JP5354863B2 - Oxime derivative, photopolymerizable composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new oxime derivative useful as a photopolymerization initiator, etc., a photopolymerizable composition exhibiting high sensitivity and having reduced precipitation of solid substance after coating and a colored filter using the same and to provide a method for producing a color filter. <P>SOLUTION: The specific oxime compound is represented by general formula (1). The photopolymerizable composition comprises a photopolymerization initiator using the compound and a radically polymerizable monomer. The color filter is obtained by using the photopolymerizable composition. The method for producing a color filter is provided. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention is characterized by containing a novel oxime derivative and a photoinitiator having a specific structure, and is suitable for UV ink, UV inkjet, color filters used in liquid crystal display elements and solid-state image sensors, black matrices, and the like. The present invention relates to a photopolymerizable composition, a color filter and a method for producing the same.

Oxime derivatives are widely used as pharmaceuticals, agricultural chemicals, antibacterial agents, synthetic intermediates, and photosensitive compounds. Examples of the photosensitive compound include a photopolymerization initiator, a photoacid generator, and a photobase generator.
The photopolymerization technique is used as a technique for producing an adhesive, a printing plate, a semiconductor, a liquid crystal, a color filter for a solid-state image sensor, and the like.
As photopolymerization initiators, which are constituent components, various oxime derivatives are disclosed in Patent Documents 1 to 10.

  However, in the photopolymerization technique, there is a demand for a photopolymerization initiator having higher sensitivity, higher thermal stability and storage stability, and reduced precipitation after being applied to a substrate.

The photopolymerization technique is a useful technique applied to various uses. Examples of the composition using the photopolymerization technique include the following.
Pigmented or non-pigmented paints or varnishes, powder coatings, printing inks, inkjet inks, UV inks, printing plates, adhesives, dental compositions, gel coats, electronic photoresists such as electroplating resists, etching resists, Composition in the manufacturing process of both liquid and dry thin film, composition for producing solder resist, composition for producing color filter for various display device applications, plasma display panel, electroluminescent display device, and LCD Composition, composite composition, including photoresist, resist, color filter material, black matrix, composition for encapsulating electrical and electronic components, magnetic recording material, micromechanical component, waveguide, optical switch , Plating mask, etching mask, color test system, glass fiber Composition for producing stencil for screen coating, screen printing stencil, composition for producing three-dimensional object by stereolithography, image recording material, especially image recording material for holographic recording, fine electronic circuit, microcapsule A composition as a decoloring material for an image recording material using the composition, and a composition for forming a dielectric layer in sequential lamination of a printed circuit board.
Patent Documents 4, 5, and 8 to 10 disclose photopolymerizable compositions using a specific oxime compound as a photopolymerization initiator.
In addition, a color filter used for a liquid crystal display element (LCD) or a solid-state liquid crystal display element (CCD, CMOS, etc.) among the above applications will be described.
As a method for producing a color filter used for a liquid crystal display element (LCD) or a solid-state imaging element (CCD, CMOS, etc.), a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate with a spin coater or a roll coater and dried to form a coating film, and then this coating film is subjected to pattern exposure and development. A colored filter is formed, and a color filter is obtained by repeating this operation for each color according to the desired number of hues. As such a pigment dispersion method, there is one in which an example using a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is described (for example, Patent Documents 11 to 15). reference).
On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices, and there is also a technology that uses organic solvent-soluble dyes (hereinafter sometimes simply referred to as “dyes”) instead of pigments. Proposed. (For example, refer to Patent Document 16).
U.S. Pat. No. 3,558,309 U.S. Pat. No. 4,255,513 JP 61-24558 A JP 2000-80068 A JP 2001-233842 A JP 2002-519732 A JP 2002-323762 A JP-T-2004-534797 International Publication No. 04/050653 Pamphlet International Publication No. 05/080337 Pamphlet JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 JP 2005-99488 A

However, in the composition using such photopolymerization, in order to improve manufacturability, further improvement in sensitivity and reduction in solid precipitation after the composition is required are required.
In particular, when used for color filters and black matrix formation for liquid crystal display elements (LCD) and solid-state liquid crystal display elements (CCD, CMOS, etc.), both the method using pigments and the method using dyes can increase the There is a great demand for sensitivity. This is because the negative curable composition containing a colorant is less sensitive than other negative curable compositions, because the light absorption of the colorant is large, and the light absorption of the photosensitive component. It is assumed that this is because the efficiency is low from the beginning. There is also a need for improved developer resistance after photopolymerization of the composition.
This invention is made | formed in view of the above, and makes it a subject to achieve the following objective.
That is, an object of the present invention is to provide a novel oxime derivative that is usefully used for a photopolymerization initiator and the like.
Another object of the present invention is to provide a photopolymerizable composition exhibiting high sensitivity and further reduced precipitation of solids after the composition is formed.
In particular, when used for forming color filters and black matrices used in liquid crystal display elements (LCD) and solid-state liquid crystal display elements (CCD, CMOS, etc.), in addition to the above effects, development after photopolymerization of the composition An object is to provide a composition having improved liquid resistance.
Another object of the present invention is to provide a color filter that is excellent in hue and resolving power and has a good pattern using a photopolymerizable composition.
Furthermore, an object of the present invention is to provide a method for producing a color filter using the photopolymerizable composition, which can produce the color filter with high productivity (high cost performance).

In view of the above circumstances, the present inventors have conducted extensive research and found that the above-mentioned problems can be solved by using a specific photopolymerization initiator and the present invention, thereby completing the present invention.
That is, the present invention is achieved by the following means.

<1> A compound represented by the formula (I).

[In formula (I) , R ^la represents —CH ₂ CH ₂ SC ₆ H ₄ Cl . R ^2a represents an alkanoyl or aryloyl group. n is indicates an integer of 1-2, when n is 1, R ^{1 'represents} the structure: P1, when n is 2 and R ^1' is to display the following structure P2. ]

According to the present invention, the photopolymerization initiator other usefully employed in, Ru can provide novel oxime derivatives.

Hereinafter, the oxime derivative, the photopolymerizable composition, the color filter and the production method thereof of the present invention will be described in detail. The oxime derivative of the present invention has the following structure.
In the present invention, in formula (I), R ^la represents —CH ₂ CH ₂ SC ₆ H ₄ Cl described later . R ^2a represents an alkanoyl group or an aryloyl group described later. n represents an integer of 1 to 2, and when n is 1, R ^{1 ′} represents the structure P1, and when n is 2, R ^{1 ′} represents the structure P2.

In formula (I), R ^{1 ′} is an aromatic ring or a heteroaromatic ring, or an ether group, amino group, thioether group, carbonyl group, ester group, amide group, urethane group, urea group, sulfinyl group, sulfonyl group , A sulfonic acid ester group, a sulfonamide group, an imide group, a sulfonylamide group, a disulfonylimide group, and a fragrance bonded to a carbon atom of an oxime group via one partial structure selected from the following phosphine oxide groups Represents a ring or a heteroaromatic ring .
The aromatic ring in the present invention may be a single ring or a condensed ring structure. Specific examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring. Among them, a benzene ring, a naphthalene ring, and an anthracene ring are preferable, and a benzene ring and a naphthalene ring are particularly preferable.
The heteroaromatic ring in the present invention may be a single ring or a condensed ring structure. Specific examples include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, an oxazole ring, an imidazole ring, an indole ring, and an acridine ring, among which a pyrrole ring, a thiophene ring, an indole ring, and an acridine ring are preferable, and a pyrrole ring Thiophene ring and acridine ring are more preferable, and thiophene ring, indole ring and acridine ring are particularly preferable.
These aromatic rings or heteroaromatic rings may further have a group described as a “substituent” described later. Among these substituents, a halogen atom , an alkoxy group, a hydroxyl group, an alkyl group, an alkanoyl group, an aryloyl group, a heterocyclic ring, and a heterocyclic carbonyl group are preferable, and a halogen atom , an alkoxy group, a hydroxyl group, an alkanoyl group, and an aryloyl group are more preferable. An alkoxy group, a hydroxyl group, an alkanoyl group, and an aryloyl group are particularly preferable. These substituents may be bonded to a carbon atom on the aromatic ring or heteroaromatic ring to form a condensed ring structure.

As the “substituent containing an aromatic ring or heteroaromatic ring” for R ^{1 ′} , the above-mentioned aromatic ring and / or heteroaromatic ring itself, or the above-mentioned aromatic ring and / or heteroaromatic ring, It is an arbitrary combination with one partial structure selected from the group (B) in the term “group”.
The aromatic ring or heteroaromatic ring is as described above.
The “substituent containing an aromatic ring or heteroaromatic ring” as R ^{1 ′} is ^{one selected} from the aforementioned aromatic ring and / or heteroaromatic ring and the group (B) in the “Substituent” section described later In this case, the partial structure selected from the group (B) is preferably a carbonyl group, a sulfinyl group, a sulfonyl group, or a phosphine oxide group, more preferably a carbonyl group, a sulfonyl group. Group, a phosphine oxide group, more preferably a carbonyl group and a phosphine oxide group.

R ^{1 ′} is an n-valent group, and substitutes n groups containing an oxime derivative from an arbitrary position in the structure of R ^{1 ′} . Although n is 1-6, 1-5 are preferable and 1-3 are still more preferable.
For example, when n = 1, R ^{1 ′} is preferably a phenyl group which may have a substituent or a benzoyl group which may have a substituent, and further an unsubstituted phenyl group or benzoyl group Or a phenyl group or a benzoyl group substituted with an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group.
In the case of n = 2 or more, a structure in which the structure given in the case of n = 1 becomes divalent at an arbitrary position can be mentioned.

R ^la has at least one substituent selected from the group (A) below, Ri alkyl group der, in particular, in the present ^{invention, R la} is an alkyl group having a -SAr, Ar is An aromatic ring which may have a substituent is represented .

(A) group cyano group, alkenyl group, alkynyl group, -NArAr ', -SAr, -COOH, -CONRaRb, -NRa-CO-Rb, -O-CO-NRaRb, -NRa-CO-ORb, -NRa- _{CO-NRaRb, -SO-Rc,} -SO 2 -Rc, -O-SO 2 -Rc, -SO 2 -NRaRb, -NRa-SO 2 -Ra, -CO-NRa-CORb, -CO-NRa-SO _{2 -Rb, -SO 2 -NRa-CO} -Rb, -SO 2 -NRa-SO 2 -Rc, -Si (Ra) l (ORb) m, and heterocyclic groups.

  Here, Ar and Ar ′ independently represent an aromatic ring or a heteroaromatic ring which may have a substituent, and Ra and Rb independently represent a hydrogen atom or a substituent, an alkyl group, an aromatic Rc represents a ring or a heteroaromatic ring, Rc represents an alkyl group, an aromatic ring or a heteroaromatic ring which may have a substituent, l and m each represent an integer of 0 to 3, and l + m = 3 Fulfill.

The aromatic ring or heteroaromatic ring of Ar, Ar ′, Ra, Rb and Rc is independently the same as that of R ^{1 ′} , and preferred examples are also the same.
Moreover, as the substituent which the aromatic ring or heteroaromatic ring of Ar, Ar ′, Ra, Rb, and Rc has, independently, a halogen atom , an alkoxy group, a hydroxyl group, an alkyl group, an alkanoyl group, an aryloyl group, a heterocyclic group A heterocyclic carbonyl group, a halogen atom , an alkoxy group, a hydroxyl group, an alkanoyl group, an aryloyl group, a heterocyclic group, and a heterocyclic carbonyl group are preferable, and a halogen atom , an alkoxy group, an alkanoyl group, an aryloyl group, a heterocyclic group, A heterocyclic carbonyl group is more preferable, and a halogen atom , an alkoxy group, an alkanoyl group, an aryloyl group, and a heterocyclic carbonyl group are particularly preferable.

  The alkyl groups represented by Ra, Rb, and Rc each independently represent an alkyl group of the present invention described later.

The alkyl group in the present invention may be linear, branched or cyclic, and in the case of cyclic, it may be monocyclic or polycyclic, and these may partially contain unsaturation. .
Among these, as a linear alkyl group, C1-C30 is preferable, C1-C20 is more preferable, C1-C15 is still more preferable, C1-C12 is especially preferable. The branched alkyl group is described as a straight chain having a substituent.
Moreover, as a cyclic alkyl group, C3-C20 is preferable, C4-C17 is more preferable, C5-C15 is still more preferable, C6-C12 is especially preferable.

  Specific examples of the alkyl group in the present invention include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and a 2-ethylhexyl group. And a methyl group, an ethyl group, and an n-propyl group are preferable.

Moreover, you may have a substituent further in the arbitrary positions of these alkyl groups. Further substituents include all the groups described as “substituents” described later, including the alkyl group itself. Among these substituents, a halogen atom , an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, a hydroxyl group, and an aromatic ring group are preferable, and a halogen atom , an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, and an aromatic ring group are preferable. Are more preferable, and a halogen atom , an alkoxy group, an alkoxycarbonyl group, an aryl group, and an aryloxy group are particularly preferable.

  In the case of a cyclic alkyl group, a partial structure selected from the group (B) described later may be inserted at an arbitrary position of the carbon-carbon bond constituting the ring.

The alkenyl group in the present invention may be linear, branched or cyclic. Moreover, you may have a substituent in the arbitrary positions of these alkenyl groups. Further substituents include all groups described as “substituents” described below.
In the case of a cyclic alkenyl group, a partial structure selected from the group (B) described later may be inserted at an arbitrary position of the carbon-carbon bond constituting the ring.
Specific examples of the alkenyl group include vinyl group, allyl group, 1-methylvinyl group, 3-buten-1-yl group, cyclopentan-2-en-1-yl group, and cyclohexane-2-en-1-yl. Group, cyclohexane-1-en-1-yl group, etc., among which vinyl group, allyl group, 1-methylvinyl group, 3-buten-1-yl group, cyclopentan-2-en-1-yl group , A cyclohexane-2-en-1-yl group is preferable, a vinyl group, an allyl group, a 1-methylvinyl group, and a 3-buten-1-yl group are more preferable, and a vinyl group, an allyl group, and a 1-methylvinyl group are preferable. Particularly preferred.

  The alkynyl group in the present invention is an ethynyl group, but may have a substituent instead of the hydrogen atom of the ethynyl group. Substituents include all the groups described as “substituents” described later. Among them, ethynyl group, 2-methylethynyl group, 2-ethylethynyl group, 2-phenylethynyl group are preferable, and ethynyl group, 2-methyl An ethynyl group and a 2-ethylethynyl group are more preferable, and an ethynyl group and a 2-methylethynyl group are particularly preferable.

The heterocycle in the present invention has a heteroatom (for example, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be a saturated ring, an unsaturated ring, or a monocyclic ring. Or a condensed ring. However, it is distinguished from a heteroaromatic ring (= heteroaryl).
Heterocycles include tetrahydrofuranyl, dihydrofuranyl, dihydrofuranyl, tetrahydropyranyl, dihydropyranyl, oxocanyl, dioxanyl, tetrahydrothiophenyl, dithianyl, pyrrolidinyl, pyrrolinyl, tetrahydro A pyridinyl group, a piperazinyl group, a homopiperazinyl group, a piperidinyl group, etc. can be mentioned. Moreover, you may have a substituent further in the arbitrary positions of these heterocyclic groups. Further substituents include all groups described as “substituents” described below.

<Substituent>
As the “substituent” in the present invention, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, cyano group, nitro group, carboxylic acid group, sulfonic acid group, sulfinic acid group, alkyl group ( Linear, branched, and cyclic), alkenyl groups (including linear, branched, and cyclic), alkynyl groups, aromatic rings, heteroaromatic rings, heterocyclic rings, and formyl groups, or the following (B) An arbitrary combination of one partial structure selected from the group and one partial structure selected from an alkyl group, an alkenyl group, an alkynyl group, a hetero ring, an aromatic ring, and a hetero aromatic ring.
Group (B): ether group, amino group, thioether group, carbonyl group, ester group, amide group, urethane group [—O—CO—N (R) —], urea group [—N (R) —CO—N (R) -], a sulfinyl group [-SO-], a sulfonyl group [-SO ₂ -], a sulfonic acid ester group _[-SO 2 -O-], a sulfonamide group _[-SO 2 -N (R) -] , Imide group [—CO—N (R) —CO—], sulfonylamide group [—SO ₂ —N (R) —CO—], disulfonylimide group [—SO ₂ —N (R) —SO ₂ — A phosphine oxide group having the following structure:

  N represented by the formula (I) represents an integer of 1 to 6, preferably 1 to 4, and more preferably 1 to 2.

“Aryl” has the same meaning as the “aromatic ring” described above. “Heteroaryl” has the same meaning as the above-mentioned “heteroaromatic ring”.
Rd is preferably an alkyl group, an aryl group, or a heteroaryl group, and more preferably an alkyl group or an aryl group.

As R ^1a represented by the formula (I), a cyano group, an alkenyl group, —SAr, —COOH, —CONRaRb, —NRa—CO—Rb, —NRa—CO—NRaRb, —SO ₂ —Rc, —SO _{2 -NRaRb, -NRa-SO 2 -Ra} , -CO-NRa-SO 2 -Rb, -SO 2 -NRa-CO-Rb, -Si (Ra) l (ORb) m, is selected from heterocyclic groups It is preferably an alkyl group having at least one substituent, and is a cyano group, an alkenyl group, —SAr, —COOH, —CONRaRb, —NRa—CO—Rb, —SO ₂ —Rc, —SO ₂ —NRaRb, — _{NRa-SO 2 -Ra, -CO-} NRa-SO 2 -Rb, -SO 2 -NRa-CO-Rb, Al having at least one substituent selected from the heterocyclic group More preferably Le group.
R1a is more preferably an alkenyl group or an alkyl group substituted with at least one -SAr. Most preferably the R ^1a, R ^1a -SAr is at least one substituted alkyl group.
When R ^1a is an alkyl group substituted with at least one —SAr, it is preferable to have at least one substituent other than a hydrogen atom on the Ar.

R ^2a represented by the formula (I) is an alkanoyl group, alkenoyl group, aryloyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, heteroaryloxycarbonyl group, alkylthiocarbonyl group, arylthiocarbonyl group , A heterocyclic thiocarbonyl group, a heteroarylthiocarbonyl group, —CO—CO—Rd (Rd represents an alkyl group, an aromatic ring or a heteroaromatic ring which may have a substituent).

R ^2a is preferably an alkanoyl group, an aryloyl group, an alkylthiocarbonyl group, an arylthiocarbonyl group or a heteroarylthiocarbonyl group, more preferably an alkanoyl group or an aryloyl group.

The alkanoyl group represented by R ^2a may be unsubstituted or substituted, preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and particularly preferably has 1 to 12 carbon atoms. . Examples of the substituent include the include the "substituent" include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, preferably a halogen atom, an alkoxy group, an amino group is more preferable.
As specific examples, an acetyl group, an ethylcarbonyl group, and a dimethylaminomethylcarbonyl group are preferable.

The aryloyl group represented by R ^2a may be further unsubstituted or substituted, preferably has 6 to 25 carbon atoms, more preferably has 6 to 17 carbon atoms, and particularly preferably has 6 to 12 carbon atoms. . Examples of the substituent include the "substituent" and the like, a halogen atom, an alkoxy group, an aryloxy group, preferably an alkoxycarbonyl group, a halogen atom, an alkoxy group, an aryloxy group is more preferable.
As specific examples, a benzoyl group and a 4-chlorobenzoyl group are preferable, and a benzoyl group is more preferable.

The alkoxycarbonyl group represented by R ^2a may be unsubstituted or substituted, preferably has 2 to 20 carbon atoms, more preferably has 2 to 15 carbon atoms, and particularly has 2 to 12 carbon atoms. preferable. Examples of the substituent include the above-mentioned “substituent”, and a halogen atom and an alkoxy group are preferable, and a halogen atom is more preferable.
As specific examples, a methoxycarbonyl group and an ethoxycarbonyl group are preferable, and a methoxycarbonyl group is more preferable.

The aryloxycarbonyl group represented by R ^2a may be unsubstituted or substituted, preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and has 6 to 12 carbon atoms. Particularly preferred. Examples of the substituent include the above-mentioned “substituent”, and a halogen atom , an alkoxy group and an aryloxy group are preferable, and a halogen atom and an alkoxy group are more preferable.
As specific examples, a phenyloxycarbonyl group and a naphthaleneoxycarbonyl group are preferable, and a phenyloxycarbonyl group is more preferable.

The heterocyclic oxycarbonyl group represented by R ^2a may be further unsubstituted or substituted, preferably has 5 to 20 carbon atoms, more preferably has 5 to 15 carbon atoms, and has 5 to 12 carbon atoms. Is particularly preferred. Examples of the substituent include the above-mentioned “substituent”, and a halogen atom , an alkoxy group and an alkyl group are preferable, and a halogen atom and an alkoxy group are more preferable.
As specific examples, a tetrahydrofurfuryloxycarbonyl group and a 2-morpholinooxycarbonyl group are preferable, and a tetrahydrofurfuryloxycarbonyl group is more preferable.

The heteroaryloxycarbonyl group represented by R ^2a may be further substituted or unsubstituted, preferably has 5 to 20 carbon atoms, more preferably has 5 to 15 carbon atoms, and has 5 to 12 carbon atoms. Is particularly preferred. Examples of the substituent include the above-mentioned “substituent”, and a halogen atom , an alkyl group and an alkoxy group are preferable, and a halogen atom and an alkoxy group are more preferable.
As specific examples, 4-pyridineoxycarbonyl group and 2-thiophenoxycarbonyl group are preferable, and 2-thiophenoxycarbonyl group is more preferable.

The alkylthiocarbonyl group represented by R ^2a may be unsubstituted or substituted, preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and has 1 to 12 carbon atoms. Particularly preferred. Examples of the substituent include the above-mentioned “substituent”, and a halogen atom , an alkoxy group, a hydroxyl group and an alkyl group are preferable, and a halogen atom , an alkoxy group and an alkyl group are more preferable.
As specific examples, a methylthiocarbonyl group, an ethylthiocarbonyl group, and a propylthiocarbonyl group are preferable, and a methylthiocarbonyl group and an ethylthiocarbonyl group are more preferable.

The arylthiocarbonyl group represented by R ^2a may be further unsubstituted or substituted, preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and has 6 to 12 carbon atoms. Particularly preferred. Examples of the substituent include the include the "substituent" include a halogen atom, an alkoxy group, a hydroxyl group, an alkyl group Gaha androgenic atom, an alkoxy group, an alkyl group more preferred.
As specific examples, a phenylthiocarbonyl group and a 4-methylphenylthiocarbonyl group are preferable, and a phenylthiocarbonyl group is more preferable.

The heterocyclic thiocarbonyl group represented by R ^2a may be further unsubstituted or substituted, preferably has 5 to 20 carbon atoms, more preferably has 5 to 15 carbon atoms, and has 5 to 12 carbon atoms. Is particularly preferred. Examples of the substituent include the above-mentioned “substituent”, and a halogen atom , an alkoxy group, a hydroxyl group and an alkyl group are preferable, and a halogen atom , an alkoxy group and an alkyl group are more preferable.
As specific examples, a tetrahydrofuran 2-thiocarbonyl group and a 2-morpholinothiocarbonyl group are preferable, and a tetrahydrofuran 2-thiocarbonyl group is more preferable.

The heteroarylthiocarbonyl group represented by R ^2a may be further substituted or unsubstituted, preferably has 5 to 20 carbon atoms, more preferably has 5 to 15 carbon atoms, and has 5 to 12 carbon atoms. Is particularly preferred. Examples of the substituent include the above-mentioned “substituent”, and a halogen atom , an alkoxy group, a hydroxyl group and an alkyl group are preferable, and a halogen atom , an alkoxy group and an alkyl group are more preferable.
As specific examples, a thiophen-2-thiocarbonyl group and a furan-2-thiocarbonyl group are preferable, and a thiophen-2-thiocarbonyl group is more preferable.

As -CO-CO-Rd represented by R ^2a , Rd represents an alkyl group, an aromatic ring or a heteroaromatic ring which may have a substituent.
The alkyl group represented by Rd is the same as the alkyl group in the present invention, and preferred examples are also the same.
The aromatic ring and heteroaromatic ring represented by Rd are each independently the same as the aromatic ring and heteroaromatic ring in R ^{1 ′} , and preferred examples are also the same.

  (B) R substituted on the nitrogen atom in the group is any one of a hydrogen atom, an alkyl group, an alkenyl group, an aromatic ring group, a heteroaromatic ring group, and a heterocyclic group. Among these, a hydrogen atom, an alkyl group, an alkenyl group, an aromatic ring group, a heteroaromatic ring group, and a heterocyclic group are preferable, and a hydrogen atom, an alkyl group, an alkenyl group, an aromatic ring group, a heteroaromatic ring group, and a heterocyclic group are more preferable. .

  The alkyl group represented by R is an alkyl group of the present invention, and among them, a methyl group, an ethyl group, and an n-propyl group are preferable, and a methyl group and an ethyl group are more preferable.

  The alkenyl group represented by R is an alkenyl group of the present invention, and among them, a vinyl group, an allyl group, and a 2-ethylvinyl group are preferable, and a vinyl group and an allyl group are more preferable.

  The aromatic ring group represented by R is the aromatic ring group of the present invention, and among them, a phenyl group, a tolyl group, a naphthyl group, and an anthryl group are preferable, and a phenyl group, a tolyl group, and a naphthyl group are more preferable.

  The heteroaromatic ring group represented by R is a heteroaromatic ring group of the present invention, among which a furyl group, a thienyl group, a pyrrolyl group, and an indolyl group are preferable, and a thienyl group, a pyrrolyl group, and an indolyl group are more preferable. .

  The heterocyclic group represented by R is a heterocyclic group of the present invention, and among them, a tetrahydrofuryl group and a morpholyl group are preferable, and a morpholyl group is more preferable.

  The oxime derivative of the present invention has the following isomers (A) and (B) due to the compound structure, and may exist as a mixture of isomers.

  Specific examples of the oxime derivative represented by the formula (I) are shown below. However, as described above, the oxime derivative may exist as a mixture of isomers, and the present invention is not limited thereto.

  When the oxime derivative of the present invention is used as a photopolymerization initiator, the photopolymerization characteristics such as sensitivity and curing speed can be further improved and promoted by combining with various sensitizers. Examples of such a sensitizer include compounds described in JP-A-2000-80068 [0112] to [0118].

  The oxime derivative of the present invention is useful as a photopolymerization initiator when producing pharmaceuticals, agricultural chemicals, antibacterial agents, synthetic intermediates, adhesives, printing plates, semiconductors, liquid crystals, color filters for solid-state imaging devices, and the like. In particular, it is useful as a component of a photocurable composition when producing a color filter.

  The oxime derivative described in the present invention is not particularly limited and can be synthesized by a known synthesis method.

<Synthesis method of oxime derivative>
Next, a scheme of a method for synthesizing the oxime derivative is shown below. The method for synthesizing the oxime derivative is not limited to this.

a) hydroxylamine or a halogen embodying or anhydrides ^{R 2a} of a base ^{/ R 2a} such bases / nitrites c) NaOH, such as a salt thereof b) NaOMe, or halogen embodying the amine ^{/ R 2a} such as pyridine or R ^2a Anhydride Here, X and Y are the same groups as R ^{1a in} formula (1) or a precursor thereof, and R ^2a has the same meaning as that in formula (1).

  As conditions suitable for this synthesis method, the conditions described in JP-A-2000-80068 [0067] can be employed.

<< Photopolymerizable composition >>
The photopolymerizable composition of the present invention (hereinafter sometimes referred to as "composition of the present invention") includes a photopolymerization initiator represented by (A) pre above formula (I), (B) a radical polymerizable And a monomer as an essential component.
Moreover, it can comprise using (E) other components, such as a crosslinking agent, a photosensitizer, a sensitizer, and surfactant, as needed.

(A) the formula composition of the photopolymerization initiator present invention represented by the general formula (I), before following formula photopolymerization initiator (I) (hereinafter is sometimes referred, also referred to as "oxime derivative".) Containing To do.
The photopolymerization initiator represented by the formula (I) is as described above.
Specific examples of the oxime derivative represented by the formula (I) are shown below. However, as described above, the oxime derivative may exist as a mixture of isomers, and the present invention is not limited thereto.

  The oxime derivative described in the present invention has high sensitivity to photopolymerization when used as a photopolymerizable composition, and solid precipitation when the photopolymerizable composition is formed or when the composition is applied to a substrate. Is reduced.

  The oxime derivative described in the present invention is not particularly limited and can be synthesized by a known synthesis method.

<Synthesis method of oxime derivative>
Next, a scheme of a method for synthesizing the oxime derivative is shown below. The method for synthesizing the oxime derivative is not limited to this.

a) hydroxylamine or a halogen embodying or anhydrides ^{R 2a} of a base ^{/ R 2a} such bases / nitrites c) NaOH, such as a salt thereof b) NaOMe, or halogen embodying the amine ^{/ R 2a} such as pyridine or R ^2a Anhydride Here, X and Y are the same groups as R ^{1a in} formula (1) or a precursor thereof, and R ^2a has the same meaning as that in formula (1).

  As conditions suitable for this synthesis method, the conditions described in JP-A-2000-80068 [0067] can be employed.

  The oxime derivative as a photopolymerization initiator in the present invention can further promote photopolymerization characteristics such as sensitivity and curing rate by combining with various sensitizers. Examples of such a sensitizer include compounds described in JP-A 2000-80068, [0112] to [0118].

As content of the photoinitiator represented by Formula (I) in this invention, Preferably it is 0.5-35 mass% as solid concentration of the composition of this invention, More preferably, it is 1-25 mass %, More preferably 2 to 20% by mass.
When the concentration of the polymerization initiator represented by the formula (I) is less than 0.5% by mass, photopolymerization characteristics such as sensitivity and curing speed may be too low, and when the concentration exceeds 35% by mass. In some cases, light does not transmit to the deep part and the sensitivity is lowered, and the strength of the photopolymerized portion and the developer resistance may be lowered.
In the present invention, two or more photopolymerization initiators represented by the formula (I) may be used.

The composition of the present invention may be mixed with a known photopolymerization initiator other than the compound of the formula (I).
The known photopolymerization initiator is not particularly limited as long as it can polymerize the (B) radical polymerizable monomer described later, but is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. Preferably.

  Examples of the photopolymerization initiator that can be used as the known photopolymerization initiator include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds; 3-aryl-substituted coumarin compounds And lophine dimers; benzophenone compounds; acetophenone compounds and derivatives thereof; cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds other than formula (I), acylphosphine (oxide) compounds, and the like.

  Examples of the active halogen compound which is a halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) -1,3,4-oxadiazole.

  Examples of the active halogen compound which is a halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428. 1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specifically, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1 , 3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1-p -Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)- , 6-Bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical, T manufactured by PANCHIM Series (eg, T-OMS, T-BMP, TR, TB), Irgacure series (eg, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc. Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 261), Darocur series (for example Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholino tyrofe Non, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2-morpholinopro Pan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like.
Although it does not specifically limit as said acylphosphine (oxide) type compound, Irgacure 819, Darocur 4265, Darocur TPO, etc. by Ciba Specialty Chemicals are mentioned.

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also useful.

Examples of oxime photopolymerization initiators composed of oxime compounds include oxime initiators described in, for example, JP 2000-80068 A, International Publication WO-02 / 100903 A1, and JP 2001-233842 A. It has been.
Examples of the oxime compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). ) Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [ 4- (phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime) -1- [4- (Methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) Enyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) Examples include, but are not limited to, -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

  These photopolymerization initiators may be added to the formula (I) alone or in admixture of two or more.

  When using the said well-known photoinitiator, it is preferable to use as the content within the range of content of said Formula (I).

(C) Colorant In the photopolymerizable composition of the present invention, a colorant can be contained depending on its use.
The colorant is not particularly limited, and dyes, pigments and the like can be used.
Among the above dyes, dyes that are soluble in organic solvents are preferable.
Examples of the organic solvent-soluble dye include known dyes conventionally used for color filter applications, such as JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP 6-11614, No. 2592207, US Pat. No. 4,808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5 -333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, and the like.

  Chemical structures include triphenylmethane, azo (pyrazole azo, anilinoazo, pyrazolotriazole azo, pyridone azo, etc.), anthrapyridone, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, Azomethine (such as pyrrolopyrazole azomethine), xanthene, phthalocyanine, benzopyran, and indigo dyes can be used.

In the case where the resist system is developed with water or alkali, acidic dyes and / or derivatives thereof are preferable from the viewpoint of completely removing the binder and / or dye by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
Hereinafter, the acidic dye and its derivative will be described.

-Acid dyes and their derivatives-
The acidic dye is not particularly limited as long as it is a dye having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developing solution used at the time of development processing, and forms a salt with a basic compound. It is selected in consideration of all required performances such as properties, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

Specific examples of acid dyes are given below. However, the present invention is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 108,112,113,120,129,138,147,150,158,171,182,192,210,242,243,249,256,259,267,278,280,285,290,296,315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,308,312,315,316,339,341,345,346,349,382 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19, 49;

  acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;

Food Yellow 3;
Solvent Yellow 14, 82, 94, 162;
Solvent Orange 2,7,11,15,26,56;
Solvent Blue 25, 35, 37, 38, 55, 59, 67;
Solvent Red 49;
And derivatives of these dyes.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; I. Solvent Orange 45; Rhodamine B, Rhodamine 110, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5-[(phenylsulfonyl) amino] -2,7-naphthyl, etc. These acid dyes and derivatives of these dyes are also preferably used.

  As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group derived from sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of an acidic dye, and the like can be used in the present invention. There is no particular limitation except that it is desirable to be able to dissolve such a composition when it is prepared as a solution. Solubility in organic solvents and developer used for development, absorbance, and other components in the composition Are selected in consideration of all necessary performance such as the interaction, light resistance and heat resistance.

  The “salt of an acid dye and a nitrogen-containing compound” will be described. The salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.

  The “nitrogen-containing compound” that forms a salt with the acid dye, and the “nitrogen-containing compound” that forms the amide bond of the “sulfonamide body of the acid dye” are the solubility of the salt or amide compound in an organic solvent or developer, It is selected in consideration of all of salt forming properties, dye absorbance / color value, interaction with other components in the curable composition, heat resistance as a colorant, light resistance, and the like. When selected only from the viewpoint of absorbance and color value, the nitrogen-containing compound preferably has a molecular weight as low as possible. Among them, the molecular weight is preferably 300 or less, more preferably 280 or less, and molecular weight 250 or less. It is particularly preferred that

  Specific examples of the nitrogen-containing compound are listed below. However, the present invention is not limited to these. In the following nitrogen-containing compounds, those having no —NH— group do not correspond to nitrogen-containing compounds that form amide bonds.

  The molar ratio (n) of “nitrogen-containing compound / number of acidic functional groups of the acid dye” in the salt of the acid dye and the nitrogen-containing compound is a value that determines the molar ratio between the acid dye molecule and the amine compound that is a counter ion. The acid dye-amine compound can be freely selected depending on the salt formation conditions. Specifically, a numerical value between 0 <n ≦ 5 is frequently used in practice, and it is soluble in organic solvents and developers used for development, salt-forming properties, absorbance, and interaction with other components in the composition. , Light resistance, heat resistance, etc. are selected in consideration of all necessary performance. When selected from the standpoint of absorbance only, n is preferably a numerical value satisfying 0 <n ≦ 4.5, more preferably a numerical value satisfying 0 <n ≦ 4, and particularly preferably a numerical value satisfying 0 <n ≦ 3.5. .

  Among the above, azo dyes such as pyridone azo series, pyrimidine azo series, pyrazole azo series, anilino azo series, pyrazolotriazole azo series, phthalocyanine series dyes, and azomethine series dyes are preferable.

  Specific examples of the azo dye [Exemplary compounds (1) to (72), etc.] are listed below. However, the present invention is not limited to these. In addition, tautomers of the following specific examples are also suitable.

  Furthermore, specific examples (Exemplary Compounds C-1 to C-59) are shown. However, the present invention is not limited to these.

  Furthermore, specific examples [specific examples 1 to 157] are shown. The present invention is not limited to these specific examples.

  Furthermore, specific examples (Exemplary dyes M-1 to M-84) are shown. However, it is not limited to these.

  Examples of the colorant that can be used in the present invention include conventionally known various pigments and (insulating) carbon black, in addition to the above dyes, and one or a mixture of two or more can be used.

  As the pigment that can be used in the present invention, conventionally known various inorganic pigments or organic pigments can be used. Also, considering that it is preferable that the pigment has a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment that is as fine as possible. However, in consideration of handling properties, the average particle size is preferably 0.01 μm. A pigment having a thickness of ˜0.1 μm, more preferably 0.01 μm to 0.05 μm is used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And composite oxides of the above metals.

As an organic pigment,
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
C. I. Pigment Orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment Violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Brown 25, 28;
C. I. Pigment Black 1, 7;
Etc.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the photocurable composition. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an effect.

  Among the various pigments, examples of pigments that can be preferably used in the present invention include, but are not limited to, the following.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Black 1, 7

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples are shown below. Red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them and disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments Etc. are used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. Mixing with Pigment Yellow 139 was good. The mass ratio of the red pigment to the yellow pigment was good from 100: 5 to 100: 50. Below 100: 4, the light transmittance from 400 nm to 500 nm could not be suppressed, and the color purity could not be increased. At 100: 51 or more, the dominant wavelength became shorter and the deviation from the NTSC target hue became large. In particular, the range of 100: 30 to 100: 30 was optimal. In the case of a combination of red pigments, it is adjusted according to the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment is used. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 was good. The mass ratio of the green pigment to the yellow pigment was 100: 5 to 100: 150. If it is less than 100: 5, the light transmittance from 400 nm to 450 nm cannot be suppressed, and the color purity cannot be increased. When the ratio exceeded 100: 150, the dominant wavelength became longer and the deviation from the NTSC target hue increased. A more preferred mass ratio is in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment blue 15: 6 and C.I. I. Mixing with Pigment Violet 23 was good. The mass ratio of the blue pigment to the purple pigment is preferably 100: 30 to 100: 0, more preferably 100: 10 or less.

  Further, a pigment-containing photosensitive resin having good dispersibility and dispersion stability by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer and an ethyl cellulose resin. Can be obtained.

  Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60.

As content of the coloring agent in the photopolymerizable composition of this invention, Preferably it is 1 mass%-85 mass% with respect to the total solid of a composition, More preferably, it is 5 mass%-80 mass%. is there.
If the content of the colorant is less than 1% by mass, it may not function as a color filter or ink because it does not satisfy the desired hue, and if it exceeds 85% by mass, the light absorption rate may decrease and the sensitivity may decrease.

(D) Colorant dispersant In the composition of the present invention, when a pigment is used as the colorant, for example, a dispersant for the colorant is preferably used for dispersing the organic pigment or carbon black.
As the dispersant, the following coating resin can be used, and a dispersant as described later can be used in combination.

Examples of the coating resin include the following.
1) Polyolefin polymer polyethylene, polypropylene, polyisobutylene, etc. 2) Diene polymer polybutadiene, polyisoprene, etc. 3) Polymer polyacetylene polymer having conjugated polyene structure, polyphenylene polymer, etc. 4) Vinyl polymer Polyvinyl chloride, polystyrene, vinyl acetate , Polyvinyl alcohol, poly (meth) acrylic acid, poly (meth) acrylic acid ester, polyacrylamide, polyacrylonitrile, polyvinylphenol, etc. 5) polyether polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone, polyether Ether ketone, polyacetal, etc. 6) Phenol resin novolac resin, resole resin, etc. 7) Polyester polyethylene terephthalate Polyphenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc. 8) Polyamide nylon-6, nylon 66, water-soluble nylon, polyphenyleneamide, etc. 9) Polypeptide gelatin, casein, etc. 10) Epoxy resin and modified novolac thereof 11) Other polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polysulfide, polysulfone, celluloses, etc.

  More specifically, the acrylic resin containing a carboxyl group is, for example, a monomer having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methyl, etc. Styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) ) Acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N dimethylacrylamid , N- methacryloyl morpholine, N, N- dimethylaminoethyl (meth) acrylate, N, N- dimethylaminoethyl acrylamide, polymers obtained by copolymerizing copolymerizable component such as. Among them, preferred is an acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ester as a constituent monomer, and more preferred is an acrylic resin containing (meth) acrylic acid and styrene.

  Moreover, these resins can also add an ethylenic double bond to the resin side chain. Since the photocurability is increased by imparting a double bond to the resin side chain, the resolution and adhesion can be further improved, which is preferable.

Examples of the synthesis means for introducing an ethylenic double bond include the methods described in JP-B-50-34443 and JP-B-50-34444.
Specific examples include a method of reacting a compound having both a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, or acrylic acid chloride. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained.
In particular, a resin obtained by reacting (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable.
In addition, a polymer obtained by a copolymerization reaction of at least a monomer represented by the following general formula (X) and a monomer having at least an acidic group (including the above-described copolymerization component) can also be used.

(In the formula, R represents a hydrogen atom or a methyl group, and R _{1 to} R ₅ are each independently a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group, and an aryl group.)
Here, specific examples of the halogen atom include Cl, Br, and I.
The alkyl group may be linear, branched, or cyclic, and includes a methyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, and the like, preferably having 1 to 7 carbon atoms. Examples of the aryl group include a phenyl group, a furyl group, and a naphthyl group.

The following resins can also be used as the coating resin.
A linear organic high molecular polymer which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferred. As such a linear organic polymer, those having an acid group such as a carboxy group or a phenolic hydroxyl group in the resin side chain or main chain are preferable from the viewpoint of pollution prevention because they can be alkali-developed. In particular, a resin having a carboxyl group, for example, an acrylic acid (co) polymer, a styrene / maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, and the like are preferable because of high alkali developability. Examples of the polymer having a carboxylic acid in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59- A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partial, as described in Japanese Patent No. 53836 and JP-A-59-71048 There are esterified maleic acid copolymers and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition, a polymer in which an acid anhydride is added to a polymer having a hydroxyl group is also useful. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are also suitable.
In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These polymers can be mixed in any amount.

Furthermore, the following epoxy resins can also be used.
1. 1. Glycidylamine type epoxy resin 2. Triphenylglycidylmethane type epoxy resin 3. Tetraphenylglycidylmethane type epoxy resin 4. Aminophenol type epoxy resin 5. Diamide diphenylmethane type epoxy resin 6. Phenol novolac type epoxy resin Ortho-cresol type epoxy resin8. Bisphenol A novolac epoxy resin

Among the above, as the coating resin, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable because various monomers can be selected and solubility and acid value can be controlled.
The preferred range of the weight average molecular weight Mw (mass average molecular weight) measured by gel permeation chromatography (GPC) of these coating resins is 1,000 to 300,000, more preferably 3,000 to 150,000. . By setting it to 300,000 or less, good developability can be obtained.

As the dispersant, Anti-Terra-U, Disperbyk-160, 161, 162, 163 manufactured by BYK, Solspers 20000, 24000GR, 26000, 28000 manufactured by ZENECA, DA-703-50, NDC- manufactured by Enomoto Kasei Co., Ltd. 8194L, NDC-8203L, NDC-8257L, KS-860, Homogenal L-18, L-1820, L-95, L-100 manufactured by Kao Corporation, VP5000 manufactured by Nippon Paint, E5703P manufactured by Goodrich, Union Known dispersion resins such as VAGH manufactured by Carbide, UR8200 manufactured by Toyobo, and MR113 manufactured by ZEON can be used.
Moreover, a phthalocyanine derivative (trade name: EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Zeneca), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical), (meth) acrylic acid (co-) ) Polymer Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho), and other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho); EFKA-46 , EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Dispa Polymer dispersing agents such as Suede 8, Disperse Aid 15 and Disperse Aid 9100 (manufactured by Sannopco); Solsols dispersing agents such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 ( Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) Co., Ltd.) and ISONET S-20 (manufactured by Sanyo Chemical Co., Ltd.).
These clothing resins and dispersants can be used alone or in combination.

The content of the colorant dispersant in the colorant-containing negative curable composition of the present invention is preferably 1% by mass to 90% by mass and more preferably 3% by mass with respect to the total solid content of the composition. % To 80% by mass.
When the content of the colorant dispersion is less than 1% by mass, the dispersion uniformity of the pigment may be impaired, and when it exceeds 90% by mass, the curability during photopolymerization may be reduced.

(B) Radical polymerizable monomer The photopolymerizable composition of the present invention contains at least one radical polymerizable monomer. As the radical polymerizable monomer, a compound having at least one addition-polymerizable ethylenically unsaturated double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable.

  Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and then (meth) acrylated after adding ethylene oxide or propylene oxide, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Mention polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy resins and epoxy acrylates which are reaction products of (meth) acrylic acid and mixtures thereof described in JP-B-52-30490 Can do. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  In addition to the above, radically polymerizable monomers containing carboxyl groups such as the following general formulas (V-1) and (V-2) can also be suitably used. In general formulas (V-1) and (V-2), when T or G is an oxyalkylene group, terminal carbon atoms are bonded to R, X, and W.

In the said general formula (V-1), n is 0-14 and m is 1-8. In the said general formula (V-2), W is R or X synonymous with general formula (V-1), and 3 or more W is R among six W. p is 0-14 and q is 1-8. A plurality of R, X, T, and G present in one molecule may be the same or different.
Of the radical polymerizable monomers represented by the general formulas (V-1) and (V-2), the following specific examples (Exemplary Compounds M-1 to M-12) are specifically preferred. Exemplified compounds M-2, M-3, and M-5 are preferred.

  The content of the radical polymerizable monomer in the photopolymerizable composition is preferably 3% by mass or more, and more preferably 5% by mass or more, in the solid content ratio in the total solid content of the composition. Preferably, it is most preferable to contain 7 mass% or more.

(E) Alkali-soluble resin (binder)
The photopolymerizable composition of the present invention may further use an alkali-soluble resin (binder). Moreover, other well-known resin can be suitably selected in the range which does not impair the effect of this invention.

  Hereinafter, the alkali-soluble resin (hereinafter referred to as an alkali-soluble binder) will be described.

The alkali-soluble binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone and polyethylene oxide, Polyvinyl alcohol and the like are also useful.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  In addition, the hydrophilic monomer includes a tetrahydrofurfuryl group, a phosphoric acid site, a phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid group and its salt, a morpholinoethyl group, and the like. A monomer or the like is also useful.

  In addition, from the viewpoint of improving the crosslinking efficiency, a polymer having a polymerizable group in the side chain and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Hereinafter, examples of the polymer containing these polymerizable groups are shown, but the polymer is not limited thereto as long as it contains an alkali-soluble group such as a COOH group, an OH group, and an ammonium group and an unsaturated bond between carbon atoms.

  As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used.

  As the compound having reactivity with the OH group, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can be used in addition to the epoxy ring. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd.); Biscote R-264, KS resist 106 (both made by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both made by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel Yu) CB Co., Ltd.).

  When the alkali-soluble resin (binder) is contained, the content of the resin in the photopolymerizable composition is usually 0.5 to 90% by mass with respect to the total solid content of the composition.

(F) Organic solvent In preparing the photopolymerizable composition of the present invention, generally an organic solvent (also simply referred to as “solvent” in the present specification) can be used. The solvent is not particularly limited as long as the solubility of each component and the coating property of the photopolymerizable composition are satisfied, but the photopolymerization initiator, photosensitizer, colorant (particularly dye), and colorant dispersant. The radically polymerizable monomer and the alkali-soluble resin (binder) are preferably selected in consideration of solubility, coating property, and safety.

  Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbi Tall acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

  Among the above, in terms of solubility and coating properties of each component, one or more kinds are selected from cyclohexanone, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and ethyl 3-ethoxypropionate. In addition, it is preferable to use one of ethyl lactate, propylene glycol monomethyl ether acetate, and ethyl 3-ethoxypropionate from the viewpoint of uniformity after deposition and application after dissolution of each constituent component. Or the aspect comprised by selecting 2 or more types is more preferable.

(G) Other components-surfactant-
The composition of the present invention may further use a surfactant. As the surfactant, those mentioned as the colorant dispersant may be used.
Surfactants other than those listed as the colorant dispersant can be selected from known surfactants such as nonionic, cationic, and anionic depending on the purpose and the like. For example, it is a fluorine organic compound having a fluorine content of 3 to 40% by mass. By containing such a compound, the properties of the composition as a coating solution can be further improved, and the uniformity of coating thickness and liquid-saving property can be improved. In particular, the coating property to the substrate is improved, and a coating film having a uniform film thickness with no thickness unevenness can be obtained even with a small amount of liquid.
The fluorine content of the fluorine-based organic compound is 3 to 40% by mass, preferably 5 to 30% by mass, and more preferably 7 to 25% by mass.
If the fluorine content of the fluorine-based organic compound is low, sufficient effects cannot be obtained in coating thickness uniformity and liquid-saving properties. Conversely, if the content is too large, the solubility in the composition is insufficient. There is a case.
Examples of the fluorine-based organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, manufactured by Dainippon Ink Co., Ltd.). ), FLORARD FC430, FC431, FC171 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.) and the like.
Moreover, the fluidity | liquidity as a coating liquid can be improved by containing the said fluorine-type organic compound. As a result, the interfacial tension between the substrate and the coating liquid can be reduced to improve the wettability to the substrate, and thus a coating film with small thickness unevenness can be obtained even for a thin film of about several μm. In particular, when the coating film is thin, good results are obtained for coating application, thickness unevenness, and slit coating that easily causes liquid breakage on the coating surface.
The addition amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass with respect to the total coating solution.

~ Crosslinking agent ~
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and acyloxymethyl. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from the group A phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound according to (b) (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound).

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, the phenol compound, naphthol compound or hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b). As in the case of, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to (c) is a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, It can be obtained by reacting with formalin in the presence of a basic catalyst such as ammonia or tetraalkylammonium hydroxide.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, and examples thereof include phenol and cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound or a naphthol compound, for example, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, tri (methoxymethyl) phenol, trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like Compounds obtained by methoxymethylating one to three methylol groups of methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of xymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  In the present invention, it is not always necessary to contain a crosslinking agent. When the crosslinking agent is contained, the total content of the crosslinking agents (a) to (c) in the colorant-containing negative curable composition varies depending on the material, but the total solid content (mass) of the composition. On the other hand, 1-70 mass% is preferable and 5-50 mass% is more preferable.

~ Various additives ~
In the colorant-containing negative curable composition of the present invention, various additives, for example, a filler, a polymer compound other than the above, a surfactant other than the above, an adhesion promoter, an antioxidant, An ultraviolet absorber, an aggregation inhibitor, a transition metal complex, or the like can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

  In the photopolymerizable composition of the present invention, a transition metal complex having a maximum molar extinction coefficient ε in the visible light region smaller than the molar extinction coefficient ε of the organic solvent-soluble dye can be used. This transition metal complex is one in which a negative, neutral or positive monodentate ligand or polydentate ligand is coordinated around a transition metal atom or transition metal ion, and contains the colorant of the present invention. This is effective for improving the light resistance of the photopolymerizable composition and the color filter using the same.

  A transition metal complex having a maximum molar extinction coefficient ε in the visible light region (380 to 780 nm) of 0 or more and 8000 or less is preferable in terms of color sharpness. Further, as the transition metal complex, the maximum value of the molar extinction coefficient ε in the above wavelength range is preferably 0 or more and 6000 or less, and more preferably 0 or more and 3000 or less.

  Examples of transition metals constituting transition metal atoms and transition metal ions of transition metal complexes include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), yttel Um (Yb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), Iridium (Ir), Platinum (Pt), Gold (Au), Etc.

  Preferred examples of the transition metal complex include those in which the transition metal belongs to the first series (that is, the fourth period of the long periodic table; the same applies hereinafter), that is, scandium (Sc), titanium (Ti), vanadium (V), chromium Examples include (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu). Of these, Mn, Fe, Co, Ni, and Cu are preferable.

As the ligand of the transition metal complex, the ligand alone preferably has a maximum molar extinction coefficient ε in the visible light region of 0 or more and 3000 or less, and the maximum value of ε is 0 or more and 2000 or less. Is more preferable, and the maximum value of ε is particularly preferably 0 or more and 1000 or less.
In addition, the molecular weight of one ligand in the transition metal complex is preferably 20 or more and less than 300 in terms of light resistance and alkali developability.

Further, when the alkali solubility of the uncured part is promoted and the developability of the photopolymerizable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid can be added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.
In addition, what has a carboxyl group can also be mentioned as a specific example among the said components (D).
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl. Catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful. .

The photopolymerizable composition of the present invention can be used for various purposes, for example as a printing ink, for example as a screen printing ink, offset or flexographic ink, as a transparent finish, for example as a white or colored finish against wood or metal, as a powder coating. As a coating material, especially for paper, wood, metal or plastic, building markings, road markings, photographic reproduction techniques, holographic recording materials, image recording techniques, or production of printing masters that can be developed with organic solvents or aqueous alkalis As a sun curable coating for the production of screen printing masks, as dental filling compositions, as adhesives, as pressure sensitive adhesives, as laminating resins, both liquid and dry thin film etching resists, solder resists, Electroplating cash register Or as a permanent resist, for printed circuit boards and electronic circuits, as a photoconstitutive dielectric, for various display applications, or for the formation of structures in the manufacturing process of plasma display panels and electroluminescent display devices For producing color filters (for example, US Pat. No. 5,853,446, European Patent 863,534, JP-A-9-244,230, 10-62,980, 8-171,863) No. 5,840,465, European Patent No. 855,731, JP-A-5-271,576, JP-A-5-67,405), optical switch, etc. For the production of optical gratings (interference gratings) and optical circuits, the production of three-dimensional articles by mass curing (UV curing with transparent molds) or stereolithographic techniques (eg US Pat. No. 4 575,330), composite materials (eg, styrenic polyester, which may include glass fibers and / or other fibers and other auxiliaries, if desired), and other thick layer compositions. Can be used as a resist for coating or sealing electronic components and integrated circuits, or for optical fibers, or as a coating for the production of optical lenses such as contact lenses or Fresnel lenses. The composition according to the invention is furthermore suitable for the manufacture of medical devices, aids or implants. Furthermore, the compositions according to the invention are suitable for the production of gels having thermotropic properties, as described, for example, in German Patent No. 19,700,064 and European Patent No. 678,534.
The novel photoinitiator is used as an initiator for emulsion polymerization, pearl polymerization or suspension polymerization, as a polymerization initiator for fixing the regular state of liquid crystal monomers and oligomers, or as a dye for organic materials. It may additionally be used as an initiator for fixing.
In particular, for forming colored pixels such as color filters used in liquid crystal display devices (LCDs) and solid-state imaging devices (eg, CCDs, CMOSs, etc.), electroluminescent color filters, etc., printing inks, inkjet inks, It can be suitably used for producing UV inks and paints.

<< Photopolymerization method >>
The photopolymerization method in the present invention is characterized in that the radical polymerizable monomer contained in the photopolymerizable composition is polymerized by irradiation with electromagnetic radiation, electron beam or X-ray in the range of 150 nm to 600 nm.
The radical polymerizable monomer contained in the photopolymerizable composition starts a photopolymerization reaction by the action of the photopolymerization initiator by irradiating the electromagnetic radiation, electron beam, X-ray or the like, The photopolymerizable composition is cured to form a composition film.

<< Method for Producing and Using Composition When Photopolymerizable Composition of the Present Invention Contains a Pigment as a Colorant >>
Hereinafter, a method for producing a composition and a method for using the composition when the photopolymerizable composition of the present invention contains a pigment as a colorant will be described.
Photopolymerization initiator, radical polymerizable monomer, colorant, colorant dispersant and other additives used as needed are mixed with a solvent and mixed and dispersed using various mixers and dispersers. It can prepare by passing through a dispersion | distribution process.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.
As a preferable production method, the colorant is kneaded and dispersed so that the viscosity after the kneading and dispersing treatment with the resin component is 10,000 mPa · s or higher, desirably 100,000 mPa · s or higher, and then the solvent. Is added, and the dispersion after the fine dispersion treatment is finely dispersed so that the viscosity becomes 1,000 mPa · s or less, preferably 100 mPa · s or less. Further, a high boiling point solvent or the like is added and stirred and mixed. The method is preferred.
The machines used in the kneading and dispersing treatment are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single and twin screw extruders, etc., which disperse while giving a strong shearing force. . Next, a solvent is added and finely dispersed with beads made of glass or zirconia having a particle diameter of 0.1 to 1 mm, mainly using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. To process. It is also possible to omit the kneading and dispersing process. In that case, beads are dispersed with a pigment, a dispersant or a surface treatment agent, and the acrylic copolymer and solvent in the present invention.
For details on kneading and dispersing, see T.W. C. This method is also described in Paton's “PaintFlowand Pigment Dispersion” (published by John Wiley and Sons, 1964) and the like.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, a color filter is produced using the photopolymerizable composition of the present invention described above. Specifically, a color filter having a desired hue can be produced by repeating the above-described image forming process (and, if necessary, the curing process) by the desired number of hues.

  The composition of the present invention is applied to a substrate directly or via another layer by a coating method such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method, etc. A coating film is formed, if necessary, exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, and developed with a developer to form a negative colored pattern (image forming process) . Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included. By repeating the image forming step (and the curing step if necessary) as many times as desired, a color filter having a desired hue can be produced. As the radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

  As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements, etc., and those having a transparent conductive film attached thereto, photoelectric conversion used for solid-state imaging elements, etc. An element substrate, for example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. Furthermore, a plastic substrate is also possible. The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface. On these substrates, black stripes for isolating each pixel may be formed. Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

Drying (prebaking) of the coating film of the composition of the present invention applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds with a hot plate, oven or the like.
The coating thickness (after drying) of the coating film of the composition of the present invention is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, and most preferably 0.7 to 2.5 μm. .

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the photopolymerizable composition of the present invention but does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As an organic solvent here, the above-mentioned organic solvent used when preparing the photopolymerizable composition of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with water after development.
Post-baking is heating after development to complete curing, and is usually performed at about 200 ° C. to 220 ° C. (hard baking).
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  The color filter of the present invention uses the above-described photopolymerizable composition of the present invention, and preferably has two or more colored regions (for example, red (R), green (G) and blue) on the support. (B) three colored regions) are provided in a desired pattern shape (for example, a stripe shape, a lattice shape, a delta array shape, etc.). The color filter of the present invention can be most suitably produced by the method for producing a color filter of the present invention. Therefore, a color filter can be manufactured with high productivity.

  The color filter of the present invention can be used for a liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.).

  As the application of the composition of the present invention, the application mainly to a color filter has been mainly described, but it is needless to say that the composition can also be applied to a black matrix provided between pixels of a color filter. The black matrix is formed by photo-exposure and alkali development of a composition obtained by adding a black colorant such as carbon black or titanium black to the composition of the present invention, and then post-baking to promote film curing. be able to.

  Hereinafter, although the present invention is explained in detail using an example, the present invention is not limited to this. Unless otherwise specified, “part” is based on mass.

Example 1 [Compound of the Invention: Synthesis of Photopolymerization Initiator I-1]
<Synthesis of Compound (1)>
To a 200 ml three-necked flask, 18.63 g (0.1 mol) of phenyl sulfide, 75 ml of carbon disulfide, and 14.24 g (0.1 mol) of 4-chlorobutyryl chloride were added and cooled to 0 ° C. while substituting with nitrogen gas. Thereafter, 13.47 g (0.1 mol) of aluminum (III) chloride was added little by little. After completion of the addition, the mixture was stirred at room temperature for 2 hours, and the reaction solution was poured into 100 ml of 0.5N aqueous hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was washed in turn with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, and dehydrated by adding magnesium sulfate. Magnesium sulfate was removed by filtration and the solvent was concentrated by an evaporator, followed by purification by silica gel column chromatography to obtain 22.45 g (yield 77%) of compound (1).

<Synthesis of Compound (2)>
In a 300 ml three-necked flask, 10.95 g (0.0757 mol) of 4-chlorothiophenol, 30 ml of tetrahydrofuran (THF), 20 ml of distilled water, 3.03 g (0.0757 mol) of sodium hydroxide, 1.26 g (0.0076 mol) of potassium iodide ) Was added and stirred at room temperature.
Thereto was added dropwise a solution of 22 g (0.0757 mol) of the compound (1) obtained above in 20 ml of THF over 30 minutes. After completion of the dropwise addition, the reaction solution was heated at 80 ° C. and stirred for 4 hours. Then, after allowing to cool to room temperature, the reaction solution was extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dehydrated by adding magnesium sulfate. After filtering magnesium sulfate and concentrating the solvent with an evaporator, purification was performed by silica gel column chromatography to obtain 18.12 g (yield 60%) of the following compound (2).

<Synthesis of Compound (3)>
To a 100 ml three-necked flask, 15 ml of methanol and 1.53 g (0.028 mol) of sodium methoxide were added, and the system was purged with nitrogen gas. After cooling the reaction solution to 0 ° C., a solution of the compound (2) obtained above (10.69 g, 0.0268 mol) in THF (20 ml) was added dropwise over 30 minutes.
After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and the reaction solution was kept at 10 ° C. using a thermostatic layer, and a solution of isopentyl nitrite 3.31 g (0.028 mol) in THF 10 ml was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then the reaction solution was poured into a solution of distilled water 100 ml / acetic acid 3.0 ml cooled to 0 ° C.
Thereafter, the mixture was extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dehydrated by adding magnesium sulfate. After filtering magnesium sulfate and concentrating the solvent with an evaporator, purification was performed by silica gel column chromatography to obtain 7.11 g (yield 62%) of the following compound (3).

<Compound of the present invention: Synthesis of photopolymerization initiator (I-1)>
To a 100 ml three-necked flask, 6.51 g (0.0152 mol) of the compound (3) obtained above and 20 ml of THF were added, and the system was replaced with nitrogen gas and cooled to 0 ° C. with stirring.
Thereto, a THF solution (2.18 g, 0.028 mol) in THF (5 ml) and an acetyl chloride (1.97 g, 0.025 mol) in THF (5 ml) were separately added dropwise simultaneously. After dropwise addition over 15 minutes, the mixture was further stirred at room temperature for 3 hours.
Thereafter, the reaction solution was poured into 200 ml of distilled water, extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dehydrated by adding magnesium sulfate. After filtering magnesium sulfate and concentrating the solvent with an evaporator, purification was performed by silica gel column chromatography to obtain 6.79 g (yield 95%) of a photopolymerization initiator (I-1). The chemical structure was confirmed by the following analysis results.

The obtained photopolymerization initiator (I-1) was identified by ¹ H-NMR. The ¹ H-NMR spectrum of the obtained photopolymerization initiator (I-1) is shown.
(Acetone-d6: internal standard TMS) δ [ppm]: 8.05 (d, 2H), 7.59 (m, 2H), 7.52 (m, 3H), 7.39 (m, 4H), 7.25 (d, 2H), 3.31 (t, 2H), 3.13 (t, 2H), 2.19 (s, 3H)

  Other oxime derivatives of the present invention can be synthesized by the same method.

(Examples 2 to 5, Reference Example 6, Comparative Example 1)
1) Preparation of resist solution A compound having the following composition was mixed and dissolved to prepare a resist solution.
Propylene glycol monomethyl ether acetate ... 19.20 parts (PGMEA)
-Ethyl lactate ... 36.67 parts-Resin (binder) ... 30.51 parts [Benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60: 20: 20, weight average molecular weight 15000) ) 41% PGMEA solution]
Dipentaerythritol hexaacrylate 12.20 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol): 0.0061 part Fluorosurfactant: 0.83 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator: 0.586 parts (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)

2) Production of glass substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes or more. Next, the resist solution was applied onto the silicon wafer so as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. .

3) Preparation of photopolymerizable composition containing colorant (dye) (1)
A photopolymerizable composition containing a colorant (dye) dissolved in a propylene glycol monomethyl ether acetate / ethyl lactate (6/4) mixture so that the solid content concentration is 20% by mass. Products N-1 to N-5 were prepared.

4) Exposure and development of a photopolymerizable composition containing a colorant (dye) (image forming step)
After filtering the photopolymerizable compositions N-1 to N-5 containing the colorant (dye) obtained in 3) above using a filter, the film thickness is on the silicon wafer obtained in 2) above. It apply | coated using the spin coater so that it might be set to 0.8 micrometer, and heat processing (prebaking) were performed at 100 degreeC for 120 second.

  The coating film obtained above was irradiated using an i-line reduction projection exposure apparatus with a wavelength of 365 nm through a mask having a line width of 2 μm and changing the exposure amount by 100 mJ. After irradiation, the film was developed using a developer of 60% CD-2000 (manufactured by FUJIFILM Electronics Materials) at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a colored filter film (color filter). The formation of the image was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

5) Evaluation About the photopolymerizable compositions N-1 to 5, NH-1 and color filters containing the colorant (dye) obtained in the above-described Examples and Comparative Examples, the state of the coating film is as follows. And evaluation of sensitivity. The evaluation results are shown in Table 1.

-1. Evaluation of coating film condition based on the presence or absence of precipitates
After the coating and heat treatment obtained in 4) above, the film after 24 hours was observed, and the evaluation was made with x when the precipitation component was seen and ◯ when it was not seen.

-2. Evaluation of Sensitivity In the 2 μm width pattern obtained above, the exposure amount at which the dot-to-space width was 1: 1 was defined as the appropriate exposure amount (sensitivity), and the relative value of sensitivity was determined from the following equation.
The smaller the relative value of sensitivity, the better the performance.

Relative sensitivity value =
(Sensitivity of Compositions N-1 to N-5) / (Sensitivity of Composition NH-1)

I-1: Photopolymerization initiator of the present invention (see below)
IH-1: Irgacure OXE01 (see below, manufactured by Ciba Specialty Chemicals)
C-1: Mixture of 3: 7 (mass ratio) of the aforementioned exemplary compound (M-2) of radical polymerizable monomer and dipentaerythritol hexaacrylate

  Colorant: The compounds shown in Table 1 are as follows.

  As the colorant A4-1, one synthesized as in the following scheme was used.

<Synthesis of Intermediate Product B>
Compound A (25.0 g, 0.162 mol) was dissolved in a mixed solvent of methanol (100 ml) and triethylamine (23 ml), and this was cooled and stirred at 5 ° C., and further 9 ml of 30% hydrogen peroxide solution was added dropwise while maintaining the internal temperature at 25 ° C. did. The reaction solution after dropping was further stirred at 25 ° C. for 30 minutes, cooled again to 5 ° C., 15 ml of concentrated hydrochloric acid was added dropwise with stirring, 200 ml of water was further added, and the mixture was stirred at 25 ° C. for 1 hour. The precipitated crystals were filtered, washed thoroughly with water, and dried to obtain 24.7 g of intermediate product B as white crystals (yield 99.5%).

<Synthesis of Intermediate Products C, D, and E>
Subsequently, 100 ml of toluene and 0.25 ml of dimethylacetamide were added to 17.5 g (0.114 mol) of the intermediate product B obtained above, and further 25 ml of thionyl chloride was added dropwise over 10 minutes under reflux. This was further heated under reflux for 1 hour and then concentrated under reduced pressure to obtain a viscous liquid. On the other hand, while adding 10 ml of dimethylacetamide and 100 ml of acetonitrile to 38.0 g (0.235 mol) of diethoxyethylamine and stirring at 10 ° C., the viscous liquid was kept at 15 ° C. over 15 minutes. It was dripped. After further stirring for 30 minutes, this was poured into a mixed solution of 100 ml of water and 100 ml of ethyl acetate, and the ethyl acetate phase was separated and washed twice with 100 ml of water. The ethyl acetate phase was dried using magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain an intermediate product C which was a pale yellow viscous liquid.

  Next, 50 ml of water, 200 ml of ethanol, and 12 g of zinc powder were added to the intermediate product C, and a solution obtained by diluting 10 ml of sulfuric acid in 40 ml of water was added dropwise over 20 minutes under reflux with heating. The mixture was further heated and stirred for 30 minutes and then cooled, and insoluble matters were separated by filtration. To the resulting solution were added 50 ml of saturated brine and 100 ml of ethyl acetate, and the mixture was separated, and the ethyl acetate phase was washed twice with 100 ml of water. The ethyl acetate phase was dried using magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure to obtain an intermediate product D which was a pale yellow viscous liquid.

  Next, 70 ml of dimethylacetamide and 15 g (0.108 mol) of potassium carbonate were added to this intermediate product D under stirring in a nitrogen atmosphere, and 19.7 g (0. 113 mol) was gradually added while maintaining the temperature below 25 ° C. This was further stirred for 30 minutes, and then poured into 300 ml of water with stirring. The obtained crystals were filtered, and the crystals were thoroughly washed with water. The obtained crystals were recrystallized with 70 ml of methanol, and the precipitated crystals were washed with 30 ml of cold methanol and dried to obtain 35.0 g of an intermediate product E as white crystals (yield 72.6%).

<Synthesis of A4-1>
Next, 150 ml of butanol, 6.7 g (0.070 mol) of ammonium carbonate, and 4.7 g (0.035 mol) of copper chloride are added to 34.4 g (0.081 mol) of the intermediate product E, followed by stirring with heating. For 7 hours. Then, butanol was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography to obtain 25 g of A4-1 powder (yield 72.7%). When the maximum absorption wavelength (λ _max ) and molar extinction coefficient (ε) of the obtained dye were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λ _max 706. It was 8 nm and ε55,600.

  The colorant A5-10 used was synthesized as follows.

(1) 29.6 g of phthalic anhydride, 22.2 g of 4-bromo-substituted phthalic anhydride, and 16.7 g of pyridine-2,3-dicarboxylic anhydride (molar ratio: 2/1/1) are mixed. Further, 144 g of urea, 9.9 g of cuprous chloride, 1.6 g of ammonium molybdate, and 400 ml of 1-chloronaphthalene were added and heated to synthesize a compound having a bromo-substituted tetraazaporphyrin skeleton.
(2) After charging 13.1 g of the compound of (1) into 2.5 g of chlorosulfonic acid and raising the temperature, 10 g of thionyl chloride is further added dropwise. This was cooled, poured into water and filtered to remove solids, and then charged with 400 g of ice water, and 2.80 g of bis (2-methoxyethyl) amine was added dropwise, and the resulting solid was filtered and dried. The following compound A5-10 was obtained.

  From Table 1 above, it can be seen that, compared with the comparative example, the example has no precipitation after coating and has good sensitivity, and the photopolymerizable composition of the present invention exhibits excellent performance.

Claims (1)

A compound represented by formula (I).

[In formula (I) , R ^la represents —CH ₂ CH ₂ SC ₆ H ₄ Cl . R ^2a represents an alkanoyl group or an aryloyl group . n is indicates an integer of 1-2, when n is 1, R ^{1 'represents} the structure: P1, when n is 2 and R ^1' is to display the following structure P2. ]