JP2008179611A5 - - Google Patents

Description

Oxime ester compound, photopolymerization initiator, photopolymerizable composition, color filter, and liquid crystal display device

The present invention relates to an oxime ester compound useful as a photopolymerization initiator, a photopolymerization initiator containing the compound, and uses thereof.
The photopolymerizable composition containing the photopolymerization initiator of the present invention is useful for the production of an optical color filter used for a color television, a liquid crystal display device, a solid-state imaging device, a camera and the like. The photopolymerizable composition containing the photopolymerization initiator of the present invention is particularly sensitive and excellent in resolution, so that it is a black matrix with high definition and high light-shielding properties (hereinafter abbreviated as “BM”). Can be manufactured). Further, by using such a photopolymerizable composition, a high-definition and high-quality color filter and liquid crystal display device can be realized.

  In addition, since the oxime ester compound of the present invention is a highly sensitive photopolymerization initiator, it is not limited to BM or color filter pixel formation applications, photo spacers, ribs (liquid crystal split alignment protrusions), etc. It can also be used for a transparent photopolymerizable composition that does not use a color material, and its application technical field is wide.

  Conventionally, as a method for producing a color filter using a pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method and the like are known.

  In the case of the pigment dispersion method, a photopolymerizable composition obtained by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. to a pigment dispersion obtained by dispersing a pigment with a dispersant or the like is usually on a glass substrate. After coating and drying, a photomask is used for exposure, and development is performed to form a colored pattern. Then, the pattern is fixed by heating to form pixels. These steps are repeated for each color to form a color filter.

  Such a photopolymerizable composition used for image formation of a color filter is required to have characteristics such as sufficient resolution, adhesion to a substrate, and low development residue. Furthermore, in recent years, a pixel having a high color density and a resin black matrix having a high optical density are required, and the content of a color material such as a pigment or carbon black in the photopolymerizable composition tends to be high. When the content of the color material is increased, there is a problem that the above-described resolution, adhesion to the substrate, developability and the like are deteriorated, so that not only the productivity is lowered but also the accuracy and reliability required for the color filter are obtained. It becomes impossible.

As one means for solving such problems, various photopolymerization initiators have been proposed in order to improve the sensitivity of the photopolymerizable composition to the irradiation light for curing. Techniques using oxime ester compounds have been proposed (see Patent Documents 1 to 5). However, in order to meet the demands for further improvement in color density and light-shielding properties and improvement in production efficiency, a photopolymerization initiator with higher sensitivity is required.
JP 2000-80068 A JP 2006-53569 A WO02 / 100903 Publication WO 2006/018405 JP 2006-36750 A

  The present invention solves the above-mentioned problems, and can easily form a light-shielding pattern with a thin film by a photolithography method, and can realize a photopolymerizable composition having sufficient sensitivity and resolution. A specific photopolymerization initiator is provided. By using the photopolymerizable composition containing this photopolymerization initiator, it becomes possible to manufacture the resin BM for the color filter with high accuracy and at low cost. Furthermore, the liquid crystal display device using the color filter manufactured by the photopolymerizable composition of the present invention is excellent in display capability such as contrast.

  In recent years, in order to achieve the “high density” required for color filters, that is, high color density and light-shielding properties, it has been necessary to increase the color material density in the color composition to be used. When the colorant concentration in the product is increased, the light transmittance of the colored composition is lowered. Therefore, in order to maintain and improve the image forming performance, a photopolymerizable material with higher sensitivity is required. The present invention solves this problem.

  In addition, photo spacers used in the manufacture of liquid crystal display devices, photosensitive compositions for ribs, and photo-polymerizable compositions using photo-polymerizable materials in general also have high-precision and low-cost manufacturing techniques. There is a growing demand, and there is a need for photopolymerizable imaging materials with higher sensitivity. The present invention also solves this problem.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have used, as a photopolymerization initiator, an oxime ester compound having a specific structure that further improves the photopolymerization efficiency, and further, carboxylated as an organic binder. It has been found that such an object can be achieved by combining an epoxy acrylate resin having a group.

  Furthermore, it has been found that such a specific oxime ester compound is a novel compound per se and is effective as an excellent photopolymerization initiator regardless of the presence or absence of a coloring material.

  The present invention has been achieved on the basis of such findings and has the following gist.

〔式中、Ｒ¹は、水素原子、炭素数１〜２０のアルキル基、炭素数２〜２５のアルケニル基、炭素数３〜２０のヘテロアリール基または炭素数４〜２５のヘテロアリールアルキル基を示し、これらはいずれも置換基を有していてもよい。あるいは、Ｒ¹はＸまたはＹと結合し、環を形成してもよい。
Ｒ²は、炭素数２〜２０のアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数４〜８のシクロアルカノイル基、炭素数７〜２０のアリーロイル基、炭素数２〜１０のアルコキシカルボニル基、炭素数７〜２０のアリールオキシカルボニル基、炭素数２〜２０のヘテロアリール基、炭素数３〜２０のヘテロアリーロイル基または炭素数２〜２０のアルキルアミノカルボニル基を示し、これらはいずれも置換基を有していてもよい。
Ｘは、置換基を有していてもよい、２個以上の環が縮合してなる、２価の芳香族炭化水素基および／または芳香族複素基を示す。
Ｙは、フェニル基または芳香族複素環単環由来の１価の基に、１以上の環が縮合してなる縮合環基を表し、該縮合環基は置換基を有していてもよい。〕 [1] A photopolymerization initiator composed of an oxime ester compound represented by the following general formula (I).

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl group having 4 to 25 carbon atoms. These may all have a substituent. Alternatively, R ¹ may be bonded to X or Y to form a ring.
R ² is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.
X represents a divalent aromatic hydrocarbon group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Y represents a condensed ring group formed by condensing one or more rings to a monovalent group derived from a phenyl group or an aromatic heterocyclic monocycle, and the condensed ring group may have a substituent. ]

[2] In the general formula (I), Y is a condensed ring group formed by condensing one or more rings to a phenyl group, and the condensed ring group may have a substituent. [1] The photoinitiator described in 1.

[3] In the general formula (I), Y is a 5- or 6-membered ring at least at one position selected from the 2,3-position, 3,4-position and 4,5-position of the phenyl group. The photopolymerization initiator according to [2], which is a group derived from 2 to 4 condensed rings formed by condensation of 3 units, and the group may have a substituent.

[4] The photopolymerization initiator according to [2] or [3], wherein in the general formula (I), the ring condensed with the phenyl group in Y is a hydrocarbon ring.

[5] The photopolymerization initiator according to [2] or [3], wherein in the general formula (I), the ring condensed with the phenyl group in Y is an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring.

[6] In the general formula (I), Y is a condensed ring group formed by condensing one or more rings to a monovalent group derived from an aromatic heterocyclic ring, and the group has a substituent. The photopolymerization initiator according to [1].

[7] The photopolymerization initiator according to any one of [1] to [6], wherein in the general formula (I), Y is a 2-4 condensed ring group which may have a substituent.

〔式中、Ｒ^１、Ｒ^２およびＹは、前記一般式（Ｉ）におけると同義である。環Ｘ^２は、ベンゼン環Ｘ^１に縮合した環を表し、単環でも、２以上の環からなる縮合環でもよい。また環Ｘ^２は、ベンゼン環Ｘ^１のどの位置に縮合していてもよい。ベンゼン環Ｘ^１およびこれに縮合する環Ｘ^２は、さらに置換基を有していてもよい。〕 [8] The photopolymerization initiator according to any one of [1] to [7], wherein the compound represented by the general formula (I) is a compound represented by the following structural formula (i).

[Wherein, R ¹ , R ² and Y have the same meaning as in the general formula (I). Ring X ² represents a ring condensed with benzene ring X ¹ , and may be a single ring or a condensed ring composed of two or more rings. Ring X ² may be condensed at any position of benzene ring X ¹ . The benzene ring X ¹ and the ring X ² condensed thereto may further have a substituent. ]

[9] The In the general formula (i), the ring ^{X 2} is a heterocyclic, photopolymerization initiators described in [8].

[10] Formula in (i), fused ring group consisting of a benzene ring ^{X 1} and ring ^{X 2} is a divalent group derived from 2 or 3 fused rings, as defined in [8] or [9] Photopolymerization initiator.

[11] In the photopolymerizable composition containing (A) an organic binder, (B) a photopolymerization initiator, and (C) a photopolymerizable monomer, (B) the photopolymerization initiator is [1]. Thru | or the photopolymerizable composition containing the photoinitiator in any one of [10].

[12] The content of the oxime ester compound represented by the general formula (I) is 5 parts by weight or more based on 100 parts by weight of the total amount of (A) the organic binder and (C) the photopolymerizable monomer. The photopolymerizable composition according to [11].

[13] The photopolymerizable composition according to [11] or [12], wherein (A) the organic binder is an epoxy acrylate resin having a carboxyl group.

〔式中、ｐおよびｑは各々独立に０〜４の整数を表し、Ｒ¹¹およびＲ¹²は各々独立してアルキル基またはハロゲン基を表す。Ｒ¹³およびＲ¹⁴は各々独立してアルキレン基を表す。ｍおよびｎは各々独立して０以上の整数を表す。〕 [14] The epoxy acrylate resin having a carboxyl group is a novolak epoxy resin, or an epoxy resin (a) represented by the following general formula (X), an α, β-unsaturated monocarboxylic acid and / or [13] An epoxy acrylate resin obtained by reacting a reaction product with an α, β-unsaturated monocarboxylic acid ester (b) having a carboxyl group in the ester moiety and a polybasic acid anhydride (c). The photopolymerizable composition described in 1.

[Wherein, p and q each independently represent an integer of 0 to 4, and R ¹¹ and R ¹² each independently represent an alkyl group or a halogen group. R ¹³ and R ¹⁴ each independently represents an alkylene group. m and n each independently represents an integer of 0 or more. ]

[15] The photopolymerizable composition according to any one of [11] to [14], further comprising (D) a color material.

[16] The photopolymerizable composition according to any one of [11] to [15], further comprising (E) a solvent.

[17] A color filter having an image formed by the photopolymerizable composition according to any one of [11] to [16].

[18] A liquid crystal display device formed using the color filter according to [17].

〔式中、Ｒ¹は、炭素数１〜３のアルキル基、または下記式（IIａ）で表される基を表す。

（式中、Ｒ^１０１およびＲ^１０２は各々独立に、水素原子、フェニル基またはＮ−アセチル−Ｎ−アセトキシアミノ基を表す。）
Ｒ²は、炭素数２〜４のアルカノイル基を示し、Ｘは、窒素原子が炭素数１〜４のアルキル基で置換されていてもよい２価のカルバゾリル基を表す。Ｙ^aは、モルホリノ基で置換されていてもよいナフチル基を示す。〕 [19] An oxime ester compound having a structure represented by the following general formula (II).

[Wherein, R ¹ represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (IIa).

(Wherein R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group.)
R ² represents an alkanoyl group having 2 to 4 carbon atoms, and X represents a divalent carbazolyl group in which a nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Y ^a represents a naphthyl group which may be substituted with a morpholino group. ]

  The oxime ester compound of the present invention can be used as a novel and highly sensitive photopolymerization initiator. A photopolymerizable composition useful for color filter applications can be formed by combining this oxime ester compound with an organic binder and a colorant. In particular, a photopolymerizable composition using this oxime ester compound in combination with a black pigment as a photopolymerization initiator has high sensitivity at low cost and high quality because it is highly light-shielding in a thin film. The resin BM can be formed.

  Since the color filter in which the resin BM is formed using the photopolymerizable composition of the present invention is excellent in accuracy, flatness, and durability, the display quality of the liquid crystal element can be improved. In addition, since the manufacturing process and the color filter itself do not contain harmful substances, the danger to the human body is reduced and the environmental safety is improved.

  The photopolymerization initiator and the photopolymerizable composition of the present invention are not limited to those for BM, and are also transparent photopolymerizable compositions that do not use a color material such as a photo spacer and a rib (liquid crystal split alignment protrusion). It can be used, and its application technology field is very wide.

  Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

  In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acryloyl”. “(Poly) hydroxy” means “hydroxy and / or polyhydroxy”.

  In the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant. . The measuring method will be described later.

[Photopolymerizable composition]
First, the photopolymerizable composition of the present invention (hereinafter sometimes referred to as “resist” or “resist liquid”) will be described.

  The photopolymerizable composition of the present invention is a photopolymerizable composition containing (A) an organic binder, (B) a photopolymerization initiator, and (C) a photopolymerizable monomer. It contains a specific compound as an initiator.

{Formulation ingredients}
(A) Organic binder Although the organic binder used for the photopolymerizable composition of this invention is not specifically limited, Especially the epoxy acrylate resin which has a carboxyl group is used preferably.

  The epoxy acrylate resin is obtained by adding an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester (b) having a carboxyl group to the ester moiety to the epoxy resin (a), and Synthesize | combined by making a polybasic acid anhydride (c) react. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As the raw material epoxy resin (a), (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, The epoxy resin etc. which are shown by general formula (X) can be used conveniently.

〔式中、ｐおよびｑは各々独立に０〜４の整数を表し、Ｒ¹¹およびＲ¹²は各々独立してアルキル基またはハロゲン基を表す。Ｒ¹³およびＲ¹⁴は各々独立してアルキレン基を表す。ｍおよびｎは各々独立して０以上の整数を表す。〕

[Wherein, p and q each independently represent an integer of 0 to 4, and R ¹¹ and R ¹² each independently represent an alkyl group or a halogen group. R ¹³ and R ¹⁴ each independently represents an alkylene group. m and n each independently represents an integer of 0 or more. ]

  Among these, a novolak type epoxy resin or an epoxy resin represented by the above general formula (X) is preferable, and in particular, from the viewpoint of a balance between resistance to alkali developer and developability, the unsaturated bond concentration is high, A resin having a suitable carboxylic acid concentration and a solid core is preferable, and an epoxy resin represented by the general formula (X) is particularly preferable.

In the general formula (X), the alkyl group of R ¹¹ and R ¹² is preferably an alkyl group having 1 to 10 carbon atoms, and the halogen group includes Cl, Br, F and the like. R ¹¹ and R ¹² are particularly preferably each independently an alkyl group having 1 to 5 carbon atoms.
Although the details of the mechanism of action of the alkyl groups and halogen groups of R ¹¹ and R ¹² are not clear, it is assumed that they affect the three-dimensional structure and control the ease of dissolution in the developer. .
Therefore, from the above viewpoint, p and q in the general formula (X) each independently represent an integer of 0 to 4, preferably 1 or 2.

または

に対してｏ−位が好ましい。 The bonding position of R ¹¹ and R ^{12 to} the benzene ring is not particularly limited,

Or

The o-position is preferred.

R ¹¹ and R ¹² may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.

Examples of the alkylene group for R ¹³ and R ¹⁴ include an alkylene group having 1 to 10 carbon atoms, and it is particularly preferable that they are each independently an ethylene group or a propylene group.

  m and n each independently represents an integer of 0 or more, but is usually about 0 to 6, preferably about 0 to 3. In general, the larger m and n are, the higher the solubility is, but if too large, the sensitivity may be lowered.

R ¹³ and R ¹⁴ may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.

  The molecular weight of these epoxy resins (a) is usually in the range of 200 to 200,000, preferably 300 to 100,000 as the weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC). If the molecular weight is less than the above range, there are many cases where a problem occurs in the film forming property. Conversely, if the resin exceeds the above range, gelation easily occurs during the addition reaction of the α, β-unsaturated monocarboxylic acid, and the production is difficult. There is a risk of becoming.

  Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable.

  The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred.

  A known method can be used for the addition reaction of the α, β-unsaturated monocarboxylic acid and / or its ester (b) with the epoxy resin (a). For example, the α, β-unsaturated monocarboxylic acid and / or its ester (b) and the epoxy resin (a) can be reacted at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .

  The epoxy resin (a), the α, β-unsaturated monocarboxylic acid and / or the α, β-unsaturated monocarboxylic acid ester (b) having a carboxyl group in the ester portion, and the esterification catalyst are all one kind. May be used alone, or two or more may be mixed and used.

  The amount of α, β-unsaturated monocarboxylic acid and / or its ester (b) used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 1 equivalent of the epoxy group of the raw material epoxy resin (a). Is in the range of 0.7 to 1.1 equivalents. If the amount of α, β-unsaturated monocarboxylic acid and / or ester (b) used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with polybasic acid anhydride (c) becomes insufficient. . Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid and / or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride (c) to be further added to the epoxy resin (a) to which the α, β-unsaturated carboxylic acid and / or its ester (b) is added includes maleic anhydride, succinic anhydride, itaconic anhydride. Acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, anhydrous Examples thereof include one or more of chlorendic acid, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc., preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride Acid, hexahydrophthalic anhydride, pyromellitic anhydride, tri Mellitic acid, biphenyltetracarboxylic dianhydride, and particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride.

  A known method can also be used for the addition reaction of the polybasic acid anhydride (c), which is the same as the addition reaction of the α, β-unsaturated carboxylic acid and / or its ester (b) to the epoxy resin (a). Can be obtained by continuing the reaction under various conditions. The addition amount of the polybasic acid anhydride (c) is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mg-KOH / g, more preferably 20 to 140 mg-KOH / g. Is particularly preferred. When the resin acid value is less than the above range, alkali developability is poor, and when it exceeds the above range, a tendency to be inferior in curing performance is recognized.

  In addition, it is good also as what introduce | transduced polyfunctional alcohol, such as a trimethylol propane, a pentaerythritol, dipentaerythritol, and introduce | transduced the multibranched structure at the time of this addition reaction of a polybasic acid anhydride.

  (A) The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) measurement of an epoxy acrylate resin having a carboxyl group used as an organic binder is usually 1,000 or more, preferably 1,500 or more. Usually, it is 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, and particularly preferably 8,000 or less. If the molecular weight is too large, the developability may be deteriorated. On the other hand, if the molecular weight is too small, the alkali resistance may be inferior.

  As the organic binder (A), in addition to the epoxy acrylate resin having a carboxyl group obtained as described above, the following resins can also be used. In addition, some of the resins described below partially overlap with those belonging to the epoxy acrylate resin, and are not classified as different substances.

That is, a homopolymer or copolymer such as (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, or a carboxyl group Preferable examples include a vinyl-containing resin, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, and acetyl cellulose.
Among these, from the viewpoint of alkali developability and image formability, the epoxy acrylate resin having a carboxyl group and the carboxyl group-containing vinyl resin are preferable, and the epoxy acrylate resin having a carboxyl group is more preferable.

  As the carboxyl group-containing vinyl resin, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other unsaturated carboxylic acids, styrene, α-methylstyrene , Hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethyl Aminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl And copolymers with vinyl compounds such as (meth) acrylamide and vinyl acetate.

  Among the above copolymers, a styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and 3-30 mol% styrene, 10-70 mol% (meth) acrylate, 10 (meth) acrylic acid. A copolymer consisting of ˜60 mol% is more preferred, and a copolymer consisting of 5 to 25 mol% styrene, 20 to 60 mol% (meth) acrylate, and 15 to 55 mol% (meth) acrylic acid is particularly preferred. The acid value of these carboxyl group-containing vinyl resins is usually 30 to 250 mg-KOH / g, preferably 50 to 200 mg-KOH / g, more preferably 70 to 150 mg-KOH / g.

  Furthermore, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in the side chain are suitable. For example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl is added to the carboxyl group-containing polymer. (Meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Saturated compounds, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] deci 2-yl] an alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate is reacted with 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer. Reaction products obtained and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N -Compounds having two or more unsaturated groups such as diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meta ) Acrylate, vinyl crotonate, vinyl (meth) acryl The ratio of the compound having two or more kinds of unsaturated groups such as luamide and the unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the unsaturated group. The reaction product etc. which were copolymerized so that it may become 10-90 mol%, preferably about 30-80 mol% are mentioned.

The weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC) of the carboxyl group-containing vinyl resin is usually 1,000 or more, preferably 1500 or more, more preferably 2000 or more, and usually 100,000 or less. preferably 50,00 0 hereinafter, more preferably 20,000 or less, particularly preferably 10,000 or less. If the molecular weight is too large, the developability may be deteriorated. On the other hand, if the molecular weight is too small, the alkali resistance may be insufficient.

In addition, when using the photopolymerizable compound of this invention for formation of a liquid crystal division | segmentation alignment protrusion, it is polystyrene conversion by the gel permeation chromatography (GPC) measurement of the epoxy acrylate resin which has a carboxyl group as an (A) organic binder. The weight average molecular weight is usually 1,000 or more, preferably 1,500 or more, usually 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, and particularly preferably 5,000 or less. . The weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC) of the carboxyl group-containing vinyl resin is usually 1,000 or more, preferably 1500 or more, more preferably 2000 or more, and usually 100, 000 or less, preferably 50,00 0 hereinafter, more preferably 20,000 or less, particularly preferably 10,000 or less.
When the organic binder having the molecular weight range is contained, the photopolymerizable composition is preferably deformed at the time of heating, so that an arch-shaped protrusion having a good shape of the liquid crystal split alignment protrusion is formed.

(B) Photopolymerization initiator The photopolymerizable composition of the present invention is an oxime ester compound represented by the following general formula (I) (hereinafter referred to as “oxime ester compound (I)”) as a photopolymerization initiator. Contain).

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl group having 4 to 25 carbon atoms. These may all have a substituent. Alternatively, R ¹ may be bonded to X or Y to form a ring.
R ² is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.
X represents a divalent aromatic hydrocarbon group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Y represents a condensed ring group formed by condensing one or more rings to a monovalent group derived from a phenyl group or an aromatic heterocyclic monocycle, and the condensed ring group may have a substituent. ]

In the oxime ester compound (I), the Y-C (= O) -X moiety forms a light-absorbing part, and the oxime structure part: -C (-R ¹ ) = N-OR ² part becomes a radical generating site. . Absorbing part: Y—C (═O) —X efficiently absorbs light, and the absorbed energy is efficiently transferred to the oxime structure part to achieve high sensitivity. In the light absorption part represented by the YC (= O) -X part, particularly when added at a high concentration in the composition, the molecules associate with each other, and apparently a plurality of molecules behave as a single molecule. Therefore, it is considered that the absorbance and the absorption efficiency tend to decrease. The oxime ester-based compound (I) of the present invention can have a high absorbance even when added at a high concentration by making the Y portion a bulky group.

  In addition, it is important that the YC (= O) -X moiety generates high-efficiency triplet energy that can be easily used for radical generation in the oxime structure part, achieving efficient energy transfer within the molecule. Therefore, it is important to make the YC (═O) —X portion and the oxime structure portion spatially close as much as possible.

The compound represented by the general formula (I) contains a benzophenone structure having a high efficiency of state change from a singlet state to a triplet state or a similar structure in the YC (= O) -X moiety. Therefore, the absorbed light can be efficiently converted into triplet energy.
Furthermore, the compound represented by the general formula (I) is a compound in which the benzophenone structure or a similar structure is likely to overlap with the oxime structure portion due to spatial rotation in the molecule. Efficient energy transfer is possible and higher sensitivity can be achieved.

In the general formula (I), X represents a divalent aromatic hydrocarbon group and / or an aromatic heterocyclic group, which may have a substituent and is formed by condensation of two or more rings.
X is specifically a group derived from a condensed ring composed of an aromatic hydrocarbon ring such as a naphthalene ring, anthracene ring, chrysene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring or indene ring; Examples thereof include a group derived from a condensed ring composed of an aromatic hydrocarbon ring and an aromatic heterocyclic ring such as a nanthridine ring, a xanthene ring, a carbazole ring, a phenazine ring, a phenothiazine ring, a phenoxazine ring and a benzothiazole ring.
Any of these may have an arbitrary substituent. This “optional substituent” will be described later.

Among the compounds represented by the general formula (I), in particular, a compound represented by the following general formula (i), that is, the X group in the general formula (I) is a benzene ring X ¹ in the general formula (i) and A compound having a structure represented by ring X ² to be condensed is preferable.

〔式中、Ｒ^１、Ｒ^２およびＹは、前記一般式（Ｉ）におけると同義である。環Ｘ^２は、ベンゼン環Ｘ^１に縮合した環を表し、単環でも、２以上の環からなる縮合環でもよい。また環Ｘ^２は、ベンゼン環Ｘ^１のどの位置に縮合していてもよい。ベンゼン環Ｘ^１およびこれに縮合する環Ｘ^２は、さらに置換基を有していてもよい。〕

[Wherein, R ¹ , R ² and Y have the same meaning as in the general formula (I). Ring X ² represents a ring condensed with benzene ring X ¹ , and may be a single ring or a condensed ring composed of two or more rings. Ring X ² may be condensed at any position of benzene ring X ¹ . The benzene ring X ¹ and the ring X ² condensed thereto may further have a substituent. ]

In the compound represented by the general formula (i), the benzene ring X ¹ can form a benzophenone structure or a similar structure together with —C (═O) —Y. This is preferable because the excitation efficiency to the state is high.

X in the general formula (I) is preferably a group containing an aromatic heterocycle, and particularly preferred is the case where the ring X ² fused to the benzene ring X ¹ in the general formula (i) is a heterocycle.

  X is usually a divalent group derived from 2 to 4 condensed rings, and is preferably a divalent group derived from 2 or 3 condensed rings from the viewpoint of relatively low molecular weight. From the viewpoint of easily adapting to the wavelength of irradiation light used for curing, a divalent group derived from a tri-fused ring is more preferable.

As the structure formed by X in general formula (I) and benzene ring X ¹ and ring X ² in general formula (i), a group derived from a carbazole ring is particularly preferable. When X is a group derived from a carbazole group, it is preferable because it is a robust skeleton in addition to the compatibility with irradiation light during exposure.

In the general formula (I), R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroaryl having 4 to 25 carbon atoms. Represents an alkyl group, and these alkyl groups, alkenyl groups, heteroaryl groups, and heteroarylalkyl groups may all have a substituent. By making R ¹ such a group, the sensitivity to light is higher than that of a compound in which R ¹ is a phenyl group or the like. Moreover, since the synthesis | combination of a compound is also easy, it is preferable also from an industrial viewpoint.

Examples of the alkyl group having 1 to 20 carbon atoms of R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
Examples of the alkenyl group having 2 to 25 carbon atoms for R ¹ include a vinyl group and a propenyl group, preferably an alkenyl group having 3 to 12 carbon atoms such as a propenyl group, more preferably an alkenyl group having 2 to 5 carbon atoms. .
Examples of the heteroaryl group having 3 to 20 carbon atoms of R ¹ include a thionyl group, a furyl group, an imidazolyl group, a benzthiazolyl group, a benzoxazolyl group, preferably 3 to 15 carbon atoms, more preferably a carbon number. 4 to 10 heteroaryl groups.
Examples of the heteroarylalkyl group having 4 to 25 carbon atoms of R ¹ include thionylmethyl group, furfuryl group, imidazolylmethyl group, benzthiazolylmethyl group, benzoxazolylmethyl group, and preferably 4 carbon atoms. -18, more preferably a heteroarylalkyl group having 4 to 10 carbon atoms.

  In addition, each group mentioned above may have a substituent. The substituent will be described later.

R ¹ is particularly preferably an alkyl group which may have a substituent. Among these, an unsubstituted alkyl group is preferable from the viewpoint of ease of production. Moreover, when the compound represented by general formula (I) is used for a photopolymerizable composition so that it may mention later, the alkyl group substituted by the substituted amino group from a viewpoint of the adhesiveness to the board | substrate of this composition. And an alkyl group substituted with an N-acetyl-N-acetoxyamino group is most preferable.

Examples of the alkanoyl group having 2 to 20 carbon atoms of R ² in the general formula (I) include an acetyl group, a propanoyl group, a butanoyl group, and the like, preferably 2 to 12 carbon atoms such as acetyl, more preferably 2 carbon atoms. -7 alkanoyl groups.
Examples of the alkenoyl group having 3 to 25 carbon atoms of R ² include a crotonoyl group and an acryloyl group, preferably an alkenoyl group having 3 to 12 carbon atoms, such as crotonoyl, and more preferably 3 to 7 carbon atoms.
Examples of the cycloalkanoyl group having 4 to 8 carbon atoms of R ² include a cyclohexylcarbonyl group, a methylcyclohexylcarbonyl group, and a cyclopentylcarbonyl group, preferably 4 to 8 carbon atoms such as cyclohexylcarbonyl, and more preferably 4 carbon atoms. A cycloalkanoyl group of ˜7.
Examples of the aryloyl group having 7 to 20 carbon atoms of R ² include a benzoyl group, a methylbenzoyl group, and a naphthoyl group. Preferably, the aryloyl group has 7 to 12 carbon atoms, such as naphthoyl, and more preferably 7 to 10 carbon atoms. It is.
Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms of R ² include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group, preferably 2 to 10 carbon atoms such as a methoxycarbonyl group, more preferably a carbon number. 2 to 8 alkoxycarbonyl groups.
Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms of R ² include phenoxycarbonyl group, p-methylphenoxycarbonyl group, naphthoxycarbonyl group and the like, preferably 7 to 15 carbon atoms such as naphthoxycarbonyl group, More preferred is an aryloxycarbonyl group having 7 to 10 carbon atoms.
Examples of the heteroaryl group having 2 to 20 carbon atoms of R ² include a thiophenyl group, a pyrrolyl group, and a pyridyl group, and preferably a heterocycle having 2 to 12 carbon atoms, such as a thiophenyl group, and more preferably 2 to 7 carbon atoms. An aryl group.
Examples of the hetero aryloyl group having 3 to 20 carbon atoms of R ² include a thiophenecarbonyl group, a pyrrolylcarbonyl group, and a pyridinecarbonyl group, preferably 5 to 15 carbon atoms such as a thiophenecarbonyl group, more preferably carbon. It is a hetero aryloyl group of several 7 to 10.
The alkylamino group of a carbon number 2 to 20 R ^2, molar morpholinocarbonyl group, dimethylaminocarbonyl group, and the like methylaminocarbonyl group, preferably 2 to 12 carbon atoms such as dimethylaminocarbonyl, More preferred is an alkylaminocarbonyl group having 2 to 10 carbon atoms.

Among the groups described above, from the viewpoint of exposure sensitivity, A Le as R ² Kanoiru groups, cycloalkanoyl, preferably aryloyl group, Akanoiru group, aryloyl group is more preferable.

In addition, although the substituent which each group mentioned above as R < ² > may have is mentioned later, as each group mentioned above, what does not have a substituent is especially preferable.

  In general formula (I), Y represents a condensed ring group formed by condensing one or more rings to a monovalent group derived from a phenyl group or an aromatic heterocyclic monocycle, and the condensed ring group has a substituent. You may do it. As described above, the compound represented by the general formula (I) is a benzophenone having a phenyl group or an aromatic heterocyclic part contained in Y via a — (C═O) — group and a part of X. This is preferable because it forms a structure or a similar structure.

  In addition, as described above, the compound represented by the general formula (I) is a compound in which the benzophenone structure or a similar structure is likely to overlap with the oxime structure portion due to spatial rotation in the molecule. It is preferable because efficient energy transfer within the molecule is possible and higher sensitivity can be achieved.

  When Y is a condensed ring group formed by condensing one or more rings to a phenyl group, at least one position selected from 2,3-position, 3,4-position and 4,5-position of the phenyl group In addition, a group derived from 2 to 4 condensed rings formed by condensing 1 to 5 5- or 6-membered rings is preferable. Further, the ring condensed with the phenyl group in Y is preferably a hydrocarbon ring, an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring. The ring condensed with the phenyl group in Y is preferably a hydrocarbon ring from the viewpoint of high quantum yield, and is preferably an aromatic ring from the viewpoint of widening the absorption wavelength.

  Specific examples of Y include a naphthalene ring, anthracene ring, chrysene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, a group derived from an aromatic hydrocarbon ring such as an indene ring, or an acridine ring, Examples thereof include a group derived from a condensed ring composed of an aromatic hydrocarbon ring such as a phenanthridine ring, a xanthene ring, a carbazole ring, a phenazine ring, a phenothiazine ring, a phenoxazine ring and a benzothiazole ring, and an aromatic heterocycle.

  Y may be a condensed ring group obtained by condensing one or more rings to a monovalent group derived from an aromatic heterocycle. In this case, a group derived from “a condensed ring composed of an aromatic hydrocarbon ring and an aromatic heterocycle” and a group in which a bond extends from the aromatic heterocycle can be mentioned.

Y is preferably a 2-4 condensed ring group, more preferably a 2-3 condensed ring group, and particularly preferably a 2 condensed ring group from the viewpoint that the molecular weight does not become too large. In addition, when Y is a group derived from a 3-4 condensed ring, it is industrially preferable because the absorption wavelength region becomes relatively long and adapts to an inexpensive light source.
Y is most preferably a naphthyl group among the two condensed ring groups.

Examples of the substituent which the condensed ring group in Y described above may have include, for example, an alkylthio group having 1 to 20 carbon atoms such as a methylthio group and an ethylthio group; —SO ₃ R (where R is a methyl group or an ethyl group) Alkyl group having 1 to 20 carbon atoms such as alkyl group having 1 to 20 carbon atoms; alkoxy group having 5 to 20 carbon atoms such as pentyloxy group and hexyloxy group; and 5 to 5 carbon atoms such as cyclopentyl group and cyclohexyl group. A cycloalkyloxy group having 20 to 20 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group; a cyclic amino group having 5 to 20 atoms such as a morpholino group and a piperidino group; a diisopropylamino group and a di-t A dialkylamino group having 4 to 20 carbon atoms such as a butylamino group; an aryl group such as a phenyl group or a naphthyl group; Heteroaryl group such; Cl, Br, I, halogen atom such as F, and the like.
Among these, an alkoxy group, —SO ₃ R, a cyclic amino group, or a dialkylamino group is preferable, and a cyclic amino group or a dialkylamino group is particularly preferable from the viewpoint of improving sensitivity.

  Among the compounds represented by the general formula (I), a compound in which X is a group derived from a carbazole ring which may have a substituent, which is a particularly preferred form, is represented by, for example, the following general formula (III) .

〔式中、Ｒ¹、Ｒ²およびＹは、前記一般式（Ｉ）におけると同義である。Ｒ³〜Ｒ⁹は各々独立に水素原子または後述する任意の置換基Ｚを表す。〕

[Wherein, R ¹ , R ² and Y have the same meanings as in the general formula (I). R ^{3 to} R ⁹ each independently represent a hydrogen atom or an optional substituent Z described later. ]

Substituents that X in the general formula (I) can have (substituents that the benzene ring X ¹ in general formula (i) and the ring X ² condensed thereto can have), general formulas (I), (i ) And (III) R ¹ and R ² may have a substituent, and R ^{3 to} R ⁹ in the general formula (III) are each independently selected from the following substituents Z.

[Substituent group Z]
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; nitro group; cyano group; any organic group.
The arbitrary organic groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group, n- C1-C18 linear or branched alkyl groups such as heptyl, n-octyl and t-octyl; C3-C18 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl A linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group or a cyclohexenyl group; a methoxy group Ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-amyloxy group a linear or branched alkoxy group having 1 to 18 carbon atoms such as a t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, n-amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, t A linear or branched alkylthio group having 1 to 18 carbon atoms such as an octylthio group; an aryl group optionally substituted with an alkyl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, or a mesityl group; Aralkyl groups having 7 to 18 carbon atoms such as benzyl group and phenethyl group; vinyloxy group, propenyloxy group, hexenyloxy group Linear or branched alkenyloxy group having 2 to 18 carbon atoms; represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group Carboxyl group; acyloxy group represented by —OCOR ¹⁸ ; amino group represented by —NR ¹⁹ R ²⁰ ; acylamino group represented by —NHCOR ²¹ ; carbamate group represented by —NHCOOR ²² ; A carbamoyl group represented by ²³ R ²⁴ ; a carboxylic acid ester group represented by —COOR ²⁵ ; a sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; a sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl, 2-pyridyl, furyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, morpholino, pyrrolidi Examples thereof include saturated or unsaturated aromatic heterocyclic groups such as nyl group and tetrahydrothiophene dioxide group, and trialkylsilyl groups such as trimethylsilyl group.

R ^{17 to} R ²⁸ are each a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkanoyl group, an optionally substituted alkylcarbonyloxy group, or optionally substituted. An alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group is represented. These positional relationships are not particularly limited, and when they have a plurality of substituents, they may be the same or different.

  In the above, a plurality of substituents may be bonded to each other to form a ring, and the formed ring may be a saturated or unsaturated aromatic hydrocarbon ring or aromatic heterocyclic ring, and further on the ring. Each may have a substituent, and the substituent may further form a ring.

In the general formula (III), R ^{3 to} R ⁹ are each independently selected from a hydrogen atom or the above substituent group Z, and among the substituent group Z, it may preferably have a substituent. An alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group which may have a substituent; pyridyl which may have a substituent A heteroaryl group having 3 to 20 carbon atoms such as a group; an aralkyl group having 7 to 18 carbon atoms which may have a substituent; and a trialkylsilyl group which may have a substituent are particularly preferable. Is an alkyl group.

In addition, what is preferable as the substituent which X in the general formula (I) may have (the benzene ring X ¹ in the general formula (i) and the ring X ² condensed thereto) may have the above R ^3. it is the same as those preferred to R ^9.

As the substituent that R ¹ may have, an amino group and an aryl group represented by —NR ¹⁹ R ²⁰ are preferable, and R ¹⁹ and R ²⁰ may be an alkanoyl group that may be substituted, or may be substituted. An alkylcarbonyloxy group is preferred. As described above, an amino group represented by —NR ¹⁹ R ²⁰ such as an N-acetyl-N-acetoxyamino group is particularly preferable because it is effective for improving the adhesion of the composition.

  Of the compounds represented by the general formula (I) of the present invention, the compound represented by the following general formula (II) is most preferable.

（式中、Ｒ^１０１およびＲ^１０２は各々独立に、水素原子、フェニル基またはＮ−アセチル−Ｎ−アセトキシアミノ基を表す。）
Ｒ²は、炭素数２〜４のアルカノイル基を示し、Ｘは、窒素原子が炭素数１〜４のアルキル基で置換されていてもよい２価のカルバゾリル基を表す。Ｙ^aは、モルホリノ基で置換されていてもよいナフチル基を示す。〕 [Wherein, R ¹ represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (IIa).

(Wherein R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group.)
R ² represents an alkanoyl group having 2 to 4 carbon atoms, and X represents a divalent carbazolyl group in which a nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Y ^a represents a naphthyl group which may be substituted with a morpholino group. ]

  Specific examples of the photopolymerization initiator suitable for the present invention are illustrated below, but the photopolymerization initiator used in the present invention is not limited to the following. In the following, Me represents a methyl group.

  As a photoinitiator of this invention, 1 type of the oxime ester type compound represented by the said general formula (I) may be used independently, and 2 or more types may be used together. In addition, these oxime ester compounds (I) and other photopolymerization initiators can be used in combination, and in some cases, high sensitivity can be expected by the combined use. Examples of other photopolymerization initiator compounds that can be used in combination with the oxime ester compound (I) according to the present invention include the following compounds.

  For example, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Halomethylated triazine derivatives such as (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4- Oxadiazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl Halomethylated oxadiazole derivatives such as -5-furyl-1,3,4-oxadiazole, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4, 5-diphenylimidazole dimer, imidazole derivatives such as (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether 2-methylanthraquinone, 2-ethylanthraquinone, -Anthraquinone derivatives such as t-butylanthraquinone and 1-chloroanthraquinone, benzanthrone derivatives, benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2- Benzophenone derivatives such as carboxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1- Methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-mol Acetophenone derivatives such as holino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone Thioxanthone derivatives such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, 9-phenylacridine, 9- (p- Acridine derivatives such as methoxyphenyl) acridine, phenazine derivatives such as 9,10-dimethylbenzphenazine, bis-cyclopentadienyl-Ti-dichloride, bis-cyclopentadienyl-Ti-bis-phenyl, Su-cyclopentadienyl-Ti-bis- (2,3,4,5,6-pentafluorophen-1-yl), bis-cyclopentadienyl-Ti-bis- (2,3,5,6 -Tetrafluorophen-1-yl), bis-cyclopentadienyl-Ti-bis- (2,4,6-trifluorophen-1-yl), bis-cyclopentadienyl-Ti-2,6- Di-fluorophen-1-yl, bis-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl, bis-methylcyclopentadienyl-Ti-bis- (2,3,4, 5,6-pentafluorophen-1-yl), bis-methylcyclopentadienyl-Ti-bis- (2,6-di-fluorophen-1-yl), bis-cyclopentadienyl-Ti-2 , 6-Di-fluoro-3 (Pill-1-yl) - titanocene derivatives of 1-yl and the like, and the like.

  In addition to the photopolymerization initiator component, a sensitizing dye can be further added to the photopolymerizable composition of the present invention. In order to cause a photopolymerization reaction in a highly light-shielding resin composition, it is preferable to add a sensitizing dye.

  Examples of such a sensitizing dye include a coumarin compound having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and a 3-ketocoumarin compound described in JP-A 63-221110. Xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, pyromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292. (P-dialkylaminobenzylidene) ketone and styryl dye described in JP-A-56-166154 and JP-A-59-56403, and a julolidyl group described in JP-A-6-295061. Examples thereof include sensitizing dyes and diaminobenzene compounds described in JP-A No. 11-326624.

  Of these sensitizing dyes, amino group-containing sensitizing dyes and xanthene dyes are particularly preferable.

(C) Photopolymerizable monomer As the photopolymerizable monomer used in the present invention, a compound having one or more ethylenically unsaturated groups (hereinafter referred to as an ethylenic compound) is used. Specifically, ester of aliphatic (poly) hydroxy compound and unsaturated carboxylic acid, ester of aromatic (poly) hydroxy compound and unsaturated carboxylic acid, unsaturated carboxylic acid, polyvalent carboxylic acid and aliphatic poly Esters obtained from hydroxy compounds, ethylene oxide of aromatic polyhydroxy compounds, esterification reaction products of propylene oxide adducts and unsaturated carboxylic acids, ethylene oxides of aliphatic polyhydroxy compounds, caprolactone-modified polyhydric alcohols and unsaturated carboxylic acids Esters, polyhydric alcohols, polyisocyanates and unsaturated carboxylic acids, styryl-terminated compounds, phosphoric acid unsaturated compounds, polyepoxy and unsaturated carboxylic acid adducts, and the like.

  Among these, specific examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylol propane tri Acrylate esters such as acrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylic acid with the acrylate of the exemplified compound replaced with methacrylate Ether, similarly itaconic acid ester instead itaconate, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced crotonate.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

  Typical examples of esters obtained by reacting unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds include (meth) acrylic acid, phthalic acid and ethylene glycol condensates, (meth) acrylic. Examples include condensates of acids, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin. These are not necessarily a single substance, but may be a mixture of compounds having a plurality of similar structures.

  In addition, as examples of the ethylenic compound used in the present invention, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.

  Among the ethylenic compounds listed above, preferred are those having a (meth) acryloyl group, more preferably an acryloyl group. Such compounds include trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. Is mentioned.

  These photopolymerizable monomers may be used alone or in combination of two or more.

(D) Coloring material In the photopolymerizable composition of the present invention, a coloring material is not an essential component, but is used in combination in many applications. Here, the colorant refers to a component that colors the photopolymerizable composition.

  As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  As the black pigment, a single black pigment or a black pigment obtained by mixing red, green, blue, or the like can be used. These black pigments can be appropriately selected from inorganic or organic pigments and dyes, and can be used alone or in combination.

  Examples of the single black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among these, carbon black and titanium black are particularly preferable from the viewpoints of light shielding rate and image characteristics. Examples of commercially available carbon black include the following brands.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.

  Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Special BlackS, 350c, p

  Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS480, PEARLS480, etc.

  Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040 and the like.

  Next, the black pigment by mixing will be described. Specific examples of the color material used as a base for mixing include Victoria Pure Blue (42595), Auramine O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), no. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  The carbon black may be used in combination with other black or colored inorganic or organic pigments. Other pigments naturally have a light shielding property or image characteristic lower than that of carbon black, so the mixing ratio is naturally limited.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

  Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

  These color materials may be used alone or in combination of two or more.

  As described above, the photopolymerizable composition of the present invention can be used for various applications, but its high sensitivity to irradiation light and excellent image forming properties were used for forming a black matrix for a color filter. It is particularly effective when. When using for black matrix formation, (D) Use the black pigments such as carbon black and titanium black described above as the color material, or mix multiple types of pigments other than black and adjust to black. That's fine.

(E) Solvent The photopolymerizable composition of the present invention is usually blended with (A) an organic binder, (B) a photopolymerization initiator, (C) a photopolymerizable monomer, if necessary ( D) Used in a state in which a coloring material and optional components described later are dissolved in (E) a solvent.

  (E) As a solvent, it is possible to dissolve or disperse each component constituting the composition, and it is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120-170 ° C.

Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, profile propylene glycol monomethyl ether, propylene glycol -t- butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Glycol monoalkyl ethers such as ethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol monomethyl ether acetate, 3- Glycol alkyl ether acetates such as methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate Rate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone Linear or cyclic esters such as
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile;
Etc.

  Solvents corresponding to the above include mineral spirit, Valsol # 2, Apco # 18 Solvent, Apco Thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, diglyme and other commercial products.

  Among the various solvents described above, from the viewpoint of volatility, stability, solubility of each component, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, butyl acetate, propyl acetate, amyl acetate, ethylene glycol acetate, ethyl pro Pionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl Tearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone Are preferred, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, butyl acetate, propyl acetate , Amyl acetate, ethylene glycol acetate, ethyl propionate, propyl propionate, 3-ethoxypropio More preferred are methyl acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate and γ-butyrolactone.

  These solvents may be used alone or in combination of two or more.

(F) Other ingredients (optional ingredients)
The photopolymerizable composition of the present invention comprises (A) an organic binder, (B) a photopolymerization initiator, (C) a photopolymerizable monomer, and (D) a colorant contained as necessary. Further, optional components are added as necessary. Examples of the optional components include pigment dispersants, adhesion improvers, coatability improvers, development improvers and the like. In particular, in the composition of the present invention, it is desirable to blend a pigment dispersant because it is important for quality stability to finely disperse a color material such as a black pigment and stabilize the dispersion state.

  The pigment dispersant has affinity for both (D) a colorant such as a black pigment and (A) an organic binder, and includes surfactants such as nonions, cations and anions, polymer dispersants, and the like. It is done. Among them, polymer dispersants are preferable, and polymer dispersants having basic functional groups such as primary, secondary, or tertiary amino groups, and nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are particularly advantageously used. Is done.

  Specific examples of a chemical structure preferable as a polymer dispersant having a basic functional group include, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule, and active hydrogen in the same molecule. Examples thereof include resins obtained by reacting a compound having a tertiary amino group.

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , bicycloheptane triisocyanate, tris (isocyanate phenyl methane), tris (isocyanate phenyl) thiophosphate, etc. triisocyanate, and trimers of these, hydrogen adducts, and these polyols adducts. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. And the like. Moreover, these 2 or more types of mixtures are also mentioned.

Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and the like. The mixture of 2 or more types of these is mentioned.

Polyether ester diols include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or reacting a polyester glycol with an alkylene oxide, such as poly ( And polyoxytetramethylene) adipate.
Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diols or carbon number 1-25 Polylactone diol or polylactone monool obtained by using a monovalent alcohol as an initiator, for example, polycaprolactone glycol, poly methyl valerolactone and mixtures of two or more thereof.
Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated poly. Examples include isoprene glycol.
The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

The compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of an amino group is preferred. The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

  Examples of such compounds having active hydrogen and tertiary amino group in the same molecule are N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N-dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl- 1,4-butanediamine and the like can be mentioned.

  In addition, the tertiary amino group is an N-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, N-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Preferred as these N-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.

  Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.

  A preferable blending ratio of the dispersant raw material is 10 to 200 parts by weight, preferably 20 to 200 parts by weight of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

  The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the polymer dispersant having a basic functional group is 1,000 to 200,000, preferably 2,000 to 100,000, more preferably. It is in the range of 3,000 to 50,000. If the molecular weight of the polymeric dispersant having a basic functional group is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor and the control of the reaction is difficult. Become. The polymer dispersant is produced according to a known method for producing a polyurethane resin.

  As a solvent for producing a polymer dispersant having a basic functional group, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, ethyl acetate, butyl acetate, cellosolve acetate, etc. Esters, hydrocarbons such as benzene, toluene, xylene, hexane, diacetone alcohol, isopropanol, sec-butanol, tert-butanol and some other alcohols, chlorides such as methylene chloride and chloroform, tetrahydrofuran, diethyl ether An aprotic polar solvent such as ethers such as dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide is used.

  In the above production, a urethanization reaction catalyst is usually used. Examples of urethanation reaction catalysts include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate and other tin-based iron acetylacetonates, ferric chloride and other iron-based, triethylamine, triethylenediamine and the like. Tertiary amine system etc. are mentioned.

The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg-KOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mg-KOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease.
In addition, when an isocyanate group remains in a polymer dispersing agent by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time increases.

{Mixing ratio}
In the photopolymerizable composition of the present invention, the (B) photopolymerization initiator is usually 0.1 to 50 parts by weight, preferably 1 to 45 parts by weight, based on 100 parts by weight of the (A) organic binder (C ) The photopolymerizable monomer is usually used in an amount of 0 to 200 parts by weight, preferably 3 to 180 parts by weight, based on 100 parts by weight of the organic binder (A). The compound (I) is preferably contained in an amount of 5 parts by weight or more, particularly 8 to 20 parts by weight, based on a total of 100 parts by weight of the (A) organic binder and the (C) photopolymerizable monomer.

Moreover, the compounding quantity of (D) coloring materials, such as a black pigment, is 30 to 70 weight% normally in the total solid content except (E) solvent, Preferably it is 35 to 65 weight%.
Furthermore, the compounding quantity of the above-mentioned sensitizing dye is 0-30 weight part normally with respect to 100 weight part of (A) organic binders, Preferably it is 0-10 weight part.
Further, when a polymer dispersant is used as the pigment dispersant, its use ratio is preferably 0.1 to 30% by weight, particularly preferably 0.5 to 25% by weight, based on the color material (D).

(B) If the photopolymerization initiator is less than the above range, the sensitivity may be low and the work efficiency may be poor, and if it exceeds the above range, the coating film forming function tends to be adversely affected.
(C) If the photopolymerizable monomer is less than the above, problems such as durability and heat resistance due to a decrease in crosslinking density are likely to occur, and if it exceeds the above range, developability may be deteriorated. .
(D) If the colorant is less than the above range, the colorability such as the light shielding property is deteriorated. Therefore, particularly in the case of the photopolymerizable composition for BM, the resin BM having a sufficient optical density is formed. It can be difficult. On the other hand, if the above range is exceeded, the sensitivity, resolution, developability and the like are drastically deteriorated, so that image formation tends to be difficult.

  In addition, the photopolymerizable composition of this invention is prepared so that the solid content concentration may be 5 to 50% by weight, preferably 10 to 30% by weight, using the above-mentioned solvent (E). It is desirable.

{Production method}
Next, the manufacturing method of the photopolymerizable composition of this invention is demonstrated.
When the photopolymerizable composition of the present invention contains a pigment as a coloring material, the coloring material is usually dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. preferable. Since the color material is finely divided by the dispersion treatment, the coating characteristics of the resist are improved. Moreover, when a black pigment is used as a color material, it contributes to the improvement of light-shielding capability.

  In the dispersion treatment, the treatment is preferably carried out in a system in which a black pigment and a solvent or an organic binder having a dispersion function or the above-described pigment dispersant are further used in combination. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. Dispersion treatment with a solution in which all components to be blended as a resist solution are mixed at the same time is not preferable because a highly reactive component may be denatured due to heat generated during dispersion.

  When dispersed with a sand grinder, glass beads or zirconia beads having a diameter of 0.1 to 8 mm are preferably used. The conditions for the dispersion are usually that the temperature is from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (coloring material, solvent, dispersant) and the size of the sand grinder. The standard of dispersion is to control the gloss of the ink so that the 20-degree gloss value of the resist is in the range of 100 to 200. When the resist gloss is low, the dispersion treatment is not sufficient and rough pigment particles often remain, which is insufficient in terms of developability, adhesion, resolution, and the like. Further, when the dispersion treatment is carried out until the gloss value exceeds the above range, a large number of ultrafine particles are produced, so that the dispersion stability tends to be impaired.

  Next, the ink obtained by the above dispersion treatment and the above-mentioned other components necessary as a resist component are added and mixed to obtain a uniform solution. In the manufacturing process, fine dust is often mixed with the photosensitive solution. Therefore, the obtained resist photosensitive solution is preferably filtered through a filter or the like.

[Color filter]
Next, a color filter using the photopolymerizable composition of the present invention will be described according to its production method.
The photopolymerizable composition of the present invention can be used not only for forming a black matrix in a color filter but also for forming pixels, and for forming photo spacers, ribs (liquid crystal dividing alignment protrusions) and the like in a liquid crystal display device. It can also be used.
In the following description, the case where the photopolymerizable composition of the present invention is used for forming a black matrix in a color filter will be described as an example.

  In order to produce the color filter of the present invention, first, the photopolymerizable composition of the present invention is applied on a transparent substrate and dried, then a photomask is placed on the sample, and the photomask is passed through the photomask. A light-blocking resin BM image is formed by image exposure, development, and heat curing or photocuring as necessary, and this operation is repeated for each of the three RGB colors to form a color filter image.

{Transparent substrate}
The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited. For example, polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, polycarbonate, polymethyl methacrylate, A thermoplastic plastic sheet such as polysulfone, an epoxy resin, a polyester resin, a thermosetting plastic sheet such as poly (meth) acrylic resin, or various glass plates can be used. In particular, a glass plate and a heat-resistant plastic sheet are preferably used from the viewpoint of heat resistance.

  In order to improve physical properties such as surface adhesion, such a transparent substrate can be previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agents and urethane polymers, and the like. .

{Coating and drying of photopolymerizable composition}
The method for applying the photopolymerizable composition to the transparent substrate is not particularly limited, but is usually performed using an application apparatus such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray.
In the drying after the application, a hot plate, IR oven, convection oven or the like can be used. Preferred drying conditions are 40 to 150 ° C., and the drying time is in the range of 10 seconds to 60 minutes.

  The film thickness of the resin BM after coating and drying is 0.1 to 2 μm, preferably 0.1 to 1.5 μm, and more preferably 0.1 to 1 μm. The resin BM of the color filter of the present invention preferably has an optical density of 3.0 or more at a film thickness of 1 μm from the viewpoint of light shielding properties. Moreover, it is advantageous that the 20 degree gloss value of BM is 100 to 200 as an indicator of the dispersion state of solid components such as pigments.

{Exposure and development}
Light sources used for exposure are, for example, xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and the like, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers. And the like. In the case where only the wavelength of specific irradiation light is used, an optical filter can also be used.

  The solvent used for the development treatment is not particularly limited as long as it is a solvent capable of dissolving the resist film in the unexposed area. For example, an organic solvent such as acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, since many organic solvents have environmental pollution, harmfulness to human body, fire risk, etc., it is preferable to use an alkaline developer without such danger.

Examples of such an alkali developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethanolamine, tetraalkylammonium hydroxide salt, etc. And an aqueous solution containing an organic alkali agent.
If necessary, the alkaline developer may contain a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, and the like. In particular, it is preferable to add a surfactant since many surfactants have an improving effect on developability, resolution, and background stains.

  For example, as a surfactant for a developer, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Can be mentioned.

  Although there is no restriction | limiting in particular about the image development processing method, Usually, it is carried out by methods, such as immersion image development, spray image development, brush image development, ultrasonic wave development, at 10-50 degreeC, Preferably it is 15-45 degreeC.

The photopolymerizable composition is applied, dried, exposed, and developed for BM and RGB three colors to produce a color filter. At this time, the photopolymerizable composition of the present invention can be used for BM formation and RGB pixel formation.
In addition, when forming a pixel of a color filter using the photopolymerizable composition of the present invention, since it has very high sensitivity and high resolution, exposure and development can be performed without providing an oxygen blocking layer such as polyvinyl alcohol. Thus, an image can be formed.

[Liquid Crystal Display (Panel)]
The liquid crystal display device of the present invention can be manufactured using the color filter as follows.
First, an alignment film is formed on a color filter, a spacer is disposed on the alignment film, and then a liquid crystal cell is formed by being attached to a counter substrate. Next, liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete.

  The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method or a flexographic printing method is usually employed, and the thickness of the alignment film is usually 10 to 100 nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state capable of adjusting the tilt of the liquid crystal.

  A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. To do. The degree of vacuum in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, Preferably it is 50-90 degreeC. The warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

The type of the liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like. The thermotropic liquid crystal, nematic liquid crystal, smelling click ticks liquid crystal, but such a cholesteric liquid crystal are known, may be any of these.

[Other uses]
The photopolymerizable composition of the present invention can be used to form photo spacers and ribs (liquid crystal split alignment protrusions) in addition to the resin BM and RGB three-color pixels of the color filter as described above.
Hereinafter, this usage pattern will be described.

<Photo spacer>
The photospacer is formed by applying the photopolymerizable composition of the present invention to a substrate, drying, exposing, developing, and thermosetting.
In forming the photospacer, the photopolymerizable composition of the present invention is usually supplied onto the substrate in a state dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred.
The coating amount is usually in the range of 0.5 to 10 μm, preferably 1 to 8 μm, particularly preferably 1 to 5 μm as a dry film thickness. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an inkjet method or a printing method.

  The drying after supplying the photopolymerizable composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature. Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying conditions are usually selected in the range of 15 to 5 minutes at a temperature of 40 to 100 ° C., preferably 50 to 90 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

The exposure is performed by overlaying a negative mask pattern on the coating film of the photopolymerizable composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. Further, a scanning exposure method using laser light may be used. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, excimer lasers, nitrogen laser, Heriumukado Miu Mureza, blue-violet semiconductor laser, and the like laser light source such as a near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

  After performing the exposure described above, an image pattern can be formed on the substrate by development using an aqueous solution containing an alkaline compound and a surfactant or an organic solvent. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), co The organic alkaline compound such emissions and the like. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.

  The substrate after development is preferably subjected to a thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.

<Rib (Liquid crystal alignment protrusion)>
Ribs (liquid crystal split alignment protrusions) are protrusions formed on a transparent electrode in order to improve the viewing angle of a liquid crystal display device, and the liquid crystal is locally tilted by using the slope of the protrusions within one pixel. The liquid crystal is divided in multiple directions.

  In order to form ribs with the photopolymerizable composition of the present invention, three color pixels of BM and RBG are formed, a color filter, and 150 nm thick ITO is vapor-deposited thereon, usually 0.1 to 2 mm thick transparent The photopolymerizable composition of the present invention is applied onto a substrate using an application device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray. The coating film thickness of the composition is usually 0.5 to 5 μm. After the coating film made of the composition is dried, a photomask is placed on the dried coating film, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel. Usually, an image obtained after development is required to have a fine line reproducibility of a width of 5 to 20 μm, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display. In order to stably reproduce high-definition fine lines, the cross-sectional shape of the fine line image after development is a rectangular shape with a clear contrast between the non-image and the image area, such as development time, developer aging, physical stimulation of the development shower, etc. A wide development margin is preferable.

When the photopolymerizable composition of the present invention is used, the developed image has a cross-sectional shape close to a rectangular shape. In order to obtain an arched shape necessary for the rib shape, it is usually 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, usually 400 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. or lower. And a heat treatment for 10 minutes or more, preferably 15 minutes or more, more preferably 20 minutes or more, usually 120 minutes or less, preferably 60 minutes or less, more preferably 40 minutes or less, and a rectangular cross-sectional shape. Is deformed into an arch shape to form ribs having a width of 0.5 to 20 μm and a height of 0.2 to 5 μm.
As the range of deformation during heating, the photopolymerizable composition and heating conditions are adjusted as appropriate, and the contact angle (W1) formed from the side surface of the thin line image (rectangular image cross-sectional shape) before heating and the substrate plane is the above heating. When the contact angle (W2) formed from the side surface of the thin line image after processing and the substrate plane is compared, W1 / W2 is usually 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, usually It should be 10 or less, preferably 8 or less. The higher the heating temperature or the longer the heating time, the larger the deformation rate. Conversely, the lower the heating temperature or the shorter the heating time, the lower the deformation rate.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to a following example, unless the summary is exceeded.

[Synthesis Example 1 (Synthesis of epoxy acrylate resin having carboxyl group)]
In a 500 mL four-necked flask, 245 g (epoxy equivalent 245) of bisphenolfluorene type epoxy resin represented by the following formula (a-1), 110 mg of tetramethylammonium chloride, 2,6-di-t-butyl-4-methyl 100 mg of phenol and 72.0 g of acrylic acid and 300 g of propylene glycol monomethyl ether acetate were charged, and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 mL / min.
Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. Here, although the solution gradually became transparent and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mg-KOH / g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate.
Next, after adding 300 g of propylene glycol monomethyl ether acetate to 617.0 g of the bisphenolfluorene type epoxy acrylate thus obtained, biphenyl-3,3 ′, 4,4′-tetracarboxylic acid diacid is dissolved. 73.5 g of anhydride and 1 g of tetraethylammonium bromide were mixed, gradually heated to react at 110 to 115 ° C. for 4 hours.
After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to give an acid value of 100 mg-KOH / g, molecular weight (gel per A polystyrene-reduced weight average molecular weight (MPC) measurement 4200 was obtained.

[Synthesis Example 2 (Synthesis of epoxy acrylate resin having carboxyl group)]
Synthesis Example 1 except that 261 g of a bisphenolfluorene type epoxy resin (epoxy equivalent 261) represented by the following formula (a-2) was used instead of the bisphenolfluorene type epoxy resin represented by the formula (a-1) And a resin having an acid value of 103 mg-KOH / g and a molecular weight of 4400 was obtained.

[Synthesis Example 3 (Synthesis of epoxy acrylate resin having carboxyl group)]
Instead of the bisphenolfluorene type epoxy resin represented by the formula (a-1), 261 g of a bisphenolfluorene type epoxy resin (epoxy equivalent 261) represented by the above formula (a-2) was used, and biphenyl-3,3 ′ , 4,4'-Tetracarboxylic acid dianhydride added 73.5 g when changed to 28.3 g, 1,2,3,6-tetrahydrophthalic anhydride added 38.0 g changed to 117 g A resin having an acid value of 109 mg-KOH / g and a molecular weight of 2600 was obtained in the same manner as in Synthesis Example 1 except that.

[Synthesis Example 4 (Synthesis of epoxy acrylate resin having carboxyl group)]
Synthesis Example 1 except that 235 g of a bisphenolfluorene type epoxy resin (epoxy equivalent 235) represented by the following formula (a-3) was used instead of the bisphenolfluorene type epoxy resin represented by the formula (a-1) Synthesis was performed in the same manner to obtain a resin having an acid value of 100 mg-KOH / g and a molecular weight of 3900.

[Synthesis Example 5 (Preparation of Polymer Dispersant Solution)]
32 g of tolylene diisocyanate trimer (Mitsubishi Chemical Co., Ltd., Mytec GP750A, resin solid content 50 wt%, butyl acetate solution) and 0.02 g of dibutyltin dilaurate as a catalyst were diluted with 47 g of propylene glycol monomethyl ether acetate (PGMEA) Dissolved.
While stirring, 14.4 g of polyethylene glycol (manufactured by NOF Corporation, UNIOX M-1000) having a methoxy group at one end and polypropylene glycol having a number average molecular weight of 1,000. A mixture of 9.6 g (Sanix PP-1000, manufactured by Sanyo Chemical Industries, Ltd.) was dropped, and the mixture was further reacted at 70 ° C. for 3 hours.
Next, 1 g of N, N-dimethylamino-1,3-propanediamine was added, and the mixture was further reacted at 40 ° C. for 1 hour. The amine value of the solution containing the polymer dispersant thus obtained was determined by neutralization titration to be 14 mg-KOH / g. The resin content was 40% by weight as determined by the dry-up method (at 150 ° C. for 30 minutes, the solvent was removed on a hot plate and the resin concentration was calculated from the weight change).

[Synthesis Example 6 (Synthesis of Oxime Ester Compound B-1)]
<Diketone body>

Ethylcarbazole (5 g, 25.61 mmol) and l -naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then AlCl ₃ (3. 41 g, 25.61 mmol) was added. Further, after stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of acetyl chloride (2.11 g, 26.89 mmol) was added to the reaction solution, AlCl ₃ (4.1 g, 30.73 mmol) was added, and another 1 hour 30 minutes. Stir. The reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over magnesium sulfate and then evaporated to obtain a white solid (10 g).

<Oxime body>

Diketone (1.4 g, 3.59 mmol), NH ₂ OH · HCl (0.261 g, 3.76 mmol), and sodium acetate (0.32 g, 3.9 mmol) were mixed with 15 ml of isopropanol and refluxed for 3 hours. .
The whole was evaporated, 30 ml of ethyl acetate was added, washed with 30 ml of saturated brine, dried over magnesium sulfate and evaporated to give 1.82 g of a solid. This was purified by column chromatography to obtain 1.09 g of crystals.

<Oxime ester body>

The oxime (1.09 g, 2.67 mmol) and acetyl chloride (1.04 g, 13.4 mmol) were dissolved in 20 g of dichloromethane and ice-cooled, and triethylamine (1.35 g, 13.4 mmol) was added dropwise. The reaction was performed at room temperature for 4 hours. After confirming the disappearance of the raw materials by thin layer chromatography, water was added, 30 g of dichloromethane was added, the organic layer was separated, washed with NH ₄ Cl aqueous solution twice, and 5% Na ₂ CO ₃ aqueous solution three times, and then saturated. Washed twice with brine, dried over sodium sulfate and evaporated. The residue was purified by a column of ethyl acetate / hexane = 2/1 to obtain 0.79 g of white crystals.

  NMR σ 1.50 (t, 3H), 2.30 (s, 3H), 2.50 (s, 3H), 4.45 (q, 2H), 7.45-7.7 (m, 6H), 7.95-8.1 (m, 4H), 8.18 (dd, 1H), 8.39 (d, 1H), 8.63 (d, 1H)

[Synthesis Example 7 (Synthesis of Oxime Ester Compound B-2)]
The following oxime ester compound (B-2) was synthesized in the same manner as in Synthesis Example 6.
NMR σ 1.20 (t, 3H), 1.51 (t, 3H), 2.19 (s, 3H), 2.33 (s, 3H), 3.15-3.75 (m, 2H), 4.45 (q, 2H), 7.45-7.7 (m, 6H), 7.95-8.1 (m, 4H), 8.17 (dd, 1H), 8.45 (d, 1H), 8.67 (d, 1H)

[Synthesis Example 8 (Synthesis of Oxime Ester Compound B-7)]
In the same manner as in Synthesis Example 6, the following oxime ester compound (B-7) was synthesized.
NMR σ 1.50 (t, 3H), 1.18 (d, 3H), 1.50 (t, 3H), 1.83 (s, 3H), 2.20 (s, 3H), 2.32 ( s, 3H), 3.6-3.83 (m, 2H), 4.43 (q, 2H), 4.9 (br, 1H), 7.22-7.33 (m, 4H), 7 .44-7.68 (m, 6H), 7.87-8.1 (m, 4H), 8.16 (dd, 1H), 8.23 (d, 1H), 8.60 (d, 1H) )

[Synthesis Example 9 (Synthesis of Oxime Ester Compound B-10)]
In the same manner as in Synthesis Example 6, the following oxime ester compound (B-10) was synthesized.
NMR σ1.21 (d, 3H), 1.51 (t, 3H), 1.84 (s, 3H), 2.20 (s, 3H), 2.32 (s, 3H), 3.2 3.4 (m, 2H), 4.43 (q, 2H), 4.9 (br, 1H), 7.4-7.6 (m, 4H), 7.92-8.0 (m, 3H), 8.02 (dd, 1H), 8.18 (dd, 1H), 8.60 (s, 1H), 8.83 (d, 1H)

[Synthesis Example 10 (Synthesis of Oxime Ester Compound B-3)]
The following oxime ester compound (B-3) was synthesized in the same manner as in Synthesis Example 6.
NMR σ1.48 (t, 3H), 2.27 (s, 3H), 2.48 (s, 3H), 3.23 (t, 4H), 4.03 (t, 4H), 4.42 ( q, 2H), 7.13 (d, 1H), 7.43-7.57 (m, 4H), 7.61 (d, 1H), 7.94-7.97 (dd, 1H), 8 15-8.2 (m, 2H), 8.3 (d, 1H), 8.39 (d, 1H), 8.59 (d, 1H).

[Synthesis Example 11 (Synthesis of Oxime Ester Compound B-4)]
The following oxime ester compound (B-4) was synthesized in the same manner as in Synthesis Example 6.
NMR σ 1.18 (d, 3H), 1.48 (t, 3H), 1.82 (s, 3H), 2.18 (s, 3H), 2.30 (s, 3H), 3.22 ( t, 4H), 3.29 (m, 1H), 4.03 (t, 4H), 4.41 (q, 2H), 7.12 (d, 1H), 7.43-7.56 (m , 4H), 7.61 (d, 1H), 7.93 (dd, 1H), 8.14 (dd, 1H), 8.18-8.22 (m, 1H), 8.27-8. 32 (m, 1H), 8.45 (d, 1H), 8.64 (d, 1H)

[Synthesis Example 12 (Synthesis of Oxime Ester Compound B-6)]
The following oxime ester compound (B-6) was synthesized in the same manner as in Synthesis Example 6.
NMR σ1.48 (t, 3H), 1.84 (s, 3H), 2.04 (s, 3H), 2.26 (s, 3H), 2.96 (t, 4H), 3.26 ( t, 4H), 4.6-4.8 (m, 1H), 4.41 (quartet, 2H), 7.11 (doublet, 1H), 7.17 (t, 1H), 7.25-7 .30 (m, 5H), 7.39-7.52 (m, 4H), 7.86 (dd, 1H), 8.00 (dd, 1H), 8.30 (d, 1H), 8. 56 (d, 1H).

[Synthesis Example 13 (Synthesis of Oxime Ester Compound B-5)]
The following oxime ester compound (B-5) was synthesized in the same manner as in Synthesis Example 6.
NMR σ 1.46 (t, 3H), 2.26 (s, 3H), 2.46 (s, 3H), 3.87 (s, 3H), 4.39 (q, 2H), 7.10 ( s, 1H), 7.3 (s, 1H), 7.4-7.5 (m, 3H), 7.55-7.60 (m, 1H), 7.84 (t, 1H), 7 .88 (s, 1H), 8.1-8.2 (dd, 2H), 8.61 (d, 1H), 8.65 (d, 1H).

[Type of organic binder]
In the following examples and comparative examples, the following were used as organic binders.

Ａ−５；ＡＣＡ２００Ｍ（ダイセル化学工業社製。アクリル系ポリマーのカルボン酸基に、エポキシ基を有したアクリルモノマーを付加させてなるポリマー。すなわち側鎖にアクリル基を有するアクリル系ポリマー）
Ａ−６；合成例４で合成したカルボキシル基を有するエポキシアクリレート樹脂 A-1; Epoxy acrylate resin having a carboxyl group synthesized in Synthesis Example 1 A-2; Epoxy acrylate resin having a carboxyl group synthesized in Synthesis Example 2 A-3; Epoxy acrylate having a carboxyl group synthesized in Synthesis Example 1 1: 1 (weight ratio) mixture of resin and epoxy acrylate resin having a carboxyl group synthesized in Synthesis Example 3 A-4; organic binder shown below having weight average molecular weight of 2000 and acid value of 100 mg-KOH / g

A-5; ACA200M (manufactured by Daicel Chemical Industries, Ltd., a polymer obtained by adding an acrylic monomer having an epoxy group to a carboxylic acid group of an acrylic polymer, that is, an acrylic polymer having an acrylic group in a side chain)
A-6: Epoxy acrylate resin having a carboxyl group synthesized in Synthesis Example 4

[Types of photopolymerization initiator]
In the following examples and comparative examples, the following were used as photopolymerization initiators.

  B-8: “OXE-02” manufactured by Ciba Specialty Chemicals, B-9: a compound described in JP-A No. 2006-36750.

[Examples 1 to 12 and Comparative Examples 1 and 2 (Evaluation of Black Resist)]
<Dispersion of carbon black>
Carbon black for color (manufactured by Mitsubishi Chemical Co., Ltd., MA-220) 50 parts by weight, the polymer dispersant prepared in Synthesis Example 5 as a solid content in a ratio of 5 parts by weight, and the solid content concentration becomes 50% by weight Were added with carbon black, polymer dispersant solution and PGMEA. The total weight of the dispersion was 50 g. This was thoroughly stirred with a stirrer and premixed.
Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion, the beads and the dispersion were separated by a filter.

<Preparation of resist solution>
Using the carbon black dispersion ink described above, each component was added so as to have the following blending ratio as a solid content, and stirred and dissolved with a stirrer to prepare a black resist photosensitive solution.

(Mixing ratio)
(1) Black pigment Carbon black (manufactured by Mitsubishi Chemical Corporation, MA-220) 50 g
(2) Organic binder 25g of the compounds listed in Table 1
(3) Photopolymerizable monomer: ethylenic compound dipentaerythritol hexaacrylate 14 g
(4) Photopolymerization initiator 14 g of the photopolymerization initiator described in Table 1
(5) Organic solvent 300 g of propylene glycol monomethyl ether acetate
(6) Polymer dispersant (prepared in Synthesis Example 5) 5 g
(7) Surfactant (Sumitomo 3M, FC-430) 100 ppm

<Evaluation of resist>
A black resist photosensitive solution was applied to a glass substrate (Corning Corp., 7059) with a spin coater, and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured with a stylus type film thickness meter (manufactured by Tencor, α-step) and found to be 1 μm. Next, this sample was image-exposed through a mask while changing the exposure amount with a high-pressure mercury lamp. A resist pattern was obtained by spray development using an aqueous sodium carbonate solution having a temperature of 25 ° C. and a concentration of 0.8 wt%.
Sensitivity, resolving power and light shielding properties were evaluated according to the following criteria, and the results shown in Table 1 were obtained.

1. Sensitivity A 20 μm mask pattern was displayed with an appropriate exposure amount (mj / cm ² ) that can be formed according to dimensions. That is, a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount.

2. Residue During the time when the unexposed portion is dissolved, the resist was completely developed and removed, and the unexposed portion was observed in detail and evaluated according to the following criteria.
There is no complete film. : ○
The white film is thin, but if the time is further doubled, the film cannot be seen completely. : △
A white film is seen. Even if the time is extended twice, the membrane remains. : ×

3. Alkali resistance At a light exposure that faithfully reproduces a 20 μm mask pattern, the minimum resist pattern size that can be resolved with a development time of 80 seconds was observed with a microscope at a magnification of 200 × and evaluated according to the following criteria.
Minimum pattern dimension is 10μm or less: ◎
Minimum pattern size is 10~15μ m: ○
Minimum pattern dimension exceeds 15 μm: ×

4). Light-shielding property The optical density (OD) of the image area was measured with a Macbeth reflection densitometer (TR927, manufactured by Kolmorgun). The OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding property.

[Examples 13 and 14, Reference Examples 1 and 2, and Comparative Examples 3 to 6 (clear resist evaluation)]
Each component was added so that it might become the following mixture ratio as solid content, it stirred and melt | dissolved with the stirrer, and the clear resist photosensitive solution was prepared.

(Mixing ratio)
Organic binder (A-4) 46.6 parts by weight Photopolymerizable monomer (dipentaerythritol hexaacrylate) 6.5 parts by weight Crystal violet 0.1 part by weight Fluorosurfactant (Dainippon Ink Co., Ltd.) 0.0015 parts by weight Photopolymerization initiator (described in Table 2)
300 parts by weight of organic solvent (propylene glycol monomethyl ether acetate)

The clear resist sensitizing solution was applied to a glass substrate (Corning Corp., 7059) with a spin coater and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured with a stylus type film thickness meter (manufactured by Tencor, α-step) and found to be 1 μm. A resist pattern was obtained by spray development using a sodium carbonate aqueous solution having a temperature of 25 ° C. and a concentration of 0.8%.
Next, this sample was image-exposed through a mask with a high-pressure mercury lamp using a step tablet at an exposure amount of 200 mJ / cm ² . For the step tablet, the transmittance at the 0th step was 100%, and the transmittance decreased by 50% for every second step, and the sensitivity was expressed by the number of steps at which an image was formed.

Claims (19)

A photopolymerization initiator composed of an oxime ester compound represented by the following general formula (I).

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl group having 4 to 25 carbon atoms. These may all have a substituent. Alternatively, R ¹ may be bonded to X or Y to form a ring.
R ² is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.
X represents a divalent aromatic hydrocarbon group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Y represents a condensed ring group formed by condensing one or more rings to a monovalent group derived from a phenyl group or an aromatic heterocyclic monocycle, and the condensed ring group may have a substituent. ]   2. The general formula (I) according to claim 1, wherein Y is a condensed ring group obtained by condensing one or more rings to a phenyl group, and the condensed ring group may have a substituent. Photopolymerization initiator.   In the general formula (I), Y is 1 to 3 5- or 6-membered rings in at least one position selected from the 2,3-position, 3,4-position, and 4,5-position of the phenyl group. The photopolymerization initiator according to claim 2, which is a group derived from a condensed ring having 2 to 4 condensed rings, and the group may have a substituent.   The photopolymerization initiator according to claim 2 or 3, wherein in the general formula (I), the ring condensed with the phenyl group in Y is a hydrocarbon ring.   The photopolymerization initiator according to claim 2 or 3, wherein, in the general formula (I), the ring condensed with the phenyl group in Y is an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring.   In the general formula (I), Y is a condensed ring group formed by condensing one or more rings to a monovalent group derived from an aromatic heterocyclic ring, and the group may have a substituent. The photopolymerization initiator according to claim 1.   The photopolymerization initiator according to any one of claims 1 to 6, wherein in the general formula (I), Y is a 2-4 condensed ring group which may have a substituent. The photopolymerization initiator according to any one of claims 1 to 7, wherein the compound represented by the general formula (I) is a compound represented by the following structural formula (i).

[Wherein, R ¹ , R ² and Y have the same meaning as in the general formula (I). Ring X ² represents a ring condensed with benzene ring X ¹ , and may be a single ring or a condensed ring composed of two or more rings. Ring X ² may be condensed at any position of benzene ring X ¹ . The benzene ring X ¹ and the ring X ² condensed thereto may further have a substituent. ] Wherein In the general formula (i), the ring X ² is a heterocyclic, a photopolymerization initiator according to claim 8. Wherein in formula (i), fused ring group consisting of a benzene ring X ¹ and ring X ² is a divalent group derived from 2 or 3 fused rings, the photopolymerization initiator according to claim 8 or 9.   The photopolymerizable composition containing (A) an organic binder, (B) a photopolymerization initiator, and (C) a photopolymerizable monomer, wherein (B) the photopolymerization initiator is according to claims 1 to 10. The photopolymerizable composition containing the photoinitiator of any one.   The content of the oxime ester compound represented by the general formula (I) is 5 parts by weight or more with respect to 100 parts by weight of the total amount of (A) the organic binder and (C) the photopolymerizable monomer. The photopolymerizable composition according to claim 11.   The photopolymerizable composition according to claim 11 or 12, wherein the organic binder (A) is an epoxy acrylate resin having a carboxyl group. The epoxy acrylate resin having a carboxyl group is a novolak type epoxy resin or an epoxy resin (a) represented by the following general formula (X) and an α, β-unsaturated monocarboxylic acid and / or ester moiety The epoxy acrylate resin obtained by reacting a polybasic acid anhydride (c) with a reaction product with an α, β-unsaturated monocarboxylic acid ester (b) having a carboxyl group. Photopolymerizable composition.

[Wherein, p and q each independently represent an integer of 0 to 4, and R ¹¹ and R ¹² each independently represent an alkyl group or a halogen group. R ¹³ and R ¹⁴ each independently represents an alkylene group. m and n each independently represents an integer of 0 or more. ]   Furthermore, (D) The photopolymerizable composition of any one of Claim 11 thru | or 14 containing a coloring material.   The photopolymerizable composition according to any one of claims 11 to 15, further comprising (E) a solvent.   A color filter having an image formed by the photopolymerizable composition according to claim 11.   A liquid crystal display device formed using the color filter according to claim 17. An oxime ester compound having the structure of the following general formula (II).

[Wherein, R ¹ represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (IIa).

(Wherein R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group.)
R ² represents an alkanoyl group having 2 to 4 carbon atoms, and X represents a divalent carbazolyl group in which a nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Y ^a represents a naphthyl group which may be substituted with a morpholino group. ]