、
ｋは、Ａ^１が取り得る置換基の数以下の正の整数であり、
ｋ≧２の場合は、複数存在するＲ^１５が各々異なる場合があり、
ｍは、Ａ^２が取り得る置換基の数以下の正の整数であり、
ｍ≧２の場合は、複数存在するＲ^１９が各々異なる場合があり、
Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５及びＲ^３６（以下、Ｒ^１３〜Ｒ^１５、Ｒ^１７〜Ｒ^１９及びＲ^３１〜Ｒ^３６とも記載）で表される炭素原子数１〜２０の炭化水素基又はＲ^１３〜Ｒ^１５、Ｒ^１７〜Ｒ^１９及びＲ^３１〜Ｒ^３６で表される複素環を含有する炭素原子数２〜２０の基の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、メルカプト基、イソシアネート基、カルボキシル基又は炭素原子数２〜２０の、複素環含有基で置換される場合があり、Ｒ^１３〜Ｒ^１５、Ｒ^１７〜Ｒ^１９及びＲ^３１〜Ｒ^３６で表される炭素原子数２〜２０の炭化水素基又はＲ^１３〜Ｒ^１５、Ｒ^１７〜Ｒ^１９及びＲ^３１〜Ｒ^３６で表される複素環を含有する炭素原子数２〜２０の基中のメチレン基は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^３７−、−ＮＲ^３７ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＳＣＯ−又は−ＣＯＳ−で置換される場合もあり、
Ｒ^３７は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、
Ｒ^１３とＲ^１４、Ｒ^１４とＲ^１５、Ｒ^１７とＲ^１８、Ｒ^１８とＲ^１９、ｋ≧２の場合は、異なるＲ^１５同士、ｍ≧２の場合は、異なるＲ^１９同士は、結合して環を形成する場合もあり、
Ｒ^１３、Ｒ^１４及びＲ^１５の少なくとも一つは上記一般式（Ｉ）で表される基であり、
Ｒ^１７、Ｒ^１８及びＲ^１９の少なくとも一つは上記一般式（Ｉ）で表される基である。〕

[Wherein, R ¹² and R ¹⁶ each independently represent R ³¹ , OR ³¹ , SR ³¹ , PR ³² R ³³ , NR ³² R ³³ or NHPR ³² R ³³ ;
R ³¹ , R ³² and R ³³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms,
R ³² and R ³³ may combine to form a ring,
R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently represented by a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or the above general formula (I). R ³⁴ , OR ³⁴ , SR ³⁴ , NR ³⁵ R ³⁶ , COR ³⁴ , SOR ³⁴ , SO ₂ R ³⁴ , CONR ³⁵ R ³⁶ , a carbon atom containing a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring Represents a group of 2 to 20,
R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
Ring A ¹ and Ring A ² represent a group having 2 to 20 carbon atoms containing an aromatic ring or heterocyclic ring having 4 to 20 carbon atoms,
k is a positive integer equal to or less than the number of substituents that A ¹ can take;
When k ≧ 2, a plurality of R ¹⁵ may be different from each other,
m is a positive integer equal to or less than the number of substituents that A ² can take;
When m ≧ 2, a plurality of R ¹⁹ may be different from each other,
R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ (hereinafter referred to as R ^{13 to} R ¹⁵ , R ^{17 to} R ¹⁹ and A hydrocarbon group having 1 to 20 carbon atoms represented by R ^{31 to} R ³⁶ ) or a carbon containing a heterocyclic ring represented by R ^{13 to} R ¹⁵ , R ^{17 to} R ^19, and R ^{31 to} R ^36. The hydrogen atom of the group having 2 to 20 atoms is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, mercapto group, isocyanate group, carboxyl group or C2-20, may be substituted with a heterocycle-containing ^{group, a} hydrocarbon of ^{R 13 ~R 15, R 17 ~R} 19 and C2-20 represented by ^R 31 ^{to R 36} Containing group or a methylene group ^R 13 ^{to R 15,} the radical of R 17 ^{to R 19} and C2-20 containing heterocyclic ring represented by ^R 31 ^{to R 36} is, -O -, - CO- , —COO—, —OCO—, —NR ³⁷ —, —NR ³⁷ CO—, —S—, —SO ₂ —, —SCO— or —COS— may be substituted,
R ³⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , if k ≧ 2, different R ¹⁵ , if m ≧ 2, different R ¹⁹ are bonded To form a ring,
At least one of R ¹³ , R ¹⁴ and R ¹⁵ is a group represented by the above general formula (I),
At least one of R ¹⁷ , R ¹⁸ and R ¹⁹ is a group represented by the above general formula (I). ]

  As the oxime ester compound of the present invention, a compound represented by the following general formula (IVa) or (IVb) is particularly preferable because it is excellent in transparency and becomes highly sensitive when used as a polymerization initiator.

〔式中、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５、Ｒ^４６、Ｒ^４７、Ｒ^４８、Ｒ^４９、Ｒ^５０、Ｒ^５１、Ｒ^５２、Ｒ^５３、Ｒ^５４、Ｒ^５５及びＲ^５６（以下、Ｒ^４１〜Ｒ^５６とも記載）は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、トリフルオロメチル基、ホルミル基、スルホ基、上記一般式（Ｉ）で表される基、Ｒ^７０、ＯＲ^７１、ＳＲ^７１、ＮＲ^７２Ｒ^７３、ＣＯＲ^７１、ＳＯＲ^７１、ＳＯ_２Ｒ^７１、ＣＯＮＲ^７２Ｒ^７３、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
Ｒ^７１、Ｒ^７２及びＲ^７３は、それぞれ独立に、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
Ｒ^４１〜Ｒ^５６、Ｒ^７１、Ｒ^７２及びＲ^７３（以下、Ｒ^４１〜Ｒ^５６及びＲ^７１〜Ｒ^７３とも記載）で表される炭素原子数１〜２０の炭化水素基又はＲ^４１〜Ｒ^５６及びＲ^７１〜Ｒ^７３で表される複素環を含有する炭素原子数２〜２０の基の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、メルカプト基、イソシアネート基、カルボキシル基又は複素環を含有する炭素原子数２〜２０の基で置換される場合があり、Ｒ^４１〜Ｒ^５６及びＲ^７１〜Ｒ^７３で表される炭素原子数２〜２０の炭化水素基又はＲ^４１〜Ｒ^５６及びＲ^７１〜Ｒ^７３で表される複素環を含有する炭素原子数２〜２０の基中のメチレン基は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^７４−、−ＮＲ^７４ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＳＣＯ−又は−ＣＯＳ−で置換される場合もあり、
Ｒ^７４は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、
Ｒ^４１とＲ^４２、Ｒ^４２とＲ^４３、Ｒ^４３とＲ^４４、Ｒ^４５とＲ^４６、Ｒ^４６とＲ^４７、Ｒ^４７とＲ^４８、Ｒ^４８とＲ^４９、Ｒ^４９とＲ^５０、Ｒ^５０とＲ^５１、Ｒ^５１とＲ^５２、Ｒ^５３とＲ^５４、Ｒ^５４とＲ^５５、Ｒ^５５とＲ^５６又はＲ^５６とＲ^４１は、結合して環を形成する場合もあり、
Ｒ^４１〜Ｒ^５６の少なくとも一つは上記一般式（Ｉ）で表される基である。〕

[Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ (hereinafter also referred to as R ^{41 to} R ⁵⁶ ) are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, trifluoromethyl group, formyl group, sulfo group, the above general formula ( A group represented by I), R ⁷⁰ , OR ⁷¹ , SR ⁷¹ , NR ⁷² R ⁷³ , COR ⁷¹ , SOR ⁷¹ , SO ₂ R ⁷¹ , CONR ⁷² R ⁷³ , a hydrocarbon group having 1 to 20 carbon atoms or a complex Represents a group of 2 to 20 carbon atoms containing a ring,
R ⁷¹ , R ⁷² and R ⁷³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
A hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁵⁶ , R ⁷¹ , R ⁷² and R ⁷³ (hereinafter also referred to as R ^{41 to} R ⁵⁶ and R ^{71 to} R ⁷³ ) or R ^{41 to} R The hydrogen atom of the group having 2 to 20 carbon atoms containing a heterocyclic ring represented by ⁵⁶ and R ^{71 to} R ⁷³ is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, or acryloyl. May be substituted with a group having 2 to 20 carbon atoms containing a group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group, a carboxyl group or a heterocyclic ring, and R ^{41 to} R ⁵⁶ and R ^{71 to} R ⁷³ The methylene group in the group having 2 to 20 carbon atoms or a hydrocarbon group having 2 to 20 carbon atoms or a heterocyclic ring represented by R ^{41 to} R ⁵⁶ and R ^{71 to} R ⁷³ is represented by —O − ^{-CO -, - COO -, -} OCO -, - NR 74 -, - NR 74 CO -, - S -, - SO 2 -, - SCO- or -COS- in some cases be substituted,
R ⁷⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ⁴¹ and ^{R 42, R 42} and ^{R 43, R 43} and ^{R 44, R 45} and ^{R 46, R 46} and ^{R 47, R 47} and ^{R 48, R 48} and ^{R 49, R 49} and ^{R 50, R 50} And R ⁵¹ , R ⁵¹ and R ⁵² , R ⁵³ and R ⁵⁴ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ or R ⁵⁶ and R ⁴¹ may combine to form a ring,
At least one of R ^{41 to} R ⁵⁶ is a group represented by the above general formula (I). ]

〔式中、Ｒ^５７及びＲ^６４は、それぞれ独立に、Ｒ^７５、ＯＲ^７５、ＳＲ^７５、ＰＲ^７６Ｒ^７７、ＮＲ^７６Ｒ^７７又はＮＨＰＲ^７６Ｒ^７７を表し、
Ｒ^５８、Ｒ^５９、Ｒ^６０、Ｒ^６１、Ｒ^６２、Ｒ^６３、Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９及びＲ^７０は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、上記一般式（Ｉ）で表される基、Ｒ^７５、ＯＲ^７５、ＳＲ^７５、ＮＲ^７６Ｒ^７７、ＰＲ^７６Ｒ^７７、ＮＨＰＲ^７６Ｒ^７７、ＣＯＲ^７５、ＳＯＲ^７５、ＳＯ_２Ｒ^７５、ＣＯＮＲ^７６Ｒ^７７、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
Ｒ^７５、Ｒ^７６及びＲ^７７は、それぞれ独立に、炭素原子数１〜２０の炭化水素基又は複素環を含有する炭素原子数２〜２０の基を表し、
Ｒ^７６とＲ^７７は、結合して環を形成する場合もあり、
Ｒ^５８、Ｒ^５９、Ｒ^６０、Ｒ^６１、Ｒ^６２、Ｒ^６３、Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９、Ｒ^７０、Ｒ^７５、Ｒ^７６、及びＲ^７７で表される炭素原子数１〜２０の炭化水素基又はＲ^５８、Ｒ^５９、Ｒ^６０、Ｒ^６１、Ｒ^６２、Ｒ^６３、Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９、Ｒ^７０、Ｒ^７５、Ｒ^７６、及びＲ^７７で表される複素環を含有する炭素原子数２〜２０の基の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、メルカプト基、イソシアネート基、カルボキシル基又は複素環を含有する炭素原子数２〜２０の基で置換される場合があり、Ｒ^５８、Ｒ^５９、Ｒ^６０、Ｒ^６１、Ｒ^６２、Ｒ^６３、Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９、Ｒ^７０、Ｒ^７５、Ｒ^７６、及びＲ^７７で表される炭素原子数２〜２０の炭化水素基又はＲ^５８、Ｒ^５９、Ｒ^６０、Ｒ^６１、Ｒ^６２、Ｒ^６３、Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９、Ｒ^７０、Ｒ^７５、Ｒ^７６、及びＲ^７７で表される複素環を含有する炭素原子数２〜２０の基中のメチレン基は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ^７８−、−ＮＲ^７８ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＳＣＯ−又は−ＣＯＳ−で置換される場合もあり、
Ｒ^７８は、水素原子又は炭素原子数１〜２０の炭化水素基を表し、
Ｒ^５７とＲ^５８、Ｒ^５８とＲ^５９、Ｒ^５９とＲ^６０、Ｒ^６０とＲ^６１、Ｒ^６１とＲ^６２、Ｒ^６２とＲ^６３、Ｒ^６４とＲ^６５、Ｒ^６５とＲ^６６、Ｒ^６６とＲ^６７、Ｒ^６７とＲ^６８、Ｒ^６８とＲ^６９又はＲ^６９とＲ^７０は、結合して環を形成する場合もあり、
Ｒ^５８、Ｒ^５９、Ｒ^６０、Ｒ^６１、Ｒ^６２及びＲ^６３の少なくとも一つは上記一般式（Ｉ）で表される基であり、
Ｒ^６５、Ｒ^６６、Ｒ^６７、Ｒ^６８、Ｒ^６９及びＲ^７０の少なくとも一つは上記一般式（Ｉ）で表される基である。〕

[Wherein, R ⁵⁷ and R ⁶⁴ each independently represent R ⁷⁵ , OR ⁷⁵ , SR ⁷⁵ , PR ⁷⁶ R ⁷⁷ , NR ⁷⁶ R ⁷⁷ or NHPR ⁷⁶ R ⁷⁷ ;
R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ and R ⁷⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, A cyano group, a hydroxyl group, a carboxyl group, a group represented by the above general formula (I), R ⁷⁵ , OR ⁷⁵ , SR ⁷⁵ , NR ⁷⁶ R ⁷⁷ , PR ⁷⁶ R ⁷⁷ , NHPR ⁷⁶ R ⁷⁷ , COR ⁷⁵ , SOR ⁷⁵ , SO ₂ R ⁷⁵ , CONR ⁷⁶ R ⁷⁷ , a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
R ⁷⁵ , R ⁷⁶ and R ⁷⁷ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
R ⁷⁶ and R ⁷⁷ may combine to form a ring,
Carbon represented by R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁵ , R ⁷⁶ , and R ⁷⁷ A hydrocarbon group having 1 to 20 atoms or R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁵ , R ⁷⁶ and a hydrogen atom of a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ⁷⁷ are a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, It may be substituted with a group having 2 to 20 carbon atoms containing an epoxy group, a vinyl group, a mercapto group, an isocyanate group, a carboxyl group or a heterocyclic ring, and R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ^{6. 2} , a hydrocarbon group having 2 to 20 carbon atoms represented by R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁵ , R ⁷⁶ , and R ⁷⁷ , or R ⁵⁸ , Contains a heterocyclic ring represented by R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁵ , R ⁷⁶ , and R ⁷⁷ methylene groups in the group of 2 to 20 carbon atoms which may, -O -, - CO -, - COO -, - OCO -, - NR 78 -, - NR 78 CO -, - S -, - SO 2 - , -SCO- or -COS-
R ⁷⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ⁵⁷ and R ⁵⁸ , R ⁵⁸ and R ⁵⁹ , R ⁵⁹ and R ⁶⁰ , R ⁶⁰ and R ⁶¹ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶⁴ and R ⁶⁵ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ And R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁸ and R ⁶⁹ or R ⁶⁹ and R ⁷⁰ may combine to form a ring,
At least one of R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² and R ⁶³ is a group represented by the above general formula (I),
At least one of R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ and R ⁷⁰ is a group represented by the above general formula (I). ]

Among the compounds represented by the general formula (IVa), an oxime ester compound in which at least one of R ⁴² , R ⁴⁷ , R ⁵⁰ and R ⁵⁵ is a group represented by the general formula (I), particularly R ^An oxime in which at least one of ⁴² and R ⁴⁷ is a group represented by the above general formula (I), and at least one of R ⁵⁰ and R ⁵⁵ is a group represented by the above general formula (I) An ester compound is preferred because of its excellent sensitivity when used as an initiator. Furthermore, among R ⁴² , R ⁴⁷ , R ⁵⁰ and R ⁵⁵ , an oxime ester compound in which at least one of the groups other than the group represented by the general formula (I) is an electron attractive group is used as an initiator. It is preferable because the sensitivity is even higher.

  Examples of the electron withdrawing group include a halogen atom, a cyano group, a nitro group, a benzoyl group, a carboxyl group, a trifluoromethyl group, a formyl group, and a sulfo group. Among these, the case of at least one selected from the group consisting of a halogen atom, a cyano group, a nitro group, a benzoyl group, a carboxyl group, and a trifluoromethyl group is preferable because of higher sensitivity.

Among the compounds represented by the general formula (IVb), an oxime ester compound in which R ⁶¹ and R ⁶⁸ are groups represented by the general formula (I) was used as an initiator. In this case, the oxime ester compound in which R ⁵⁷ and R ⁶⁴ are OR ⁷⁵ and SR ⁷⁵ is preferable because of good compatibility with the solvent.

In the above general formulas (I) to (IVb), R ^{1 to} R ¹¹ , R ^{13 to} R ¹⁵ , R ^{17 to} R ²⁷ , R ²⁹ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁵⁶ , R ^{58 to} R The hydrocarbon group having 1 to 20 carbon atoms represented by ⁶³ and R ^{65 to} R ⁷⁷ is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms and 2 to 20 carbon atoms. An alkenyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and the like. Since the sensitivity when used as a polymerization initiator is good, the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the cycloalkyl group having 3 to 10 carbon atoms, the number of carbon atoms 4-10 cycloal A kill alkyl group, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and the like are more preferable.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, and isooctyl. , 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl, etc. Is It is.

  Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, and 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8,12-tetradecatrienylallyl and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3- Pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl 3- octenyl, 3-nonenyl and 4-decenyl and the like.

  The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthracenyl Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1.1.1] pentanyl and the like.

  The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2- Cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl , 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl. , Cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl , 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, etc. It is.

  Examples of the aryl group having 6 to 20 carbon atoms include one or more of phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, the alkyl group, the alkenyl group, the carboxyl group, and the halogen atom. Substituted phenyl, biphenylyl, naphthyl, anthryl, etc., for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, etc. Examples of the aryl group having 6 to 10 include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and the like, phenyl, biphenylyl, naphthyl substituted with one or more of the above alkyl group, the above alkenyl group, carboxyl group, halogen atom, and the like. , Anthril, etc., such as 4- Rorofeniru, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, and the like.

  The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with an aryl group. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl and the like are mentioned. The arylalkyl group having 7 to 10 carbon atoms is an alkyl group in which a hydrogen atom is an aryl group. By substituted is meant a group having 7 to 10 carbon atoms. Examples include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

R ¹ , R ² , R ^{4 to} R ¹¹ , R ^{13 to} R ¹⁵ , R ^{17 to} R ²⁵ , R ²⁶ , R ²⁷ , R ^{34 to} R ³⁶ , R ^{41 in the} above general formulas (I) to (IVb) to R ^56, and the group ^R 58 ^{to R 63} and ^R 65 ^{to R 73} and ^R 75 C2-20 containing heterocyclic ring represented by ^{to R 77,} and at least one contains a heterocyclic ring, It means a group having 2 to 20 carbon atoms in the whole group. Examples of the heterocyclic ring in the group include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, Furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2- Piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl, and the like. From the sensitivity in the case that good used as agents, group having 2 to 10 carbon atoms containing heterocyclic ring is more preferable. Examples of the heterocyclic ring in the group having 2 to 10 carbon atoms containing a heterocyclic ring include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl , Quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2 -Pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl, etc. And the like. When the heterocyclic ring in the group containing a heterocyclic ring has a substituent, the total number of carbon atoms in the group may exceed 20. Specifically describing a group having 2 to 20 carbon atoms [heterocycle + linking group (Z in the following formula)] containing a heterocyclic ring and the group further having a substituent (R in the following formula), Examples thereof include a group having a structure.

（上記式中、Ｒはそれぞれ独立して、水素原子又は炭素原子数１〜６のアルキル基を表し、Ｚは直接結合又は炭素原子数１〜６のアルキレン基を表す。尚、式中の＊は、これらの式で表される基が、＊部分で、隣接する基と結合することを意味する。）

(In the above formulae, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. Means that the group represented by these formulas is bonded to an adjacent group at the * moiety.)

R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ and R ¹⁰ and R ¹¹ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ And R ¹⁸ , R ¹⁸ and R ¹⁹ , R ²³ and R ²⁴ , R ²⁶ and R ²⁷ , R ³² and R ³³ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁴⁸ and R ⁴⁹ , R ⁴⁹ and R ⁵⁰ , R ⁵⁰ and R ⁵¹ , R ⁵¹ and R ⁵² , R ⁵³ and R ⁵⁴ , R ⁵⁴ and R ⁵⁵ , ^R55 and ^R56 , ^R56 and ^R41 , ^R57 and ^R58 , ^R58 and ^R59 , ^R59 and ^R60 , ^R60 and ^R61 , ^R61 and ^R62 , ^R62 and ^R63 , ^R64 and the ^{R 65, R 65} and ^{R 66, R 66 R 67,} R 67 and ^{R 68, R 68} and ^{R 69} Different ^{R 19} together when different ^{R 15} s or m ≧ 2 in the case of R ⁶⁹ and ^{R 70,} k ≧ 2 is a ring formed bonded to, for example, cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine , Pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, 5- to 7-membered rings such as lactone ring and lactam ring, and condensed rings such as naphthalene and anthracene.

  Examples of the halogen atom in the general formulas (I) to (IVb) include fluorine, chlorine, bromine and iodine.

Examples of the ring formed by combining X ¹ and Y ¹ and X ² and Y ² include an aromatic ring. Examples thereof include benzene, furan, thiophene, pyrrole, pyrazole, pyridine and pyrimidine.

Rings A ¹ and A ² represent a group having 2 to 20 carbon atoms containing an aromatic ring or a heterocyclic ring having 4 to 20 carbon atoms, and when used as a polymerization initiator, the carbon atom has high sensitivity. An aromatic ring having 4 to 10 carbon atoms or a heterocyclic ring having 2 to 10 carbon atoms is more preferable. Examples of the aromatic ring having 4 to 20 carbon atoms include benzene, naphthalene, cyclobutadiene, cyclooctatetraene and tropone. Examples of the heterocyclic ring having 2 to 10 carbon atoms include furan, thiophene, pyrrole, Examples include pyrazole, imidazole, triazole, pyridine, pyridazine, pyrimidine and pyrazine.

  Preferable specific examples of the oxime ester compound having a skeleton in which groups having a condensed ring are adjacent to each other include the following compound Nos. 1-No. 252. However, the present invention is not limited by the following compounds.

  As a method for producing a skeleton in which groups having condensed rings are adjacent and an oxime ester having a group represented by the above general formula (I), a skeleton in which groups having a condensed ring are known and commercially available are adjacent to each other. A ketone compound is obtained by reacting the compound having acid chloride with it, and an oxime compound is obtained by reacting the ketone compound with hydroxylamine hydrochloride or isobutyl nitrite. Subsequently, the oxime compound of the present invention is obtained by reacting the oxime compound with an acid anhydride or acid chloride.

  Examples of the method for producing the oxime ester compound represented by the general formulas (IIa) and (IVa) include a method for producing the oxime ester compound by the following method according to the following reaction formula [Chemical Formula 26]. That is, a compound having a skeleton in which a group having a condensed ring that is known and commercially available is adjacent to each other by a spiro structure, and a compound having a skeleton in which a conjugated plane having a ring structure is adjacent is reacted with an acid chloride. A ketone compound is obtained by the reaction, and an oxime compound is obtained by reacting the ketone compound with hydroxylamine hydrochloride. Subsequently, the oxime compound of the present invention is obtained by reacting the oxime compound with an acid anhydride or acid chloride.

（式中、Ｒ^１、Ｒ^２、Ｒ^４１〜Ｒ^４６、Ｒ^４８〜Ｒ^５４、Ｒ^５６及びＲ^５８は、上記一般式（Ｉ）及び（IVａ）と同じである。）

(In the formula, R ¹ , R ² , R ^{41 to} R ⁴⁶ , R ^{48 to} R ⁵⁴ , R ⁵⁶ and R ⁵⁸ are the same as the above general formulas (I) and (IVa).)

  Examples of the method for producing the oxime ester compound represented by the general formulas (IIb) and (IVb) include a method for producing the oxime ester compound according to the following reaction formula [Chemical 27]. That is, a known and commercially available group having a condensed ring is reacted directly with an alcohol compound having a skeleton adjacent to each other by a direct bond, to obtain an ether compound, and the ether compound is reacted with an acid chloride. Thus, a ketone compound is obtained, and an oxime compound is obtained by reacting the ketone compound with isobutyl nitrite. Subsequently, the oxime compound of the present invention is obtained by reacting the oxime compound with an acid anhydride or acid chloride.

（式中、Ｒ^１、Ｒ^２、Ｒ^５８〜Ｒ^６０、Ｒ^６２、Ｒ^６３、Ｒ^６５〜Ｒ^６７、Ｒ^６９、Ｒ^７０、及びＲ^７５は、上記一般式（Ｉ）及び（IVｂ）と同じである。）

(Wherein R ¹ , R ² , R ^{58 to} R ⁶⁰ , R ⁶² , R ⁶³ , R ^{65 to} R ⁶⁷ , R ⁶⁹ , R ⁷⁰ , and R ⁷⁵ are the same as those in the above general formulas (I) and (IVb)). Same.)

  The novel oxime ester compound of the present invention described above is useful as a radical polymerization initiator, particularly a photopolymerization initiator or a thermal polymerization initiator. Moreover, the novel oxime ester compound of the present invention can also be suitably used as a base generator and a sensitizer.

  The polymerization initiator of the present invention contains the oxime ester compound of the present invention and can be used in combination with other polymerization initiators. As other polymerization initiators that can be used in combination, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1 -Dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholyl-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-buty Rubenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl)- s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine , Camphorquinone, N-1414, N-1717, N-1919, NCI-831, NCI-930 (manufactured by ADEKA), RGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF) and benzoyl peroxide, etc. These polymerization initiators may be used singly or in combination of two or more kinds.

  The content of the oxime ester compound of the present invention in the polymerization initiator of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

  The polymerizable composition of the present invention contains the polymerization initiator of the present invention and an ethylenically unsaturated compound as essential components.

The ethylenically unsaturated compound is not particularly limited, and those conventionally used in polymerizable compositions can be used. Examples thereof include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, and fluorine. Unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid , Allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono ( Mono (meth) of a polymer having a carboxy group and a hydroxyl group at both ends, such as (meth) acrylate ) Acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or polyfunctional (meth) having one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate; A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuxinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups Examples thereof include vinyl monomers containing vinyl monomers and polyepoxy compounds.
Among these, a mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, a polyfunctional (meth) acrylate having one carboxy group and two or more (meth) acryloyl groups, an unsaturated one A polymerization initiator containing the oxime ester compound of the present invention in an ester of a basic acid and a polyhydric alcohol or polyhydric phenol is suitable.
These ethylenically unsaturated compounds can be used alone or in admixture of two or more, and when used in admixture of two or more, they are copolymerized in advance as a copolymer. May be used.

  In addition, an ethylenically unsaturated compound having an acid group such as a carboxyl group (hereinafter also referred to as a compound having alkali developability) can be used for the purpose of imparting alkali developability to the polymerizable composition of the present invention. The compound having alkali developability is not particularly limited as long as it is soluble in an alkaline aqueous solution. For example, resins described in JP-A No. 2004-264414, copolymers of acrylic acid esters, phenols, cresol novolac epoxy resins Examples thereof include resins obtained by further allowing polybasic acid anhydrides to act on polyphenylmethane type epoxy resins having polyfunctional epoxy groups, epoxy acrylate resins and epoxy acrylate resins.

  A commercial item can be used as said ethylenically unsaturated compound, for example, Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (made by Nippon Kayaku), SPC-1000, SPC -3000 (manufactured by Showa Denko), Aronix M-140, M-215, M-350, M-450 (manufactured by Toagosei), NK ester A-DPHA-TMPT, A-DCP, A-HD-N, A- 9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Although content of the said polymerization initiator used in the polymeric composition of this invention is not specifically limited, Preferably it is 0.5-30 mass parts with respect to 100 mass parts of said ethylenically unsaturated compounds. More preferably, it is 0.5-10 mass parts, Most preferably, it is 0.5-5 mass parts.

The colored polymerizable composition of the present invention is obtained by further adding a coloring material to the polymerizable composition of the present invention.

  Examples of the color material include pigments, dyes, and natural pigments. These color materials can be used alone or in admixture of two or more.

Examples of the pigment include a nitroso compound; a nitro compound; an azo compound; a diazo compound; a xanthene compound; a quinoline compound; an anthraquinone compound; a coumarin compound; a phthalocyanine compound; an isoindolinone compound; an isoindolinone compound; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; furnace method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with an epoxy resin, carbon black previously dispersed in a resin in a solvent and adsorbed 20 to 200 mg / g of resin, an acid or alkaline surface treated carbon black, average Graphite having a particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, and a total oxygen amount calculated from CO and CO ₂ in a volatile content at 950 ° C. of 9 mg or more per 100 m ² of the surface area of carbon black; Graphite , Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series , Ferrocyanide Organic or inorganic such as phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber Pigments can be used. These pigments can be used alone or in combination.

  Commercially available pigments can also be used as the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

  As the above dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.

  In the colored polymerizable composition of the present invention, the content of the coloring material is preferably 50 to 350 parts by mass, more preferably 100 to 250 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound.

If necessary, a solvent capable of dissolving or dispersing the polymerization initiator, the ethylenically unsaturated compound, and the coloring material can be added to the polymerizable composition. For example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-di Ether solvents such as ethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amino Alcohol solvents such as alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propio Ether ester solvents such as nates; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene Paraffinic solvents such as mineral spirits, swazol # 310 (Cosmo Matsuyama Petroleum), Solvesso # 100 (Exxon Chemical); carbon tetrachloride, chloroform, Halogenated aliphatic hydrocarbon solvents such as chloroethylene, methylene chloride, 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents; Aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon sulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; dimethyl sulfoxide; water and the like. These solvents can be used as one or a mixture of two or more. .
Among these, ketones and ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate and cyclohexanone, have good compatibility between the ethylenically unsaturated compound and the polymerization initiator in the polymerizable composition. Therefore, it is preferable.

  As long as the effects of the present invention are not impaired, the polymerizable composition and the colored polymerizable composition of the present invention include, if necessary, a polymer excluding an ethylenically unsaturated compound (hereinafter also referred to as a polymer), an inorganic compound, and a dispersant. , Chain transfer agent, sensitizer excluding oxime ester compound of the present invention (hereinafter also referred to as sensitizer), surfactant, silane coupling agent, melamine compound, leveling agent, latent additive, ethylenically unsaturated compound Monomers, antifoaming agents, thickeners, thixotropic agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, organic fillers, antioxidants, antistatic agents, flow regulators and adhesion promoters Various resin additives such as an agent can be added.

  By using the polymer, the properties of the cured product can be improved. Examples of the polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer. Polymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, Examples include phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred. There.

  In the polymerizable composition and the colored polymerizable composition of the present invention, the content of the polymer is preferably 0 to 500 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound.

Examples of the inorganic compound include nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, alumina, and other metal oxides; layered clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Gold, silver, copper, etc. are mentioned.
Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable.

  These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

  In the polymerizable composition and the colored polymerizable composition of the present invention, the content of the inorganic compound is preferably 0 to 1000 parts by mass, more preferably 0 to 800 parts with respect to 100 parts by mass of the ethylenically unsaturated compound. Part by mass. These inorganic compounds can be used alone or in combination of two or more.

  The dispersing agent is not limited as long as it can disperse and stabilize a coloring material or an inorganic compound, and a commercially available dispersing agent such as BYK series manufactured by BYK Chemie can be used. In particular, a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as the basic functional group, and the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof. And those having an amine value of 1 to 100 mgKOH / g are preferably used.

  As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Showa Denko Karenz MT BD1, PE1, NR1, and the like.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; higher amines Cationic surfactants such as halogenates and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  As the silane coupling agent, for example, a Shin-Etsu Chemical silane coupling agent can be used, and among them, silanes having an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403. A coupling agent is preferably used.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Examples include compounds in which (at least two) are alkyl etherified.
Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other, and are methylol groups that are not alkyl etherified. May be self-condensed within one molecule or may be condensed between two molecules, resulting in the formation of an oligomer component.
Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

  A commercial item can be used as said leveling agent. Examples of commercially available leveling agents include BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK- 349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-340, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720, BYK-DYNET Tsu-made click-Chemie Japan) Polyflow No. 3, Polyflow No. 50HF, Polyflow No. 54, Polyflow No. 64HF, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 95, Polyflow No. ATF-2, Granol 100, Granol 115, Granol 400, Granol 410, Granol 420, Granol 440, Granol 450, Granol B-1484 (manufactured by Kyoeisha Chemical), MegaFuck F-114, F-251, F-253, F -281, F-410, F-430, F-444, F-477, F-510, F-552, F-553, F-554, F-555, F-556, F-558, F-559 , F-569, F-570, F-571, F-572, R-40, R-40-LM, RS-55, RS-76-E, RS-76-NS, RS-78, RS-90 (Manufactured by DIC) L-7001, L-7002, L-7006, 56ADDITIVE, 57ADDITIVE, 67ADDITIVE, 8032ADDITIV , FZ-2105, FZ-2110, FZ-2122 and FZ-2123 (manufactured by Dow Corning Toray), and the like.

The latent additive is inactive at room temperature, in the light exposure step and in the pre-bake step, and is protected at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Is activated by desorption. Examples of the effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability and adhesion.
As the latent additive, those described in the pamphlet of WO2014 / 021023 can be preferably used.

  A commercial item can be used as said latent additive, for example, Adeka Arcles GPA-5001 etc. are mentioned.

  In the polymerizable composition and colored polymerizable composition of the present invention, optional components other than the ethylenically unsaturated compound, the oxime ester compound of the present invention and the color material (however, the polymer, inorganic compound, color material and solvent are The amount of (excluding) is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the ethylenically unsaturated compound.

  The polymerizable composition and colored polymerizable composition of the present invention include a photocurable paint or varnish; a photocurable adhesive; a printing ink; a dental composition; an electronic photoresist; an electroplating resist; Solder resists; and resists for forming structures in LCD manufacturing processes; compositions for encapsulating electrical and electronic components; solder resists; magnetic recording materials; plating masks; etching masks; three-dimensional objects by stereolithography Decolorizing materials for image recording materials; Decolorizing materials for image recording materials using microcapsules; Photoresist materials for printed wiring boards; Photoresist materials for UV and visible laser direct imaging systems; Photoresist material or protective material used for dielectric layer formation in sequential lamination of printed circuit boards Can be used in various applications of film or the like, there is no particular limitation on the application.

  The polymerizable composition and the colored polymerizable composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a protrusion for a vertical alignment type liquid crystal display element. In particular, it is useful as a polymerizable composition and a colored polymerizable composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element.

  The liquid crystal display panel spacer includes (1) a step of forming a coating film of the polymerizable composition of the present invention or a colored polymerizable composition of the present invention on a substrate, and (2) a predetermined pattern shape on the coating film. It is preferably formed by a step of irradiating with radiation through a mask having: (3) a baking step after exposure, (4) a step of developing the coating after exposure, and (5) a step of heating the coating after development. The

  The polymerizable composition and colored polymerizable composition of the present invention to which an ink repellent agent is added are useful as a partition-forming resin composition for an ink jet system, and the composition is used for a color filter, and particularly has a profile angle of 50. It is preferably used for a partition for an ink jet type color filter having a temperature of at least 0 °. As the ink repellent agent, a composition comprising a fluorosurfactant and a fluorosurfactant is preferably used.

  The polymerizable composition and colored polymerizable composition of the present invention can be used as a polymerizable paste composition by containing an inorganic material (inorganic compound). The polymerizable paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.

  The cured product obtained from the polymerizable composition of the present invention or the colored polymerizable composition of the present invention is obtained by curing the polymerizable composition of the present invention or the colored polymerizable composition of the present invention by the method shown below. There is no limitation on its shape and properties.

  Specifically, the cured product of the present invention includes a step of preparing a substrate, a step of applying the polymerizable composition of the present invention or the colored polymerizable composition of the present invention to a supporting substrate, and a step of irradiating energy rays. It can be manufactured by a method.

  Examples of the material of the support substrate include soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, and the like. Examples of the coating method used in the coating step include spin coater, roll coater, bar coater, and die coater. Well-known means such as curtain coater, various printing and dipping can be used. Moreover, after once applying on support bases, such as a film, it can also transcribe | transfer on another support base | substrate.

  The light source of the energy beam used in the process of irradiating the energy beam is not particularly limited. For example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp. Xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc. High energy rays such as radiation can be used. Preferably, an ultrahigh pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, and the like that emit light having a wavelength of 300 to 450 nm are used.

  Furthermore, by using laser light as a light source for energy rays, the direct laser drawing method that directly forms an image from digital information such as a computer without using a mask is not only productive, but also resolution, positional accuracy, etc. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton Those that emit light in the visible to infrared region, such as ion lasers, various semiconductor lasers, and YAG lasers, are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  The polymerizable composition of the present invention or the cured product obtained from the colored polymerizable composition of the present invention is a printed board; a color filter in a color display liquid crystal display element such as a color television, a PC monitor, a personal digital assistant, a digital camera; Color filter of CCD image sensor; Electrode material for plasma display panel; Powder coating; Printing plate; Magnetic recording material; Micro mechanical part; Waveguide; Optical switch; Color test system; Glass fiber cable coating; Circuits; decolorizing materials; protective films; insulating films; optical elements and the like can be used, and there are no particular restrictions on the applications.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

Example 1 Compound No. 1 Production of Compound No. 1 The production of 1 and its intermediate is shown below.

<Step 1; Production of Intermediate 1A>
Toluoyl chloride (9.77 g, 63.2 mmol) and aluminum chloride (8.43 g, 63.2 mmol) were added to a solution of spirofluorene (5.0 g, 15.8 mmol) in nitromethane (65 mL) under ice cooling, and at room temperature. The reaction was performed for 2 hours. Furthermore, toluyl chloride (4.88 g, 31.5 mmol) and aluminum chloride (17.6 g, 132 mmol) were added under ice cooling, and the reaction was performed at room temperature for 1 hour. Ion-exchanged water was added dropwise under ice-cooling, extraction was performed with chloroform, the organic layer was washed with dilute hydrochloric acid and then washed with water three times, and then the solvent was distilled off at 40 ° C. under reduced pressure. Crystallization was performed by adding isopropanol, followed by filtration and drying at 40 ° C. under reduced pressure for 1 hour to obtain Intermediate 1A (8.27 g, yield 94.7%) as a colorless solid.

<Step 2: Production of intermediate 1B>
Acetyl chloride (4.70 g, 59.9 mmol) and aluminum chloride (7.98 g, 59.9 mmol) were added to a solution of intermediate 1A (8.27 g, 14.9 mmol) in nitromethane (65 mL) under ice-cooling, and room temperature. And reacted for 9 hours. Ion exchange water was added dropwise under ice cooling, and extraction was performed from chloroform. Thereafter, the organic layer was washed with dilute hydrochloric acid, washed with water three times, and the solvent was distilled off at 40 ° C. under reduced pressure. The crude product was subjected to silica gel column chromatography with chloroform to obtain Intermediate 1B (3.52 g, 36.9%) as a brown amorphous substance.

<Step 3; Production of Intermediate 1C>
Hydroxylamine hydrochloride (0.85 g, 12.2 mmol), sodium acetate (1.20 g, 14.6 mmol) in a suspension solution of intermediate 1B (3.52 g, 5.53 mmol) in ethanol-ion exchange water (25 mL-10 mL) ) And stirred at 70 ° C. for 2 hours. Dimethylacetamide (2 mL) and chloroform (2 mL) were added and reacted at the same temperature for 3 hours. After cooling, ion exchange water was added, extraction was performed using toluene, and the organic layer was washed three times with ion exchange water, and the solvent was distilled off at 40 ° C. under reduced pressure. The obtained crude product was subjected to silica gel column chromatography with a flow of ethyl acetate / chloroform (1:10 v / v) to obtain a brown amorphous oxime (2.94 g, 79.6%).

<Step 4; Compound No. Production of 1>
Triethylamine (0.98 g, 9.70 mmol) and acetyl chloride (0.73 g, 9.26 mmol) were added to a solution of intermediate 1C (2.94 g, 4.41 mmol) in chloroform (20 mL) under ice cooling, and at room temperature. Reacted for 1 hour. Water was added to the reaction solution, and after separation of oil and water, the organic layer was washed with dilute hydrochloric acid and washed with water 5 times. The solvent was distilled off at 40 ° C. under reduced pressure, subjected to silica gel column chromatography with a fraction of ethyl acetate / hexane = 1/1 (v / v), crystallized twice with ethyl acetate-isopropanol, cream Compound no. 1 (1.31 g, 39.5%) was obtained.

Example 2 Compound No. No. 172 Compound no. The production of 172 and its intermediate is shown below.

<Step 1; Production of intermediate 172A>
To a solution of (±) -BINOL (24.9 g, 86.9 mmol), 1-bromobutane (25.0 g, 182.5 mmol) in DMAc (250 mL) was added potassium carbonate (36.0 g, 260.7 mmol), and 90 ° C. And reacted for 10 hours. Furthermore, potassium carbonate (15.0 g, 108.5 mmol) and 1-bromobutane (11.5 g, 83.9 mmol) were added, and the mixture was stirred at the same temperature for 12 hours to be reacted. After cooling to room temperature, toluene and ion exchange water were added, the organic layer was washed twice with ion exchange water, and the solvent was distilled off under reduced pressure. Methanol was added to the concentrated liquid to disperse the solid content, and after filtration, the filtrate was dried under reduced pressure at 40 ° C. to obtain Intermediate 172A (32.1 g, 92.7%) as a cream solid.

<Step 2: Production of intermediate 172B>
To a solution of intermediate 172A (16.0 g, 40.1 mmol) in nitromethane (194 mL) under ice cooling, 2,5-dimethylphenylacetyl chloride (15.4 g, 84.3 mmol), aluminum chloride (11.2 g, 84.84 mmol). 3 mmol) was added, and the mixture was stirred at the same temperature for 2 hours to be reacted. The reaction solution was poured into ice-cold water and extracted with toluene. The organic layer was washed twice with ion exchange water and dilute sodium bicarbonate water, and then the solvent was distilled off at 40 ° C. under reduced pressure. Crystallization was performed with ethyl acetate / 2-propanol, and the solvent was distilled off at 40 ° C. under reduced pressure to obtain Intermediate 172B (21.3 g, 76.8%) as a white solid.

<Step 3; Compound No. 172 Production>
To a solution of intermediate 172B (13.8 g, 20.0 mmol) in 2-methyltetrahydrofuran (41.4 g) was added 2M hydrochloric acid / tetrahydrofuran solution (40 mL, 39.9 mmol) under ice-cooling, and isobutyl nitrite (5.77 g, 55.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 3 hours to be reacted. After cooling to ice cooling, toluene (150 mL) was added, acetyl chloride (4.71 g, 60.0 mmol) and triethylamine (7.29 g, 72.0 mmol) were added dropwise, and the mixture was stirred at the same temperature for 2.5 hours, Reacted. Ion exchange water was added, the organic layer was washed 5 times with water, diluted sodium bicarbonate water and ion exchange water, and the solvent was distilled off under reduced pressure. The obtained crude product was subjected to silica gel column chromatography with a flow of ethyl acetate / hexane = 1/3, and the obtained fraction was crystallized from ethyl acetate / 2-propanol. It was dried at 0 ° C., and the compound No. 1 172 (1.44 g, 9.6%) was obtained.

Example 3 Compound No. Compound No. 173 except that n-octanoyl chloride was used in place of 2,5-dimethylphenylacetyl chloride. 172 in the same manner as in 172.

[Comparative Example 1] Comparative compound No. 1 Production of Compound No. 1 except that 9,9-dimethylfluorene was used instead of spirofluorene. In the same manner as in Comparative Example No. 1 1 was produced.

[Comparative Example 2] Production of 2
Compound No. 1 was used except that 2-naphthol was used instead of (±) -BINOL. Comparative compound No. 173 was prepared in the same manner as 173. 2 was produced.

  The analysis results of the oxime ester compound are shown in [Table 1] and [Table 2].

  From the above [Table 1] and [Table 2], it is clear that the oxime ester compound of the present invention has low sublimation properties. An oxime ester compound which is adjacent by a spiro structure is particularly preferable because of this remarkable effect.

[Examples 4 and 5 and Comparative Examples 3 to 7] Preparation of polymerizable composition
Each component was prepared according to the composition of [Table 3] to obtain a polymerizable composition (Examples 4 and 5 and Comparative Examples 3 to 7). In addition, the number in a table | surface represents a mass part. The polymerization initiator was Compound No. 1, Comparative Compound No. 1 and Comparative Compound No. 1 below. 3-No. 6 was used alone.
Moreover, the code | symbol of each component in a table | surface represents the following component.
A-1 Compound No. 1 (Polymerization initiator of the present invention)
A′-2 Comparative compound No. 1 (polymerization initiator not belonging to the present invention)
A′-3 Comparative compound No. 3 (polymerization initiator not belonging to the present invention)
A′-4 Comparative compound No. 4 (polymerization initiator not belonging to the present invention)
A′-5 Comparative compound No. 5 (polymerization initiator not belonging to the present invention)
A′-6 Comparative compound No. 6 (polymerization initiator not belonging to the present invention)
B-1 SPC-1000
(Ethylenically unsaturated compound having an acid group; Showa Denko)
B-2 Aronix M-450 (ethylenically unsaturated compound; manufactured by Toagosei)
C-1 PGMEA (solvent)
D-1 KBE-403 (Silane coupling agent; manufactured by Shin-Etsu Chemical)
D-2 FZ-2122 (leveling agent; manufactured by Toray Dow Corning)
D-3 Adeka Arcles GPA-5001 (latent additive; manufactured by ADEKA)

[Evaluation Examples 1 and 2 and Comparative Evaluation Examples 1 to 5]
The polymerizable composition was evaluated for sensitivity (line width), curability (remaining film ratio) and transparency (transmittance) by the following methods. The results are shown in [Table 4].

(Line width)
The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed through the mask using the high pressure mercury lamp. After developing using a 2.5% by mass aqueous sodium carbonate solution as a developing solution, it was washed thoroughly with water and post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern. The pattern with respect to the exposure amount of 30 mJ / cm ² was observed with an electron microscope, and the line width of the mask opening 20 μm was measured. A line width of 19 μm or more was designated as A, and a line width of less than 19 μm was designated as B. The larger the line width, the better the sensitivity.

(Residual film rate)
The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed through the mask using the high pressure mercury lamp, and measured the film thickness before image development. Subsequently, after developing using a 2.5% by weight aqueous sodium carbonate solution as a developer, thoroughly washing with water, performing post-baking at 230 ° C. for 30 minutes using an oven, fixing the pattern, measuring the film thickness, The remaining film ratio was calculated from the following calculated value.
Residual film ratio (%) = (film thickness after development) / (film thickness before development) × 100
The higher the remaining film ratio, the better the curability.

(Transmittance)
The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, 100 mJ / cm < ² > was irradiated using the high pressure mercury lamp, and the evaluation sample was produced. The transmittance of the obtained sample at 400 nm was measured. A transmittance of 95% or more was designated as A, and 90% or more and less than 95% was designated as B.

  From the above [Table 3] and [Table 4], when the oxime ester compound of the present invention is used as a polymerization initiator, a polymerizable composition excellent in sensitivity is obtained, and a cured product excellent in curability and transparency is obtained. It is clear that it is obtained. Since it is excellent in photolithography, it is particularly useful as a polymerization initiator for color filters.

Production Example 1 Production of Blue Pigment Dispersion DISPERBYK-161 (12.5 parts by mass; manufactured by BYK Japan) as a dispersant, and Pigment Blue 15: 6 (15 parts by mass) as a colorant, PGMEA (72. 5 parts by mass) was dispersed using a bead mill to produce a blue pigment dispersion.

[Examples 6 and 7 and Comparative Example 8] Preparation of colored polymerizable composition
Each component was prepared according to the composition of [Table 5] to obtain colored polymerizable compositions (Examples 6, 7 and Comparative Example 8). In addition, the number in a table | surface represents a mass part. As a polymerization initiator, Compound No. 172, compound no. 173 and comparative compound no. 2 was used alone.
Moreover, the code | symbol of each component in a table | surface represents the following component.
A-7 Compound No. 172 (polymerization initiator of the present invention)
A-8 Compound No. 173 (polymerization initiator of the present invention)
A′-9 Comparative compound No. 2 (polymerization initiator not belonging to the present invention)
B-3 SPC-3000
(Ethylenically unsaturated compound having an acid group; Showa Denko)
B-4 Kayalad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku)
C-1 PGMEA (solvent)
D-1 KBE-403 (Silane coupling agent; manufactured by Shin-Etsu Chemical)
D-4 Blue pigment dispersion (Coloring material dispersion)
D-5 F-554 (fluorinated group / lipophilic group-containing oligomer; manufactured by DIC)

[Evaluation Examples 3 and 4 and Comparative Evaluation Example 6]
The polymerizable composition was evaluated for sensitivity (line width), curability (remaining film ratio) and luminance (Y value) by the following methods. The results are shown in [Table 6].

(Line width)
The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed through the mask using the high pressure mercury lamp. After developing using a 2.5% by mass aqueous sodium carbonate solution as a developing solution, it was washed thoroughly with water and post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern. The pattern with respect to the exposure amount of 40 mJ / cm ² was observed with an electron microscope, and the line width of the mask opening 30 um was measured. A line width of 29 μm or more was designated as A, and a line width less than 29 μm was designated as B. The larger the line width, the better the sensitivity.

(Residual film rate)
The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed through the mask using the high pressure mercury lamp, and measured the film thickness before image development. Subsequently, after developing using a 2.5% by weight aqueous sodium carbonate solution as a developer, thoroughly washing with water, performing post-baking at 230 ° C. for 30 minutes using an oven, fixing the pattern, measuring the film thickness, The remaining film ratio was calculated from the following calculated value.
Residual film ratio (%) = (film thickness after development) / (film thickness before development) × 100
The higher the remaining film ratio, the better the curability.

(Y value)
The polymerizable composition was spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, 100 mJ / cm < ² > was irradiated using the high pressure mercury lamp, and the evaluation sample was created. The Y value was determined from the transmittance at 380 to 780 nm of the obtained sample in accordance with JIS Z8701.

  From the above [Table 5] and [Table 6], it is clear that when the oxime ester compound of the present invention is used as a polymerization initiator, a cured product excellent in luminance can be obtained while maintaining sensitivity and curability. is there. Moreover, since the oxime ester compound of the present invention is excellent in photolithography properties, it is particularly useful as a polymerization initiator for color filters.

Claims (9)

An oxime ester compound having a skeleton in which groups having a condensed ring are adjacent to each other by a spiro structure or a direct bond and a group represented by the following general formula (I).

(In the formula, each of R ¹ and R ² independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a C 2-20 carbon atom containing a heterocyclic ring. Represents a group,
Hydrogen atom of the group having 2 to 20 carbon atoms containing heterocyclic ring represented by hydrocarbon radicals or ^{R 1} and ^{R 2} having 1 to 20 carbon atoms represented by R ¹ and ^{R 2,} a halogen atom, It may be substituted with a nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, CH ₂ ═CH—O—, mercapto group, isocyanate group or heterocyclic group-containing group. There, a methylene group in the group having 2 to 20 carbon atoms containing heterocyclic ring represented by hydrocarbon group, or ^{R 1} and ^{R 2} having 1 to 20 carbon atoms represented by ^{R 1} and ^{R 2, -O -, - CO -, -} COO -, - OCO -, - NR 3 -, - NR 3 CO -, - S -, - CS -, - SO 2 -, - SCO -, - COS -, - OCS -Or CSO- may be substituted,
R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 0 or 1. * In the formula means bonding with an adjacent group at the * portion. )   The oxime ester compound according to claim 1, wherein each of the groups having a condensed ring has one or more groups represented by the general formula (I). The oxime ester compound of Claim 1 or 2 represented by the following general formula (IIa) or (IIb).

[In General Formula (IIa), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ (hereinafter also referred to as R ^{4 to} R ¹¹ ) are each independently a hydrogen atom , Halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, trifluoromethyl group, formyl group, sulfo group, group represented by the above general formula (I), R ²⁰ , OR ²⁰ , SR ²⁰ , NR ²¹ R ²² , COR ²⁰ , SOR ²⁰ , SO ₂ R ²⁰ , CONR ²¹ R ²² , a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
X ¹ and X ² are each independently —CO—, —CR ²³ R ²⁴ —, the following general formula (III)

(In the formula, R ²⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring. * Means that it is bonded to an adjacent group at the * part.)
A group represented by or combined with the adjacent Y ¹ or Y ² represents a group forming a ring, the hydrogen atom in the groups bound to Y ¹ or Y ² to the adjacent form a ring, the general In some cases, the group may be substituted by a group represented by the formula (I),
R ²³ and R ²⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R ²³ and R ²⁴ are bonded to each other. May form a ring,
Y ¹ and Y ² may each independently bond with —CR ²⁶ R ²⁷ — or adjacent X ¹ or X ² to form a ring,
R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R ²⁶ and R ²⁷ are bonded to each other. May form a ring,
R ^{4 to} R ¹¹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ (hereinafter also referred to as R ^{4 to} R ¹¹ and R ^{20 to} R ²⁷ ) The hydrogen atom of the group having 2 to 20 carbon atoms containing a heterocyclic group represented by a hydrocarbon group having 1 to 20 carbon atoms or R ^{4 to} R ¹¹ and R ^{20 to} R ²⁷ is a halogen atom, a nitro group, It may be substituted with a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group, a carboxyl group, or a heterocyclic group, and R ^{4 to} R ¹¹ and A group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ^{20 to} R ²⁷ or a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ^{4 to} R ¹¹ and R ^{20 to} R ²⁷ Group Tylene group is substituted with —O—, —CO—, —COO—, —OCO—, —NR ²⁸ —, —NR ²⁸ CO—, —S—, —SO ₂ —, —SCO— or —COS—. Sometimes
R ²⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ or R ¹⁰ and R ¹¹ may be combined to form a ring,
At least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ is a group represented by the above general formula (I), or is bonded to Y ¹ to form a ring. At least one of the hydrogen atom in the group to be formed and the group that is bonded to Y ² to form a ring is substituted with the group represented by the general formula (I),
In the general formula (IIb), R ¹² and R ¹⁶ each independently represent R ³¹ , OR ³¹ , SR ³¹ , PR ³² R ³³ , NR ³² R ³³ or NHPR ³² R ³³ ,
R ³¹ , R ³² and R ³³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms,
R ³² and R ³³ may combine to form a ring,
R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently represented by a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or the above general formula (I). R ³⁴ , OR ³⁴ , SR ³⁴ , NR ³⁵ R ³⁶ , COR ³⁴ , SOR ³⁴ , SO ₂ R ³⁴ , CONR ³⁵ R ³⁶ , a carbon atom containing a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring Represents a group of 2 to 20,
R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
Ring A ¹ and Ring A ² represent a group having 2 to 20 carbon atoms containing an aromatic ring or heterocyclic ring having 4 to 20 carbon atoms,
k is a positive integer equal to or less than the number of substituents that A ¹ can take;
When k ≧ 2, a plurality of R ¹⁵ may be different from each other,
m is a positive integer equal to or less than the number of substituents that A ² can take;
When m ≧ 2, a plurality of R ¹⁹ may be different from each other,
R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ (hereinafter referred to as R ^{13 to} R ¹⁵ , R ^{17 to} R ¹⁹ and A hydrocarbon group having 1 to 20 carbon atoms represented by R ^{31 to} R ³⁶ ) or a carbon containing a heterocyclic ring represented by R ^{13 to} R ¹⁵ , R ^{17 to} R ^19, and R ^{31 to} R ^36. The hydrogen atom of the group having 2 to 20 atoms is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, mercapto group, isocyanate group, carboxyl group or C2-20, may be substituted with a heterocycle-containing ^{group, a} hydrocarbon of ^{R 13 ~R 15, R 17 ~R} 19 and C2-20 represented by ^R 31 ^{to R 36} Containing group or a methylene group ^R 13 ^{to R 15,} the radical of R 17 ^{to R 19} and C2-20 containing heterocyclic ring represented by ^R 31 ^{to R 36} is, -O -, - CO- , —COO—, —OCO—, —NR ³⁷ —, —NR ³⁷ CO—, —S—, —SO ₂ —, —SCO— or —COS— may be substituted,
R ³⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , if k ≧ 2, different R ¹⁵ , if m ≧ 2, different R ¹⁹ are bonded To form a ring,
At least one of R ¹³ , R ¹⁴ and R ¹⁵ is a group represented by the above general formula (I),
At least one of R ¹⁷ , R ¹⁸ and R ¹⁹ is a group represented by the above general formula (I). ] The oxime ester compound as described in any one of Claims 1-3 represented by the following general formula (IVa) or (IVb).

In [Formula ^{(IVa), R 41, R} 42, R 43, R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54, R ⁵⁵ and ^{R 56 (hereinafter,} both R 41 ^{to R 56} described) each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a trifluoromethyl group, a formyl group, a sulfo group, Group represented by the above general formula (I), R ⁷⁰ , OR ⁷¹ , SR ⁷¹ , NR ⁷² R ⁷³ , COR ⁷¹ , SOR ⁷¹ , SO ₂ R ⁷¹ , CONR ⁷² R ⁷³ , carbonized carbon atom having 1 to 20 carbon atoms Represents a group having 2 to 20 carbon atoms containing a hydrogen group or a heterocyclic ring;
R ⁷¹ , R ⁷² and R ⁷³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
A hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁵⁶ , R ⁷¹ , R ⁷² and R ⁷³ (hereinafter also referred to as R ^{41 to} R ⁵⁶ and R ^{71 to} R ⁷³ ) or R ^{41 to} R The hydrogen atom of the group having 2 to 20 carbon atoms containing a heterocyclic ring represented by ⁵⁶ and R ^{71 to} R ⁷³ is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, or acryloyl. May be substituted with a group having 2 to 20 carbon atoms containing a group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group, a carboxyl group or a heterocyclic ring, and R ^{41 to} R ⁵⁶ and R ^{71 to} R ⁷³ The methylene group in the group having 2 to 20 carbon atoms or a hydrocarbon group having 2 to 20 carbon atoms or a heterocyclic ring represented by R ^{41 to} R ⁵⁶ and R ^{71 to} R ⁷³ is represented by —O − ^{-CO -, - COO -, -} OCO -, - NR 74 -, - NR 74 CO -, - S -, - SO 2 -, - SCO- or -COS- in some cases be substituted,
R ⁷⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ⁴¹ and ^{R 42, R 42} and ^{R 43, R 43} and ^{R 44, R 45} and ^{R 46, R 46} and ^{R 47, R 47} and ^{R 48, R 48} and ^{R 49, R 49} and ^{R 50, R 50} And R ⁵¹ , R ⁵¹ and R ⁵² , R ⁵³ and R ⁵⁴ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ or R ⁵⁶ and R ⁴¹ may combine to form a ring,
At least one of R ^{41 to} R ⁵⁶ is a group represented by the above general formula (I),
In the general formula (IVb), R ⁵⁷ and R ⁶⁴ each independently represent R ⁷⁵ , OR ⁷⁵ , SR ⁷⁵ , PR ⁷⁶ R ⁷⁷ , NR ⁷⁶ R ⁷⁷ or NHPR ⁷⁶ R ⁷⁷ ,
R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ and R ⁷⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, A cyano group, a hydroxyl group, a carboxyl group, a group represented by the above general formula (I), R ⁷⁵ , OR ⁷⁵ , SR ⁷⁵ , NR ⁷⁶ R ⁷⁷ , PR ⁷⁶ R ⁷⁷ , NHPR ⁷⁶ R ⁷⁷ , COR ⁷⁵ , SOR ⁷⁵ , SO ₂ R ⁷⁵ , CONR ⁷⁶ R ⁷⁷ , a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
R ⁷⁵ , R ⁷⁶ and R ⁷⁷ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
R ⁷⁶ and R ⁷⁷ may combine to form a ring,
Carbon represented by R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁵ , R ⁷⁶ , and R ⁷⁷ A hydrocarbon group having 1 to 20 atoms or R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁵ , R ⁷⁶ and a hydrogen atom of a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ⁷⁷ are a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, It may be substituted with a group having 2 to 20 carbon atoms containing an epoxy group, a vinyl group, a mercapto group, an isocyanate group, a carboxyl group or a heterocyclic ring, and R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ^{6. 2} , a hydrocarbon group having 2 to 20 carbon atoms represented by R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁵ , R ⁷⁶ , and R ⁷⁷ , or R ⁵⁸ , Contains a heterocyclic ring represented by R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷⁵ , R ⁷⁶ , and R ⁷⁷ methylene groups in the group of 2 to 20 carbon atoms which may, -O -, - CO -, - COO -, - OCO -, - NR 78 -, - NR 78 CO -, - S -, - SO 2 - , -SCO- or -COS-
R ⁷⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
R ⁵⁷ and R ⁵⁸ , R ⁵⁸ and R ⁵⁹ , R ⁵⁹ and R ⁶⁰ , R ⁶⁰ and R ⁶¹ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶⁴ and R ⁶⁵ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ And R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁶⁸ and R ⁶⁹ or R ⁶⁹ and R ⁷⁰ may combine to form a ring,
At least one of R ⁵⁸ , R ⁵⁹ , R ⁶⁰ , R ⁶¹ , R ⁶² and R ⁶³ is a group represented by the above general formula (I),
At least one of R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , R ⁶⁹ and R ⁷⁰ is a group represented by the above general formula (I). ]   The polymerization initiator containing the oxime ester compound as described in any one of Claims 1-4.   A polymerizable composition comprising the polymerization initiator according to claim 5 and an ethylenically unsaturated compound.   A colored polymerizable composition comprising the polymerizable composition according to claim 6 and a coloring material.   A method for forming a cured product comprising the steps of preparing a substrate, applying the polymerizable composition according to claim 6 or the colored polymerizable composition according to claim 7 to the substrate, and irradiating energy rays. . A cured product of the polymerizable composition according to claim 6 or the colored polymerizable composition according to claim 7.