JP2010138251A - Dispersion composition, polymerizable composition, light shielding color filter, solid-state image sensor, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a dispersion composition with a high dispersion property and storage stability, of which dispersion of a light-shielding pigment is high and light shielding pigments, especially a titanium black pigment, is not precipitated with time; a polymerizable composition with good sensitivity from which a light-shielding molded product is formed even when pattern forming is performed; a light-shielding color filter with a highly light-shielding color pattern using the polymerizable composition; a solid-state image sensor with high image-quality; and a liquid crystal display device. <P>SOLUTION: The dispersion composition includes (A) the light-shielding pigment, (B) a dispersant having a radically polymerizable group on at least one end and a group that adsorbs to the light-shielding pigment on the other end, and (C) a solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dispersion composition containing a light-shielding pigment, a polymerizable composition containing the same, a light-shielding color filter using the same, a solid-state imaging device including the light-shielding color filter, and a liquid crystal display device.

A color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. Also in the solid-state imaging device, a black matrix is provided for the purpose of preventing noise and improving image quality. The black matrix contains a dispersion composition in which a light-shielding black color material is dispersed, a polymerizable compound, a polymerization initiator, and other components to form a polymerizable composition, which is used to form a pattern by a photolithography method or the like. It is manufactured by forming.
As a composition for forming a black matrix for a liquid crystal display device or a solid-state imaging device, a photosensitive resin composition containing a light-shielding pigment that is a black color material such as carbon black or titanium black is known.

  As a black matrix for a liquid crystal display device, a black matrix having a high light shielding property is required in order to increase contrast and improve visibility. On the other hand, a black matrix for a solid-state imaging device needs to have light shielding properties in the infrared region in addition to light shielding properties in the visible region.

A performance required for a liquid crystal display device using a color filter is high contrast. In order to meet this requirement, it is necessary to increase the optical density of the black matrix. On the other hand, thinning of the black matrix is also required from the standpoint of suppressing variation in cell gap and high definition.
There are two methods for increasing the optical density of the black matrix: a method of increasing the film thickness and a method of increasing the concentration of the light-shielding pigment. However, the method of increasing the film thickness does not meet the demand for thinning the black matrix. .
Therefore, it is necessary to increase the optical density without increasing the thickness of the black matrix, and it is necessary to increase the density of the black color material in the black matrix.

  Further, in order to meet the quality requirements of a black matrix having a high light shielding property, the usefulness of titanium black having a high light shielding property is enhanced, and various proposals have been made to improve the dispersibility of titanium black (see Patent Document 1). However, since titanium black has a large specific gravity, it is difficult to disperse, and improvement in dispersibility and dispersion stability is desired, for example, titanium black settles over time even after dispersion.

  With respect to these problems, as a compound having high sensitivity and developability and film-forming properties, a resin having an ethylenically unsaturated double bond and a carboxy group in the side chain (for example, see Patent Document 2), A method of using a monomer as a dispersant has been developed (see Patent Document 3).

As described above, for the polymerizable composition for use in color filter production, in either case for a liquid crystal display or for a solid-state imaging device, photopolymerization is an essential component for curing the polymerizable composition. The content of the colorant and the photopolymerizable monomer is limited, and since the colorant concentration is high, the sensitivity is low and sufficient curing cannot be obtained, and the adhesion to the substrate is insufficient. Has occurred.
JP 2005-266189 A JP 2003-29018 A JP 2008-191224 A

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a dispersion composition having a high dispersibility of a light-shielding pigment, a light-shielding pigment, particularly a titanium black pigment, which does not settle even after aging, and has a high dispersibility and storage stability.
A further object of the present invention is to provide a polymerizable composition having a good sensitivity and capable of forming a light-shielding cured product even in the case of pattern molding, and using the light-shielding property. An object of the present invention is to provide a light-shielding color filter having a highly colored pattern, and to provide a high-quality solid-state imaging device and a liquid crystal display device using the same.

Means for solving the above problems are as follows.
<1> (A) a light-shielding pigment, (B) a dispersant having at least one terminal capable of radical polymerization and a group adsorbing to the light-shielding pigment at the other terminal, and (C) a solvent Dispersion composition.
<2> (B) A dispersant having at least one terminal capable of radical polymerization and having a group adsorbing to the light-shielding pigment at the other terminal is at least one of a polyether linking group and a polyester linking group. The dispersion composition according to <1>, which is a dispersant having a radically polymerizable group at the terminal.

<3> (B) A dispersant having at least one terminal capable of radical polymerization and having a group adsorbing to the light-shielding pigment at the other terminal is a compound represented by the following general formula (1). The dispersion composition according to <1> or <2>.

In General Formula (1), B represents an allyl group or a (meth) acryloyl group, Q ¹ and Q ³ each independently represent a single bond or a divalent linking group, Q ² represents an alkylene group, M represents an organic group having at least one selected from a phosphoric acid group, a carboxylic acid group, a urethane group, a urea group, an amide group, and an imino group. a represents an integer of 0 to 20, b represents an integer of 0 to 100, and (a + b) is in the range of 5 to 100. n represents an integer of 1 to 4, and p represents an integer of 2 to 8, respectively.

<4> (B) A dispersant having at least one terminal capable of radical polymerization and having a group adsorbing to the light-shielding pigment at the other terminal is represented by the following general formula (2) or general formula (3): <1>-<3> which is a compound represented by any one of <1>-<3>.

In General Formula (2) and General Formula (3), B ¹ and B ² each independently represent an allyl group or a (meth) acryloyl group, and Q ⁴ , Q ⁶ , Q ⁷ , and Q ⁹ are Each independently represents a single bond or a divalent linking group, Q ⁵ and Q ⁸ each independently represent an alkylene group, M ¹ represents an (n1 + m1) -valent organic group, M ² represents a single bond, or (n2 + m2) ) Represents a valent organic group. a1 and a2 each independently represent an integer of 0 to 20, b1 and b2 each independently represent an integer of 0 to 100, and (a1 + b1) is 5 to 100, and (a2 + b2) is 5 to 100. Range. m1, m2, n1, and n2 each independently represents an integer of 1 to 4, and q and r each independently represents an integer of 2 to 8.

<5> (B) A dispersant having at least one terminal capable of radical polymerization and having a group adsorbing to the light-shielding pigment at the other terminal is represented by the following general formula (4) or general formula (5). The dispersion composition according to any one of <1> to <3>, which is a compound represented.

In General Formula (4) and General Formula (5), B ³ and B ⁴ each independently represent an allyl group or a (meth) acryloyl group, and Q ¹⁰ and Q ¹⁴ each independently represent a single bond, or A divalent linking group is represented, Q ¹¹ and Q ¹⁵ each independently represent an alkylene group, and Q ¹² , Q ¹⁶ , and Q ¹⁷ each independently represent a divalent linking group. Q ¹³ represents an n3 valent linking group, and Q ¹⁸ represents an n4 valent linking group. a3 and a4 each independently represents an integer of 0 to 20, b3 and b4 each independently represents an integer of 0 to 100, and (a3 + b3) is in the range of 5 to 100, and (a4 + b4) is in the range of 5 to 100 It is. n3 and n4 each independently represents an integer of 2 to 6, m4 represents an integer of 0 to 10, and s and t each independently represents an integer of 2 to 8.

<6> (A) The dispersion composition according to any one of <1> to <5>, wherein the light-shielding pigment is titanium black.
<7> A polymerizable composition comprising the dispersion composition according to any one of <1> to <6>, and (D) a polymerization initiator.
<8> The polymerizable composition according to <7>, wherein (D) the polymerization initiator is an oxime polymerization initiator.

<9> A light-shielding color filter having a colored pattern formed using the polymerizable composition according to <7> or <8> on a substrate.
<10> A solid-state imaging device including the light-shielding color filter according to <9>.
<11> A liquid crystal display device comprising the light-shielding color filter according to <9>.

<12> A dispersant represented by the following general formula (2), general formula (4), or general formula (5).

In General Formula (2), General Formula (4), and General Formula (5), B ¹ , B ³ , and B ⁴ each independently represent an allyl group or a (meth) acryloyl group. Q ⁴ , Q ⁶ , Q ¹⁰ , and Q ¹⁴ each independently represent a single bond or a divalent linking group, Q ⁵ , Q ¹¹ , and Q ¹⁵ represent an alkylene group, Q ¹² , Q ¹⁶ , and Q ¹⁷ each independently represents a divalent linking group. Q ¹³ represents an n3 valent linking group, and Q ¹⁸ represents an n4 valent linking group. M ¹ represents an (n1 + m1) -valent organic group, a1 represents an integer of 1 to 20, and a3 and a4 each independently represents an integer of 0 to 20. b1, b3, and b4 each independently represents an integer of 0-100, (a1 + b1) is in the range of 5-100, (a3 + b3) is in the range of 5-100, and (a4 + b4) is in the range of 5-100. Range. m1 is an integer of 1 to 4, n1 is an integer of 1 to 4, m4 is an integer of 0 to 10, n3 and n4 are each independently an integer of 2 to 6, q, s, and t are each independently 2 Each represents an integer of 8.

In particular, in a preferable embodiment of the dispersion composition of the present invention, a dispersant having a polyether linking group or a polyester linking group is used. In this embodiment, the light-shielding pigment is uniformly dispersed by exhibiting better dispersibility. Even when stored at room temperature for a long period of time, sedimentation of the light-shielding pigment could be suppressed for a long period of time. This is considered to be because the polyether linking group or the polyester linking group present in the molecule of the dispersant functions as a steric repulsion group.
Furthermore, when a specific graft compound described later is used as a dispersant, the graft chain of the specific graft compound further interacts with the solvent, so that better dispersibility and dispersion stability are obtained. Guessed.

  Conventionally, when a pattern is formed by a polymerizable composition using a dispersion composition containing a light-shielding pigment and a dispersant, the pattern is formed in the development process because the curable component in the polymerizable composition is insufficient. However, in the polymerizable composition using the dispersion composition of the present invention, since a dispersant having an allyl group capable of radical polymerization or a (meth) acryloyl group at the terminal is used, a radical crosslinking reaction is performed at the time of curing. Is sufficiently advanced, pattern formation is possible, and good sensitivity can be obtained.

According to the present invention, it is possible to provide a dispersion composition having a high dispersibility of a light-shielding pigment, a light-shielding pigment, particularly a titanium black pigment, which does not settle even after aging, and a high dispersibility and storage stability.
Furthermore, even when pattern molding is performed, a light-shielding cured product can be formed, and a polymerizable composition with good sensitivity can be provided, and a colored pattern with high light-shielding properties can be provided using the composition. A light-shielding color filter can be provided, and a high-quality solid-state imaging device and a liquid crystal display device can be provided using the light-shielding color filter.

The present invention is described in detail below.
The dispersion composition of the present invention is a dispersion composition containing (A) a light-shielding pigment, (B) a dispersant having a specific structure, and (C) a solvent.

  When the dispersion composition of the present invention is applied to a polymerizable composition in which the pigment concentration is increased in order to enhance the light-shielding property, or in which the amount of the dispersant added at the time of dispersion is increased so as not to precipitate the light-shielding pigment. It is particularly useful. In such a case, in the conventional technique, the curing component in the polymerizable composition is reduced and the sensitivity is lowered. However, when the dispersion composition of the present invention is used, the dispersant has a function of contributing to curing, so that it is good. High sensitivity and a high pigment concentration are possible, so that the light-shielding property can be enhanced.

In the present invention, the “light-shielding color filter” is obtained by exposing and developing a photosensitive polymerizable composition containing at least a dispersion composition containing a light-shielding pigment, a polymerizable compound, and a photopolymerization initiator. This refers to the light-shielding pattern. The color of the “light-shielding color filter” in the present invention may be an achromatic color such as black or gray, or a black or gray color mixed with a chromatic color.
The “light-shielding color filter” in the present invention is a photosensitive polymerizable composition containing at least a black color material containing a light-shielding pigment as a specific component of the present invention, a polyfunctional monomer, other polymerizable compounds, a polymerization initiator, and a solvent. It is obtained by exposing and developing an object, and may be rephrased as a light shielding film or a light shielding filter.
Hereinafter, each component contained in the dispersion composition of the present invention will be described.

<(A) Light shielding pigment>
In the present invention, the light-shielding pigment refers to a pigment that can absorb light of 400 nm to 1300 nm, and is preferably a pigment that can substantially shield light having a wavelength range of 600 to 1300 nm, preferably 900 to 1300 nm. Specific examples include titanium black and carbon black. The dispersion composition of the present invention is particularly useful for titanium black, and titanium black is preferred as the light-shielding pigment.
Titanium black is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation, and is coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide. In addition, treatment with a water repellent material as described in JP-A-2007-302836 is also possible.

  As a method for producing titanium black, a method of heating and reducing a mixture of titanium dioxide and titanium metal in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), an ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

  The particle size of the titanium black particles is not particularly limited, but from the viewpoint of dispersibility and colorability, the average primary particle size is preferably in the range of 3 nm to 1000 nm, more preferably the average primary particle size of 10 nm or more. It is the range of 500 nm or less, More preferably, it is the range of 10 nm or more and 100 nm or less.

The specific surface area of titanium black is not particularly limited, but the water repellency after surface treatment of such titanium black with a water repellent agent has a predetermined performance, and therefore the value measured by the BET method is usually 5 m ² / g to 150 m ² / g or less, particularly preferably 20 m ² / g to 100 m ² / g.

  Examples of commercially available titanium black products include, for example, Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N manufactured by Mitsubishi Materials Corporation, and Tilac D manufactured by Ako Kasei Co., Ltd. However, the present invention can be used without being limited thereto.

  Further, extender pigments may be added to the titanium black in the present invention as necessary. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of the extender is usually 0 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of titanium black. In the present invention, the titanium black and extender pigment can be used by modifying the surface with a polymer in some cases.

The content of the light-shielding pigment added to the dispersion composition of the present invention is adjusted so that the content of the light-shielding pigment in the dispersion composition is 20% by mass or more and 94% by mass or less. The content of the light-shielding pigment in the dispersion composition is more preferably in the range of 40% by mass to 92% by mass, and still more preferably in the range of 40% by mass to 80% by mass.
By setting it as the said range, sclerosis | hardenability of the polymeric composition of this invention becomes favorable, and a uniform film | membrane can be formed.
Further, by containing titanium black at a high concentration, sufficient light shielding properties can be obtained, and a polymerizable composition containing titanium black can be suitably used for forming a light shielding color filter.

Moreover, you may mix and use the following as a light-shielding pigment for the dispersion composition of this invention.
Such a light-shielding pigment that can be mixed is not particularly limited as long as it has absorbance in the visible light region, and the above-mentioned extender pigment, carbon black, C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, C.I. I. Pigment Brown 25, 28, C.I. I. And organic pigments such as Pigment Black 1.
Examples of using a mixture of light-shielding pigments other than titanium black include a mixture of titanium black and carbon black in a ratio of 6: 1, a mixture of titanium black and titanium oxide in a ratio of 3: 1, and the like.
The light-shielding pigment other than titanium black used by mixing can be used in the range of 0.01 to 99.99 parts by mass with respect to 100 parts by mass of titanium black. Preferably, it is the range of 20-70 mass parts.

<(B) Dispersant having at least one terminal capable of radical polymerization and a group adsorbing to the light-shielding pigment at the other terminal>
The dispersion composition of the present invention includes (B) a dispersant having at least one terminal capable of radical polymerization and a group adsorbing to the light-shielding pigment at the other terminal (hereinafter referred to as “specific dispersant”). Say). In the dispersion composition, the specific dispersant has an adsorptive group for the light-shielding pigment and can impart excellent dispersibility, so that a dispersion composition having excellent dispersibility and dispersion stability can be obtained. Can do. Furthermore, it has a radically polymerizable group, has a high sensitivity and good curability, and a polymerizable composition having excellent pattern moldability can be obtained.
In particular, since the dispersant used in the dispersion composition of the present invention has a polymerizable group at the terminal portion of the dispersant, when the dispersant is dispersed and adsorbed on the pigment to form a pigment-dispersant complex, It is considered that a polymerizable group is located on the surface of the pigment-dispersant complex, which increases the polymerization efficiency and improves the sensitivity.

The specific dispersant of the present invention preferably has a radical-polymerizable group at at least one end of a polyether linking group and a polyester linking group, and this can particularly improve dispersibility stability.
It is presumed that the polyether linking group or the polyester linking group functions as a steric repulsion group, and can exhibit a good dispersibility and uniformly disperse the light-shielding pigment. However, when these groups interact with the solvent, precipitation of the light-shielding pigment can be suppressed for a long period of time.

  Specific examples of the polyether linking group include a polyethylene glycol linking group and a polypropylene glycol linking group. Specific examples of the polyester linking group include a polybutyrolactone linking group, a polyvalerolactone linking group, and a polycaprolactone linking group. Of these, polyethylene glycol linking groups and polycaprolactone linking groups are easy to crystallize and are difficult to handle, so the specific dispersant has a polypropylene glycol linking group and a polycaprolactone linking group at the same time. It is preferable to have two or more kinds of linking groups to be simultaneously used.

  The specific dispersant in the present invention is more preferably represented by the following general formula (1).

In General Formula (1), B represents an allyl group or a (meth) acryloyl group, Q ¹ and Q ³ each independently represent a single bond or a divalent linking group, Q ² represents an alkylene group, M represents an organic group having at least one selected from a phosphoric acid group, a carboxylic acid group, a urethane group, a urea group, an amide group, and an imino group. a represents an integer of 0 to 20, b represents an integer of 0 to 100, and (a + b) is in the range of 5 to 100. n represents an integer of 1 to 4, and p represents an integer of 2 to 8, respectively.

  In the general formula (1), M functions as a site adsorbing to the pigment, and other than M is estimated to function as a steric repulsion group for preventing aggregation of the pigments. When the chain length of the steric repulsion group is increased, the steric repulsion effect is increased and the dispersibility is improved. However, since the molecular weight is increased, the adsorptive power to the light-shielding pigment is decreased and the dispersibility is decreased. For this reason, as (B) specific dispersing agent used by this invention, it is preferable that (a + b) is the range of 5-100, and it is more preferable that it is the range of 10-40.

  Specific examples of the allyl group and the (meth) acryloyl group as B include the following structures. The acryloyl group and the methacryloyl group are collectively referred to as “(meth) acryloyl group” in the present invention.

The divalent linking group represented by Q ¹ and Q ³ is a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a divalent group. Aromatic groups (eg, arylene groups, substituted arylene groups), divalent heterocyclic groups, and oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino groups Examples include a group (—NR ³¹ —, where R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a combination with a carbonyl group (—CO—), and the like.
Among these, as a divalent linking group, an alkylene group, a cycloalkylene group, an arylene group, an alkylarylene group, an alkylcycloalkylene group, an alkyleneoxy group, an oxyalkylene group, an alkylcarbonyl group, an alkylcarbonyloxy group, an oxyalkylenecarbonyl group Groups are preferred.
These divalent linking groups may have two or more.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-15 are preferable and, as for the carbon atom number of the said aliphatic group, 1-5 are more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

  6-20 are preferable, as for the carbon atom number of the said bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocycle. The heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³¹ , where R ³¹ is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

The alkylene group when Q ² represents an alkylene group has the same meaning as the divalent aliphatic group in Q ¹ and Q ³ . Specific examples include an ethylene group and an isopropylene group. Of these, isopropylene groups are preferred because they are difficult to crystallize and are easy to handle.

_{P in} —O— (C═O) —C _p H _2p — represents an integer of 2 to 8. The ester structure forming this polyester can be obtained by ring-opening polymerization of an alkyl lactone. Specific examples of the alkyl lactone used as a raw material include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, and ε-caprolactone, of which δ-valerolactone, It is preferable to use ε-caprolactone from the viewpoint of easy ring-opening polymerization.

(A + b) represents an integer of 5 to 100. (A + b) means the length of the steric repulsion group which prevents aggregation of pigments, and if it is 5 or less, the steric repulsion function is lowered and the dispersibility is not improved. On the other hand, when (a + b) exceeds 100, the molecular weight increases, and the proportion of M that exhibits relatively high adsorptivity to the pigment decreases, so that the dispersant is difficult to adsorb to the light-shielding pigment and dispersibility does not improve. . (A + b) is more preferably in the range of 5 to 40, and still more preferably in the range of 8 to 20.
a represents an integer of 0 to 20, and b represents an integer of 0 to 100. a means the polyether chain length, and b means the polyester chain length. Depending on the type and chain length, some polyether chains and polyester chains are easy to crystallize and are difficult to handle. Therefore, it is preferable to have two or more kinds of linking groups selected from polyether linking groups and polyester linking groups at the same time. That is, a is more preferably in the range of 1-20, and b is more preferably in the range of 1-20.

The organic group represented by M is not particularly limited as long as it has at least one of a phosphoric acid group, a carboxylic acid group, a urethane group, a urea group, an amide group, and an imino group. By having such an acidic or hydrogen bonding structure, it becomes easy to adsorb to the light-shielding pigment and the dispersibility is improved.
The organic group represented by M particularly preferably has an acidic phosphoric acid group or carboxylic acid group. By introducing an acid group into the dispersant, it is possible to impart a function as a resin that imparts developability for pattern formation by alkali development when a polymerizable composition is obtained.
The organic group represented by M preferably has a urea bond or a urethane bond. By introducing a urea or urethane bond into the dispersant, when a polymerizable composition is formed, a function as a resin imparting hydrophilicity can be imparted for pattern formation by alkali development.

  When the organic group represented by M is phosphoric acid or carboxylic acid, the dispersant represented by the general formula (1) used in the present invention is represented by the general formula (2) or the general formula (3). More preferably, it is a compound.

In General Formula (2) and General Formula (3), B ¹ and B ² each independently represent an allyl group or a (meth) acryloyl group, and Q ⁴ , Q ⁶ , Q ⁷ , and Q ⁹ are Each independently represents a single bond or a divalent linking group, Q ⁵ and Q ⁸ each independently represent an alkylene group, M ¹ represents an (n1 + m1) -valent organic group, M ² represents a single bond, or (n2 + m2) ) Represents a valent organic group. a1 and a2 each independently represent an integer of 0 to 20, b1 and b2 each independently represent an integer of 0 to 100, and (a1 + b1) is 5 to 100, and (a2 + b2) is 5 to 100. Range. m1, m2, n1, and n2 each independently represents an integer of 1 to 4, and q and r each independently represents an integer of 2 to 8.

In General Formula (2) and General Formula (3), B ¹ and B ² have the same meaning as B in General Formula (1). The divalent linking group of Q ⁴ , Q ⁶ , Q ⁷ , and Q ^{9 has} the same meaning as Q ¹ and Q ³ in the general formula (1). The alkylene group represented by Q ⁵ and Q ⁸ has the same meaning as Q ^{2 in} formula (1). The organic group represented by M ¹ and M ² has the same meaning as M in the general formula (1).

Specific examples of the organic group -M ^1- (COOH) _m ¹ in the general formula (2) will be given.

  As a method for synthesizing the dispersant represented by the general formula (2), for example, a polyether chain having an allyl group or (meth) acryloyl group at one end and a hydroxyl group at the other end and / or Alternatively, it can be obtained by reacting a compound having a polyester chain with a cyclic acid anhydride.

Specific examples of the general formula (2) are given. R ¹ and R ² each independently represents a hydrogen atom or a methyl group.

Specific examples of general formula (3) are given. R ¹ and R ² each independently represents a hydrogen atom or a methyl group.

  When the organic group of M is a urethane group, a urea group or an amide group, the dispersant represented by the general formula (1) used in the present invention is a compound represented by the general formula (4) or (5). It is preferable that

In General Formula (4) and General Formula (5), B ³ and B ⁴ each independently represent an allyl group or a (meth) acryloyl group, and Q ¹⁰ and Q ¹⁴ each independently represent a single bond, or It represents a divalent linking group, Q ¹¹ and Q ¹⁵ each independently represent an alkylene group, and Q ¹² , Q ¹⁶ and Q ¹⁷ each independently represent a divalent linking group. Q ¹³ represents an n3 valent linking group, and Q ¹⁸ represents an n4 valent linking group. a3 and a4 each independently represents an integer of 0 to 20, b3 and b4 each independently represents an integer of 0 to 100, and (a3 + b3) is in the range of 5 to 100, and (a4 + b4) is in the range of 5 to 100 It is. n3 and n4 each independently represents an integer of 2 to 6, m4 represents an integer of 0 to 10, and s and t each independently represents an integer of 2 to 8.

In the general formulas (4) and (5), B ³ and B ⁴ have the same meaning as B in the general formula (1). The divalent linking group of Q ¹² , Q ¹⁶ , and Q ^{17 has} the same meaning as Q ¹ and Q ^{3 in the} general formula (1). The alkylene group of Q < ¹¹ > and Q < ¹⁵ > is synonymous with Q < ² > of General formula (1).
Q ¹³ is an n3 valent linking group, preferably an alkylene group, a cycloalkylene group, an arylene group, an alkylcycloalkylene group, or an alkylarylene group. Q ¹⁸ represents an n4-valent linking group, preferably an alkylene group, a cycloalkylene group, an arylene group, an alkylcycloalkylene group, or an alkylarylene group. When Q ¹⁰ and Q ¹⁴ are a divalent linking group, an alkylene group, a cycloalkylene group, an arylene group, an alkylarylene group, an alkylcycloalkylene group, an alkyleneoxy group, an oxyalkylene group, an alkylcarbonyl group, an alkylcarbonyl group An oxy group and an oxyalkylenecarbonyl group, preferably an alkylene group, a cycloalkylene group, an arylene group, an alkylarylene group, and an alkylcycloalkylene group.

Specific examples of the n3-valent linking group -Q ^13- in the general formula (4) are given below.

Specific examples of the divalent linking group -Q ^16- in the general formula (5) include those similar to the divalent ones among the n3 valent linking group organic groups -Q ^13- in the general formula (4). Can be mentioned.

Specific examples of the divalent linking group —Q ¹⁷ — in the general formula (5) are given below.

Specific examples of the compound represented by the general formula (4) are given below. In the following formulae, R ¹ and R ² each independently represent a hydrogen atom or a methyl group. The number of repetitions d1 of the repeating structure is 9, d2 is 9, d3 is 6, d4 is 6, d5 is 13, and d6 is 13.

Specific examples of the compound represented by the general formula (5) are given below. R ¹ and R ² each independently represents a hydrogen atom or a methyl group. The number of repetitions d7 is 8, d8 is 2, d9 is 8, d10 is 13, d11 is 5, d12 is 13, d13 is 20, d14 is 2, d15 is 20, d16 is 13, d17 is 4, d18 Is 13.

  From the viewpoint of dispersibility and dispersion stability, the content of the specific dispersant relative to the total solid content of the dispersion composition of the present invention is preferably in the range of 0.1 to 50% by mass, and in the range of 5 to 40% by mass. More preferably, the range of 10-30 mass% is further more preferable.

<(C) Solvent>
The dispersion composition of the present invention uses various organic solvents as a solvent.
Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. It is preferable that the density | concentration of solid content with respect to a solvent is 2-60 mass%.

<Dispersion composition>
In the dispersion composition of the present invention, (A) a light-shielding pigment, (B) a specific dispersant, and (C) a solvent are mixed and dispersed to obtain a dispersion composition.
In addition to the above essential components, a general-purpose dispersant described later, other resins, and the like may be added to the dispersion composition of the present invention. It is also possible to facilitate dispersion by surface-treating the light-shielding pigment with a pigment derivative or the like. Furthermore, it can be configured to contain other components as required.

-Preparation of dispersion composition-
The preparation mode of the dispersion composition of the present invention is not particularly limited. For example, (A) a light-shielding pigment, (B) a specific dispersant, and (C) a solvent are used as a vertical or horizontal sand grinder, pin mill, or slit mill. It can be obtained by carrying out fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm using an ultrasonic disperser or the like.

  Prior to bead dispersion, knead using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder, etc. while applying a strong shearing force. It is also possible to perform distributed processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

<General-purpose dispersant>
Specific examples of the general-purpose dispersant usable in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA Corporation ” 4165 (polyurethane), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (Azo face) "Ajimoto Fin Techno Co., Ltd.""Ajisper PB821, PB822", Kyoeisha Chemical Co., Ltd. "Floren TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic copolymer)", Enomoto “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Kasei Corporation, manufactured by Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," Acetami 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.
These other resins may be used alone or in combination of two or more.

<Other resins>
For the purpose of adjusting the dispersibility of the light-shielding pigment, the dispersion composition of the present invention may contain a resin other than the specific dispersant (hereinafter, may be referred to as “other resin”).
Other resins that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meta ) Acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
Other resins can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

Other resins are adsorbed on the surface of the light-shielding pigment and, if desired, the pigment used in combination, and act to prevent re-aggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
On the other hand, other resins may have an effect of promoting adsorption of the specific dispersant by modifying the pigment surface.

<Pigment derivative>
The dispersion composition of the present invention can further contain a pigment derivative.
The pigment derivative preferably has a structure in which a part of an organic pigment, anthraquinones or acridones is substituted with an acidic group, a basic group or a phthalimidomethyl group. Examples of the organic pigment constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine, aminoanthraquinone, diaminodi Anthraquinone pigments such as anthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindoline Examples thereof include linone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  As an acidic group which a pigment derivative has, a sulfonic acid, carboxylic acid, and its quaternary ammonium salt are preferable. Moreover, as a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is the most preferable.

  Although there is no restriction | limiting in particular in the usage-amount of a pigment derivative, It is preferable to use 5-50 mass% with respect to a light-shielding pigment, and it is more preferable to use 10-30 mass%.

  Further, a polymer compound such as a binder polymer described later can be added to the dispersion composition. Polar groups such as acid groups contained in the binder polymer are considered effective for dispersing the light-shielding pigment, and are often effective for the dispersion stability of the dispersion composition.

<Polymerizable composition>
The dispersion composition of the present invention contains (D) a polymerization initiator and can be mixed and used as a polymerizable composition. Details of (D) the polymerization initiator and the polymerizable composition will be described below.

<(D) Polymerization initiator>
The (D) polymerization initiator used in the polymerizable composition of the present invention is decomposed by light, and includes the specific dispersant of the present invention and (E) a polymerizable compound described later added to the polymerizable composition as necessary. It is a compound that initiates and promotes polymerization, and preferably has absorption in a wavelength region of 300 nm to 500 nm. Moreover, a polymerization initiator can be used individually or in combination of 2 or more types.

  (D) Examples of the polymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples include hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-3070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241. JP, 62-21401, JP 63-70243, 63-298339, M.M. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

As the biimidazole compound, for example, a hexaarylbiimidazole compound (rophine dimer compound) is preferable.
Examples of the hexaarylbiimidazole compound include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, JP-B-6-29285, U.S. Pat. No. 3,479,185, and the like. Various compounds described in each specification such as 4,311,783 and 4,622,286, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) vididazole, 2, 2'-bis (o , O′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5 Examples include '-tetraphenylbiimidazole.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

The (E) polymerization initiator used in the present invention is preferably an oxime compound from the viewpoints of sensitivity, stability over time, and coloring during post-heating.
Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Publication No. 2004-534797 Compounds and the like.

  The oxime compound used in the present invention is more preferably a compound represented by the following formula (IV) from the viewpoint of sensitivity and stability over time. A compound in which the S atom is changed to an O atom or —CO— in the following formula (IV) is also preferable, but a compound having an S atom is more preferable.

In formula (IV), R ⁹ and X ³ each independently represent a monovalent substituent, A ⁰ represents a divalent organic group, and Ar represents an aryl group. u3 is an integer of 1-5.

The monovalent substituent represented by R ⁹ is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R ⁹ include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a group, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent May have a phosphinoyl group, a heterocyclic group which may have a substituent, an alkylthiocarbonyl group which may have a substituent, an arylthiocarbonyl group which may have a substituent, or a substituent. Dialkylaminoca Examples thereof include a sulfonyl group and a dialkylaminothiocarbonyl group which may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitro Enashiru group, and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples thereof include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, for example, methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexyl. Examples thereof include a sulfinyl group, a cyclohexylsulfinyl group, an octylsulfinyl group, a 2-ethylhexylsulfinyl group, a decanoylsulfinyl group, a dodecanoylsulfinyl group, an octadecanoylsulfinyl group, a cyanomethylsulfinyl group, and a methoxymethylsulfinyl group.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, for example, phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group. 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenyl Sulfinyl group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexyl. Sulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, perfluoroalkylsulfonyl group, etc. Can be mentioned.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, and a 2-chlorophenylsulfonyl group. 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylamino Enirusuruhoniru group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 or more and 20 or less carbon atoms. For example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1- Naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxy Benzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxy A benzoyl group etc. are mentioned.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, Examples include octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, and the like.

  The aryloxycarbonyl group which may have a substituent includes a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, and a 4-phenylsulfanylphenyloxycarbonyl group. 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fur B phenyloxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms in total, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphino group. Yl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the alkylthiocarbonyl group which may have a substituent include, for example, methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, Examples thereof include a trifluoromethylthiocarbonyl group.

  Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl. Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Boniru group, 4-methoxyphenyl thiocarbonyl group.

  Examples of the dialkylaminocarbonyl group that may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

  Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

Among these, from the viewpoint of increasing sensitivity, R ⁹ is more preferably an acyl group, and specifically, an acetyl group, an ethyloyl group, a propioyl group, a benzoyl group, and a toluyl group are preferable.

Examples of the divalent organic group represented by A ⁰ in the formula (IV) include an optionally substituted alkylene group having 1 to 12 carbon atoms, an optionally substituted cyclohexylene group, and a substituted group. An alkynylene group which may have a group is mentioned.
Examples of the substituent that can be introduced into these groups include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Aryloxy groups such as tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group Group, acyl group such as methacryloyl group, methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, Alkylamino groups such as rohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, methyl group, ethyl group, tert- In addition to alkyl groups such as butyl group and dodecyl group, phenyl groups, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and the like, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group Group, triphenylphenacylphos Niumiru group, and the like.
Among them, A ⁰ is substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. An alkylene group, an alkylene group substituted with an alkenyl group (eg, vinyl group, allyl group), an aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl) An alkylene group substituted with a group) is preferred.

The aryl group represented by Ar in the formula (IV) is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, Turnaphthalenyl group, Quarter naphthalenyl group, Heptaenyl group, Biphenylenyl group, Indacenyl group, Fluoranthenyl group, Acenaphthylenyl group, Aceantrirenyl group, Phenalenyl group, Fluorenyl group, Anthryl group, Bianthracenyl group, Teranthracenyl group, Quarter Anthracenyl group, anthraquinolyl group, phenanthri Group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, A trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like can be given. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group. Group, aryloxy group such as phenoxy group, p-tolyloxy group, methylthioxy group, ethylthioxy group, alkylthioxy group such as tert-butylthioxy group, arylthiooxy group such as phenylthioxy group, p-tolyloxy group, methoxycarbonyl Groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc. Group, Alkylsulfanyl groups such as tilsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, alkylamino groups such as methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, Dialkylamino groups such as morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as ethyl group, tert-butyl group and dodecyl group, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, di Chill sulfo Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

  In the formula (IV), it is preferable from the viewpoint of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

Examples of the monovalent substituent represented by X ³ in the formula (IV) include an alkyl group which may have a substituent, an aryl group which may have a substituent, and an alkenyl which may have a substituent. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group that may have a substituent, an acyloxy group that may have a substituent, an alkylsulfanyl group that may have a substituent, an arylsulfanyl group that may have a substituent, and a substituent. An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and a substituent Has a good acyl group and substituent An alkoxycarbonyl group which may have a substituent, a carbamoyl group which may have a substituent, a sulfamoyl group which may have a substituent, an amino group which may have a substituent, a phosphinoyl group which may have a substituent And a heterocyclic group which may have a substituent, a halogen group and the like.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group. , Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl Group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, - Nitorofenashiru group and the like.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and includes a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl group. 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o -, M-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl , Phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, tarant Senyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group. Group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylami Carbonyl methyl group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, for example, a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, or a 2-chlorophenyloxy group. 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, and the like.

  The alkylthioxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms, such as methylthioxy group, ethylthioxy group, propylthioxy group, isopropylthioxy group, butylthioxy group, isobutyl. Thioxy group, sec-butylthioxy group, tert-butylthioxy group, pentylthioxy group, isopentylthioxy group, hexylthioxy, heptylthioxy group, octylthioxy group, 2-ethylhexylthioxy group, decylthioxy group, dodecyl Examples include a thioxy group, an octadecyl thioxy group, and a benzyl thioxy group.

  The arylthioxy group which may have a substituent is preferably an arylthioxy group having 6 to 30 carbon atoms, such as a phenylthioxy group, a 1-naphthylthioxy group, a 2-naphthylthioxy group, 2-chlorophenylthioxy group, 2-methylphenylthioxy group, 2-methoxyphenylthioxy group, 2-butoxyphenylthioxy group, 3-chlorophenylthioxy group, 3-trifluoromethylphenylthioxy group, 3- Cyanophenylthioxy group, 3-nitrophenylthioxy group, 4-fluorophenylthioxy group, 4-cyanophenylthioxy group, 4-methoxyphenylthioxy group, 4-dimethylaminophenylthioxy group, 4-methyl Examples thereof include a sulfanylphenylthioxy group and a 4-phenylsulfanylphenylthioxy group.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyl. Examples thereof include an oxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, and a 2-naphthylcarbonyloxy group.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms, such as methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, hexyl. Examples thereof include a sulfanyl group, a cyclohexylsulfanyl group, an octylsulfanyl group, a 2-ethylhexylsulfanyl group, a decanoylsulfanyl group, a dodecanoylsulfanyl group, an octadecanoylsulfanyl group, a cyanomethylsulfanyl group, and a methoxymethylsulfanyl group.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, a 1-naphthylsulfanyl group, a 2-naphthylsulfanyl group, or a 2-chlorophenylsulfanyl group. 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenyl Sulfanyl group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, for example, methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexyl. Examples thereof include a sulfinyl group, a cyclohexylsulfinyl group, an octylsulfinyl group, a 2-ethylhexylsulfinyl group, a decanoylsulfinyl group, a dodecanoylsulfinyl group, an octadecanoylsulfinyl group, a cyanomethylsulfinyl group, and a methoxymethylsulfinyl group.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, for example, phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group. 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenyl Sulfinyl group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexyl. Examples include a sulfonyl group, a cyclohexylsulfonyl group, an octylsulfonyl group, a 2-ethylhexylsulfonyl group, a decanoylsulfonyl group, a dodecanoylsulfonyl group, an octadecanoylsulfonyl group, a cyanomethylsulfonyl group, and a methoxymethylsulfonyl group.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, and a 2-chlorophenylsulfonyl group. 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylamino Enirusuruhoniru group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 or more and 20 or less carbon atoms. For example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1- Naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxy Benzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxy A benzoyl group etc. are mentioned.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, Octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4 -Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl Bonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl Group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms in total, for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-butylcarbamoyl group. Group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2 -Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyano Phenylcarbamo Group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms in total, for example, sulfamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, N, N -Dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like can be mentioned. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

  The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH 2, N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) Amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, - dimethyl morpholino group, and a carbazolyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms in total, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphino group. Yl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthioxy group that may have a substituent, an arylthioxy group that may have a substituent, and a substituent. An acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, and a substituent. Good arylsulfinyl group, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl which may have a substituent Base The carbamoyl group which may have a substituent, the sulfamoyl group which may have a substituent, the amino group which may have a substituent, and the heterocyclic group which may have a substituent may be further substituted. It may be substituted with a group.

  Examples of such a substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy group. Aryloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group , Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyl Alkylamino group such as mino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl group In addition to alkyl groups such as dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, Triphenylphenacylphosphoniumyl group And the like.

Among these, X ³ has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of solvent solubility and improvement in absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio which may have a substituent A xyl group, an arylthioxy group which may have a substituent, and an amino group which may have a substituent are preferable.
Moreover, u3 in Formula (IV) represents an integer of 0 to 5, and an integer of 0 to 2 is preferable.

  Specific examples of the oxime compound represented by the formula (IV) are shown below, but the present invention is not limited thereto.

  The oxime compound represented by the formula (IV) has a function as a photopolymerization initiator that is decomposed by light and initiates and accelerates polymerization of the photopolymerizable compound. In particular, the oxime compound has excellent sensitivity to a light source of 365 nm or 405 nm.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it may be substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group. preferable. In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt having a triarylsulfonium salt having an aryloxy group or an arylthio group as a substituent and having absorption at 300 nm or more can be mentioned.

Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello
et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt, C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the polymerization initiator (D) used in the polymerizable composition of the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound are used. Compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof And a compound selected from the group consisting of a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  In particular, when the polymerizable composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is necessary to form fine pixels with a sharp shape, and therefore, a residue is left in the unexposed area along with curability. It is important that it is developed without any problems. From such a viewpoint, a polymerization initiator of an oxime compound is particularly preferable. In particular, when fine pixels are formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low. Considering these points, it is most preferable to use an oxime polymerization initiator as the polymerization initiator (D) in order to form a finely colored pattern such as a solid-state imaging device. In particular, as the oxime polymerization initiator, the compound represented by the above formula (IV) is preferable.

  The content of the polymerization initiator (D) contained in the polymerizable composition of the present invention is preferably 0.1% by mass or more and 50% by mass or less, more preferably based on the total solid content of the polymerizable composition. Is 0.5 mass% or more and 30 mass% or less, More preferably, it is 1 mass% or more and 20 mass% or less. Within this range, good sensitivity and pattern formability can be obtained.

  The content of the light-shielding pigment with respect to the total solid content of the polymerizable composition of the present invention is preferably in the range of 0.1 to 60% by mass from the viewpoint of necessary light-shielding expression, imparting developability, and the like. A range of 50% by mass is more preferred.

<(E) Polymerizable compound>
The polymerizable composition of the present invention can be further enhanced in sensitivity by including (E) a polymerizable compound, and it is preferable that (E) the polymerizable compound is contained in the polymerizable composition.
(E) The polymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such compounds are widely known in the industrial field, and can be used without any particular limitation in the present invention.

  These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (V) to a polyisocyanate compound having two or more isocyanate groups. Etc.

式（Ｖ）中、Ｒ^７、及びＲ^８は、それぞれ、Ｈ又はＣＨ_３を示す。

In formula (V), R ⁷ and R ⁸ each represent H or CH ₃ .

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Furthermore, by using polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a polymerizable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Also, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of polymeric composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, selection of a polymerizable compound is also required for compatibility and dispersibility with other components contained in the polymerizable composition (for example, a polymerization initiator, a light shielding material such as a light shielding pigment (pigment, dye), etc.). The usage method is an important factor, and for example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.

In the total solid content of the polymerizable composition, the content of the polymerizable compound (E) is preferably in the range of 5% by mass to 90% by mass, and more preferably in the range of 10% by mass to 85% by mass. More preferably, it is in the range of 20% by mass to 80% by mass.
Within this range, both adhesion sensitivity and developability are favorable and preferable without diminishing the hue.

The polymerizable composition of the present invention may further contain optional components described in detail below, if necessary. Hereinafter, optional components that the polymerizable composition may contain will be described.
[Sensitizer]
The polymerizable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
The sensitizer that can be used in the present invention is preferably a sensitizer that is sensitized by the electron transfer mechanism or the energy transfer mechanism with respect to the above-described (D) polymerization initiator.

Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryu (Eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  More preferred examples of the sensitizer that can be used in the present invention include compounds represented by the following general formulas (e-1) to (e-4).

In formula (e-1), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ¹ represents a basic nucleus of the dye in combination with adjacent A ¹ and an adjacent carbon atom. R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. May be. W represents an oxygen atom or a sulfur atom.

In formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ² —. Here -L ² - represents -O- or -S-. Moreover, W is synonymous with what was shown to Formula (e-1).

In the formula (e-3), A ² represents a sulfur atom or NR ⁵⁹ , L ³ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with the adjacent A ² and carbon atom, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a group of a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (e-4), A ³ and A ⁴ each independently represent —S— or —NR ⁶² , and R ⁶² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. , L ⁴ and L ⁵ each independently represent a nonmetallic atomic group which forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶⁰ and R ⁶¹ each independently Represents a monovalent non-metallic atomic group, or can be bonded to each other to form an aliphatic or aromatic ring.

The content of the sensitizer in the polymerizable composition is preferably 0.1% by mass or more and 20% by mass or less in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. It is more preferably 5% by mass or more and 15% by mass or less.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Further, as a preferable sensitizer that can be contained in the polymerizable composition, in addition to the sensitizer, a compound represented by the following general formula (II) and a compound represented by the general formula (III) are selected. At least one kind.
These may be used individually by 1 type, and may use 2 or more types together.

In general formula (II), R ¹¹ and R ¹² each independently represents a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. To express. u1 represents an integer of 0 to 5, u2 represents an integer of 0 to 5, and u1 and u2 are not both 0. When u1 is 2 or more, a plurality of R ¹¹ may be the same or different. When u2 is 2 or more, a plurality of R ¹² may be the same or different. In the general formula (II), the isomer by the double bond is not limited to either.

The compound represented by the general formula (II) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and ε at a wavelength of 365 nm of 3000 mol ⁻¹ · L · cm ^{−. 1} or more is more preferable, and ε at a wavelength of 365 nm is most preferably 20000 mol ⁻¹ · L · cm ⁻¹ or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Although the preferable specific example of a compound represented by general formula (II) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group.

In the general formula (III), A ⁵ represents an aromatic ring or a hetero ring which may have a substituent, X ⁴ represents an oxygen atom, a sulfur atom, or —N (R ²³ ) —, and Y represents oxygen atom, a sulfur atom, or -N ^{(R 23)} - represents a. R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A ⁵ , R ²¹ , R ²² , and R ²³ are bonded to each other to form an aliphatic group Or aromatic rings may be formed.

In the general formula (III), R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ²¹ , R ²² , and R ²³ represent a monovalent nonmetallic atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted fragrance It is preferably a group heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxy group, or a halogen atom.

In the compound represented by the general formula (III), Y is preferably an oxygen atom or —N (R ²³ ) — from the viewpoint of improving the decomposition efficiency of the polymerization initiator. R ²³ represents a hydrogen atom or a monovalent nonmetallic atomic group. Further, Y is most preferably —N (R ²³ ) —.

  Hereinafter, although the preferable specific example of a compound represented by general formula (III) is shown, this invention is not limited to this. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

[Co-sensitizer]
The polymerizable composition of the present invention preferably further contains a co-sensitizer.
In the present invention, the co-sensitizer has an action such as (D) further improving the sensitivity of the polymerization initiator or sensitizer to actinic radiation or suppressing polymerization inhibition due to oxygen.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is 0.1% by mass or more and 30% by mass or less with respect to the mass of the total solid content of the polymerizable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range of 1 mass% or more and 25 mass% or less is more preferable, and the range of 0.5 mass% or more and 20 mass% or less is still more preferable.

[Polymerization inhibitor]
In the present invention, during the production or storage of the dispersion composition and the polymerizable composition, a polymerization inhibitor is added to prevent unnecessary polymerization of (B) the specific dispersant and (E) the polymerizable compound. It is preferable to do.
Examples of the polymerization inhibitor that can be used in the present invention include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium. Examples include compounds, and transition dye compounds such as cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, FeCl 3 and CuCl 2.

  Specific examples of the polymerization inhibitor are preferably hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol) phenolic hydroxyl group-containing compounds, piperidine 1-oxyl free radical compounds, or 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- Acetamide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide-2, , 6,6-tetramethylpiperidine 1-oxyl free radical, and piperidine 1-oxyl free radical compound of 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, or N-nitrosophenyl hydroxyl N-nitrosophenylhydroxylamine compounds of amine cerium salt and N-nitrosophenylhydroxylamine aluminum salt, more preferably 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo- 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6- Tetramethylpiperidine 1-oxyl free radical, Piperidine 1-oxyl free radical compound of 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical Or N-nitrosophenylhydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine aluminum salt, more preferably -nitrosophenylhydroxylamine primary cerium salt and N-nitrosophenyl N-nitrosophenylhydroxylamine compound of hydroxylamine aluminum salt.

A preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.01 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polymerization initiator (D). It is preferable that it is in the range of 0.05 parts by mass or more and 5 parts by mass or less.
By setting it as the above range, the curing reaction in the non-image area is sufficiently suppressed and the curing reaction in the image area is sufficiently promoted, and the image formability and sensitivity are improved.

[Binder polymer]
In the polymerizable composition, a binder polymer can be further used as necessary for the purpose of improving the film properties. It is preferable to use a linear organic polymer as the binder. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such a linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or Resin copolymerized, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half esterified or half amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  In the present invention, when a copolymer is used as the binder polymer, a monomer other than the monomers listed above can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

Also, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947. Urethane-based binder polymers containing acid groups described in Japanese Patent Application Laid-Open No. 1-271741, Japanese Patent Application No. 10-116232, and acid groups and double compounds described in Japanese Patent Application Laid-Open No. 2002-107918. A urethane-based binder polymer having a bond in the side chain is very excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, an acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer that can be used in the polymerizable composition of the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably It is 1,000 or more, More preferably, it is the range of 2,000 or more and 250,000 or less. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the binder polymer that can be used in the polymerizable composition of the present invention include known compounds such as an azo initiator and a peroxide initiator.

  In the total solid content of the polymerizable composition, the content of the binder polymer is preferably 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less, and more preferably 4% by mass or more. More preferably, it is 20 mass% or less.

[Adhesion improver]
In the polymerizable composition of the present invention, an adhesion improver can be added in order to improve adhesion with a hard surface such as a substrate. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

  Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.

  Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  The addition amount of the adhesion improver is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 0.7% by mass or more and 20% by mass or less in the total solid content of the polymerizable composition.

[Other additives]
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers and plasticizers may be added to the polymerizable composition.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

  The polymerizable composition of the present invention is suitable for forming a light-shielding color filter because it has high dispersibility when the light-shielding pigment is dispersed, the residue in the unexposed area is suppressed, and the applicability when applied to the substrate is good. Can be used.

<Color filter with black matrix>
The color filter having the black matrix of the present invention is formed using the above-described polymerizable composition of the present invention. The black matrix formed using the polymerizable composition of the present invention has a reduced residue, high flatness, and can be improved in shape without steps.

  In the present invention, the step means a step observed in a black matrix having a side of about 200 μm or more formed by applying, exposing and developing a polymerizable composition. When the black matrix is observed with an optical microscope from above the film surface, the step may be observed as a line substantially similar to the pattern edge of the black matrix.

FIG. 1 is a plan view schematically showing a state in which a step occurs in the black matrix 10, and FIG. 2 is a cross-sectional view. The solid line represents the pattern edge 1 of the light-shielding color filter, and the broken line represents step 2.
The film thickness of the black matrix is the area inside the step (area surrounded by step 2 in FIG. 1) in the area outside the step (area between the pattern edge 1 and step 2 in FIG. 1). It is thinner than. In other words, the area outside the step (hereinafter also referred to as “step area”) has a low light shielding ability, which causes noise when used as a black matrix for a solid-state image sensor. Effect.
In addition, when forming a black matrix using the polymerizable composition of the present invention, it is possible to suppress a phenomenon that a region (step region) in which the film thickness is thinner than the central portion is formed in the peripheral portion of the black matrix, and the light shielding ability in the peripheral portion is reduced. Reduction can be suppressed.

The film thickness of the black matrix is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and 0.5 μm or more and 30 μm or less. More preferably, it is 0.7 μm or more and 10 μm or less.
The size (length of one side) of the black matrix is preferably 0.001 mm or more and 5 mm or less, more preferably 0.05 mm or more and 4 mm or less, and more preferably 0.05 mm or more from the viewpoint of obtaining the effect of the present invention more effectively. More preferably, it is 3.5 mm or less.

<Light-shielding color filter having black matrix and method for producing the same>
Next, the light-shielding color filter having the black matrix of the present invention and the manufacturing method thereof will be described.
The light-shielding color filter having a black matrix of the present invention is characterized by having a colored pattern formed using the polymerizable composition of the present invention on a substrate.
Hereinafter, the light-shielding color filter having the black matrix of the present invention will be described in detail through its manufacturing method.

  The method for producing a light-shielding color filter having a black matrix of the present invention comprises a step of applying a polymerizable composition of the present invention on a substrate to form a polymerizable composition layer (hereinafter referred to as “polymerizable composition layer as appropriate”). Abbreviated as “formation step”), a step of exposing the polymerizable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and developing the polymerizable composition layer after exposure. And a step of forming a colored pattern (hereinafter abbreviated as “development step” as appropriate).

Specifically, the polymerizable composition of the present invention is applied on a substrate directly or via another layer to form a polymerizable composition layer (polymerizable composition layer forming step), and a predetermined mask. By exposing only the coating film portion exposed through the pattern and curing the light (exposure process) and developing with a developer (development process), a pattern-like film composed of pixels is formed, and the light-shielding property of the present invention A color filter can be manufactured.
Hereinafter, each process in the manufacturing method of the light-shielding color filter which has the black matrix of this invention is demonstrated.

[Polymerizable composition layer forming step]
In the polymerizable composition layer forming step, the polymerizable composition layer of the present invention is coated on the substrate to form a polymerizable composition layer.

Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, solid-state imaging devices, and the like. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate and a complementary metal oxide semiconductor (CMOS).
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with an upper layer, prevent diffusion of substances, or planarize the substrate surface.

  As a coating method of the polymerizable composition of the present invention on the substrate, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.

  When producing a color filter having a black matrix for a solid-state imaging device, the coating thickness of the polymerizable composition is preferably from 0.35 μm to 1.5 μm from the viewpoint of resolution and developability. More preferably, it is 40 μm or more and 1.0 μm or less.

  The polymerizable composition applied on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower for about 2 minutes or longer and 4 minutes or shorter to form a polymerizable composition layer.

[Exposure process]
In the exposure step, the polymerizable composition layer formed in the polymerizable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. Irradiation intensity 5 mJ / cm ² or more 1500 mJ / cm ² or less is preferably 10 mJ / cm ² or more 1000 mJ / cm ² and more preferably less, 10 mJ / cm ² or more 800 mJ / cm ² or less is most preferable.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, when producing a light-shielding color filter having a black matrix for a solid-state imaging device, an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable. The development temperature is usually from 20 ° C. to 30 ° C., and the development time is from 20 seconds to 90 seconds.

  Examples of the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate as an inorganic developer, ammonia water, ethylamine as an organic alkali developer. Alkaline compounds such as diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, with a concentration of 0 An alkaline aqueous solution dissolved in an amount of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In the method for producing a color filter having a black matrix of the present invention, after the above-described polymerizable composition layer forming step, exposure step, and development step are performed, the formed colored pattern is heated and heated as necessary. A curing step of curing by exposure may be included.

Since the color filter having the black matrix of the present invention uses the polymerizable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is resistant to development. Since it is excellent, it is possible to form a high-resolution pattern that has excellent exposure sensitivity, good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape.
Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or CMOS that exceeds 1 million pixels. That is, the light-shielding color filter provided with the black matrix of the present invention is preferably applied to a solid-state image sensor.
The color filter having the black matrix of the present invention can be used as, for example, a black matrix disposed between a light receiving portion of each pixel constituting a CCD and a microlens for collecting light.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes a color filter having the above-described black matrix of the present invention and a patterned film composed of pixels of other colors (three colors or four colors) as necessary.
Since the solid-state imaging device of the present invention is provided with the black matrix of the present invention in which a decrease in light shielding ability in the peripheral portion is suppressed, noise can be reduced and color reproducibility can be improved.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the black matrix of the present invention and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. CCD image sensor, CMOS image sensor, etc.) having a plurality of photodiodes constituting a light receiving area and a light receiving element made of polysilicon, etc., and the black matrix of the present invention is formed on the surface opposite to the light receiving element forming surface of the substrate. The provided structure etc. are mentioned.

<Liquid crystal display device>
One of the liquid crystal display devices of the present invention includes at least a color filter, a liquid crystal layer, and a liquid crystal driving unit (including a simple matrix driving method and an active matrix driving method) between a pair of light-transmitting substrates. A color filter having a plurality of pixel groups as described above and having each pixel constituting the pixel group separated from each other by the black matrix of the present invention is used as the color filter. Since the black matrix has high flatness, the liquid crystal display device including the black matrix does not generate cell gap unevenness between the color filter and the substrate, and display defects such as color unevenness do not occur.

  Another aspect of the liquid crystal display device of the present invention includes at least one color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light-transmitting substrates, and the liquid crystal driving means is active. It is a polymerizable composition for producing a black matrix of the present invention having an element (for example, TFT) and between each active element.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis of Specific Dispersant 1>
Into a 500 mL three-necked flask, 114.1 g of ε-caprolactone and 11.6 g of hydroxyethyl acrylate were introduced and dissolved while stirring while blowing nitrogen. 0.05 g of monobutyltin oxide was added and heated to 100 ° C. After 6 hours, it was cooled to 80 ° C. after confirming disappearance of the raw material by 1H-NMR. After adding 0.6 g of 2,6-di-t-butyl-4-methylphenol, 11.1 g of pyromellitic anhydride was added. Three hours later, after confirming disappearance of the raw material by ¹ H-NMR, the mixture was diluted with 136.9 g of propylene glycol monomethyl ether acetate, cooled to room temperature, and the following formula (2) having a solid content concentration of 30% by mass Specific dispersant 1 was obtained.

<Synthesis of Specific Dispersant 2>
In a 500 mL three-necked flask, 107 g of Bremer AP-550 (manufactured by NOF Corporation) and 0.6 g of 2,6-di-t-butyl-4-methylphenol were mixed, and 34.5 g of trimellitic anhydride, dia After adding 3 drops of zabicycloundecene, the mixture was reacted at 120 ° C. for 3 hours. After confirming the disappearance of the raw material by ¹ H-NMR, it was diluted with 331.5 g of propylene glycol monomethyl ether acetate, cooled to room temperature, and the following structure (n is about 9) having a solid content concentration of 30% by mass The specific dispersant 2 of (2) was obtained.

<Synthesis of Specific Dispersant 3>
In a 500 mL three-necked flask, 107 g of Blemmer AP-550 (manufactured by NOF Corporation) and 4.6 g of ε-caprolactone were introduced and stirred and dissolved while blowing nitrogen. Monobutyltin oxide 0.1g was added and it heated at 120 degreeC. After 6 hours, the raw material disappeared by ¹ H-NMR, and then cooled to 80 ° C. After adding 0.6 g of 2,6-di-t-butyl-4-methylphenol, 27.9 g of 4,4-oxydiphthalic anhydride was added. After 3 hours, after confirming disappearance of the raw material by ¹ H-NMR, it was diluted with 327 g of propylene glycol monomethyl ether acetate, cooled to room temperature, and the following structure (n is about 9) having a solid content concentration of 30% by mass. A specific dispersant 3 of formula (2) was obtained.

<Synthesis of Specific Dispersant 4>
Into a 500 mL three-necked flask, 89.2 g of Bremer AP-550 (manufactured by NOF Corporation), 17.0 g of ε-caprolactam, 0.5 g of 2,6-di-t-butyl-4-methylphenol was added and nitrogen was added. The solution was stirred and dissolved while blowing. Monobutyltin oxide 0.1g was added and it heated at 120 degreeC. After 6 hours, the raw material disappeared by ¹ H-NMR, and then cooled to 80 ° C. 15.8 g of trimethylhexamethylene diisocyanate was added and reacted at 80 ° C. for 4 hours. After confirming the disappearance of the raw material by ¹ H-NMR, it was diluted with 285.8 g of propylene glycol monomethyl ether acetate, cooled to room temperature, and the following structure (n is about 9) having a solid content concentration of 30% by mass The specific dispersant 4 of (4) was obtained.

<Synthesis of Specific Dispersant 5>
In a 500 mL three-necked flask, 3.7 g of 2-ethyl-2-carboxyl-1,3-propanediol, 10.5 g of trimethylhexamethylene diisocyanate, and 100 mL of tetrahydrofuran are refluxed at 60 ° C. for 6 hours. Thereafter, 32.7 g of Bremer AP-550 (manufactured by NOF Corporation) and 0.5 g of 2,6-di-t-butyl-4-methylphenol were added and stirred and dissolved at 80 ° C. while blowing nitrogen. . After 4 hours, the mixture was diluted with 109.4 g of propylene glycol monomethyl ether acetate and cooled to room temperature to obtain a specific dispersant 5 of the formula (5) having the following structure (n is about 9) with a solid content concentration of 30% by mass. .

<Synthesis of Comparative Dispersant 2>
(1) Synthesis of precursor 30 g of N-phenylmaleimide, 20 g of methacrylic acid, 20 g of styrene, 30 g of benzyl methacrylate, 233 g of propylene glycol monomethyl ether acetate, 3.0 g of 2,2′-azobisbutyronitrile, 2,4-diphenyl 2.0 g of -4-methyl-1-pentene was mixed and reacted at 80 ° C. for 3 hours to obtain an alkali-soluble resin precursor. This resin had a polystyrene-equivalent weight average molecular weight of 15,300 and an acid value of 130 (mgKOH / g).

(2) Synthesis of Comparative Dispersant 2 20 g of the alkali-soluble resin precursor synthesized above, 0.2 g of p-methoxyphenol, 0.2 g of tetraethylammonium chloride, and 5 g of propylene glycol monomethyl ether acetate were charged in a flask. -2.1 g of epoxy cyclohexyl methyl acrylate was added and reacted at 90 ° C for 30 hours to obtain Comparative Dispersant 2 having the following structure. The polystyrene-reduced weight average molecular weight of this resin was 15900, and the acid value was 97 (mgKOH / g).

(Example 1)
<Preparation of titanium black dispersion>
The following composition 1 was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. The kneader was kneaded for 30 minutes before the high viscosity dispersion treatment.

<Composition 1>
・ 39 parts of titanium black with an average primary particle size of 75 nm (Mitsubishi Materials Corporation 13M-C) 39 parts ・ Propylene glycol monomethyl ether acetate 60 parts

  The following composition 3 and composition 4 were added to the resulting dispersion, and the mixture was stirred for 3 hours using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a disperser (trade name: manufactured by Dispermat GETZMANN) using zirconia beads having a diameter of 0.3 mm to obtain a titanium black dispersion A (hereinafter referred to as TB). Dispersion A) and titanium black dispersion B (hereinafter referred to as TB dispersion B) were obtained.

<Composition 3>
-30 parts of 30% by weight propylene glycol monomethyl ether acetate solution of specific dispersant 1 <composition 4>
45 parts of 30% by weight propylene glycol monomethyl ether acetate solution of specific dispersant 1

The following components were mixed with a stirrer to prepare polymerizable composition A and polymerizable composition B, respectively.
(Composition A: Polymerizable composition A)
Benzyl methacrylate / methacrylic acid copolymer (binder polymer) 3.0 parts (composition ratio: benzyl methacrylate / methacrylic acid copolymer = 70/30 (wt%), weight average molecular weight: 25000)
-Nippon Kayaku KAYARAD DPHA (polymerizable compound) 2.0 parts-TB dispersion A 26.0 parts-Propylene glycol monomethyl ether acetate (solvent) 10 parts-Ethyl-3-ethoxypropionate (solvent) 8 parts・ Polymerization initiator: 0.8 parts of the compounds described in Table 2 below ・ 4-methoxyphenol (polymerization inhibitor) 0.01 parts

(Composition B: Polymerizable composition B)
Benzyl methacrylate / methacrylic acid copolymer (binder polymer) 3.0 parts (composition ratio: benzyl methacrylate / methacrylic acid copolymer = 70/30 (mass%), weight average molecular weight: 25000)
-Nippon Kayaku KAYARAD DPHA (polymerizable compound) 2.0 parts-TB dispersion B 26.0 parts-Propylene glycol monomethyl ether acetate (solvent) 10 parts-Ethyl-3-ethoxypropionate (solvent) 8 parts・ Polymerization initiator: 0.8 parts of the compounds shown in Table 1 below ・ 4-methoxyphenol (polymerization inhibitor) 0.01 parts

<Exposure sensitivity of color filter with black matrix for solid-state image sensor>
Using the above polymerizable composition as a resist solution, a spine coater is applied on the undercoat layer of a silicon wafer provided with an undercoat layer of a solder resist so that the dry film thickness of the applied film is 1 μm, and is left as it is for 10 minutes. And a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at a wavelength of 365 nm by changing the exposure dose to various exposure doses of 10 to 200 mJ / cm ² .

Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd.
Next, the silicon wafer on which the coating film is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center. Then, the wafer was supplied in a shower form and rinsed, and then spray-dried to form a wafer having a black matrix.
The exposure amount at which the pattern line width after development was 20 μm was evaluated as exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

(Examples 2 to 14 and Comparative Examples 1 to 3)
In the preparation of the dispersion composition of Example 1, the dispersant was changed to the specific dispersant shown in Table 1 or the comparative dispersant, and the polymerization initiator of the polymerizable composition was changed to the polymerization initiator shown in Table 1. Were operated in the same manner as in Example 1.

The materials used in Table 1 other than those shown in the synthesis examples are shown below.
Comparative dispersant 1: Dimethylaminoethyl methacrylate (Kyoeisha Chemical Co., Ltd. Light Ester DM)
Comparative dispersant 3: Polyurethane dispersant (trade name: Disperbyk-167, manufactured by Big Chemie Japan)
Polymerization initiator compounds 1-4 and 6 are shown below.

[Evaluation]
The following evaluation was performed using the dispersion composition and the polymerizable composition obtained as described above. The results are summarized in Table 1 together with the exposure sensitivity described above.

-Viscosity of the dispersion composition-
Further, the viscosity of the dispersion composition was measured using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.). The smaller the viscosity of the dispersion composition, the higher the dispersibility.

-Evaluation of storage stability (stability over time)-
After each polymerizable composition was stored at room temperature for 1 month, the degree of sedimentation of titanium black was evaluated according to the following criteria. The numerical method is calculated from the absorbance change rate of the polymerizable composition diluted 1000-fold with propylene glycol monomethyl ether acetate by a visible light absorptiometer (CARY-5 manufactured by Varian).
-Criteria-
○: Sedimentation of titanium black of 0% or more and less than 2% was observed Δ: Sedimentation of titanium black of 2% or more and less than 5% was observed ×: Sedimentation of titanium black of 5% or more was observed

As is clear from Table 1, Examples 1 to 14 according to the dispersion composition of the present invention using a specific dispersant as a black matrix for a solid-state imaging device have a low viscosity of the dispersion composition and good dispersibility. I understand that. Moreover, it turned out that the polymeric composition using the dispersion composition of this invention showed favorable storage stability, and the exposure sensitivity was small and the sensitivity was high.
Moreover, it turns out that Examples 1-12 which used the oxime type compound as a polymerization initiator are further excellent in sensitivity.

<Creation of black matrix for liquid crystal display>
Next, using the polymerizable composition used for the solid-state imaging device as it was, a color filter having a black matrix for a liquid crystal display device was produced and evaluated.
That is, using the same polymerizable composition as that used in the production of the color filter for the solid-state imaging device, slit coating was performed on a 250 mm × 350 mm glass substrate under the following conditions, followed by vacuum drying and pre-baking (100 ° C., 80 Second) to form a polymerizable composition coating film. Then, the exposure amount was changed to various exposure amounts of 10 to 200 mJ / cm ² and exposed on the entire surface.
Shower development was performed with a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.). Thereafter, pure water was sprayed in a shower to wash away the developer. As described above, the coating film subjected to the exposure process and the development process was heat-treated (post-baked) in an oven at 220 ° C. for 1 hour to form a black matrix on the glass substrate.

The evaluation shown below was performed and the results are shown in Table 2.
-Application uniformity-
After the photosensitive resin composition is slit-coated, after waiting for 10 minutes as it is, it is further coated on a glass substrate, pre-baked on a hot plate at 90 ° C. for 60 seconds, and then streaky unevenness on the coated surface Were visually counted using a sodium light source and evaluated according to the following criteria.

-Criteria for surface evaluation of coated substrates-
○: No streak-like unevenness on the coated surface. Δ: 1-5 streaky unevennesses observed. X: 6 or more streaky unevennesses or any foreign matter observed.

-Evaluation of residue-
The presence or absence of a residue in a region (unexposed portion) where light was not irradiated in the exposure process described above was observed with an SEM, and the residue was evaluated. The evaluation criteria are as follows.
-Evaluation criteria-
○: Residue was not confirmed at all in the unexposed area. Δ: Residue was slightly confirmed at the unexposed area, but there was no practical problem. confirmed.

-Step evaluation-
The obtained black matrix (pattern formed from the polymerizable composition) was photographed with an optical microscope (magnification 10 times), and the width of the step region was measured. As shown in FIG. 1, in a black matrix (a color filter having a black matrix) 10, a pattern edge 1 which is an end portion of a pattern formed from a polymerizable composition, and a step region (from a central portion in a black matrix peripheral portion). Also, the distance between the boundary line 2 and the region where the film thickness becomes thinner was measured. This distance is divided by the length of one side of the formed pattern and is shown in% in Table 2.

As is apparent from Table 2, Examples 15 to 26, which are polymerizable compositions containing the dispersion composition of the present invention using a specific dispersant as a black matrix for a liquid crystal display device, have good coating uniformity. It was found that there was no residue, the step width was small, and the developability was excellent.
In particular, Examples 15 to 24 using an oxime compound as a polymerization initiator had a small step width and good developability.

<Production of solid-state image sensor>
-Preparation of chromatic coloring polymerizable composition-
In the same manner as in the polymerizable composition prepared in Example 1, except that the black pigment, titanium black, was replaced with the following chromatic pigment, the red (R) dispersion composition and the green (G) dispersion composition, respectively. And a dispersion composition for blue (B) were prepared.

(Chromatic pigments for RGB colored pixel formation)
-Red (R) pigment C.I. I. Pigment Red 254
-Green (G) pigment C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 [mass ratio] mixture and blue (B) pigment C.I. I. Pigment Blue 15: 6 and C.I. I. 30/70 [mass ratio] mixture with pigment violet 23

<Preparation of color filter for solid-state image sensor>
A mixed solution consisting of 40 parts of the above pigments, 50 parts of Disperbyk-161 (manufactured by BYK), 30% solution) as a dispersant, and 110 parts of propylene glycol monomethyl ether as a solvent was mixed and dispersed for 15 hours by a bead mill. Thus, each pigment dispersion was prepared.
The obtained pigment dispersions were stirred and mixed so as to have the following composition ratios, respectively, red (R) colored polymerizable composition R-1, green (G) colored polymerizable composition G-1, and A colored polymerizable composition B-1 for blue (B) was prepared.
・ Coloring agent (each pigment dispersion) 350 parts ・ Polymerization initiator (oxime polymerization initiator)
(CGI-124, manufactured by Ciba Specialty Chemicals Co., Ltd.) 30 parts · TO-1382 (manufactured by Toagosei Co., Ltd.) 25 parts (polymerizable compound, carboxyl group-containing pentafunctional acrylate manufactured by Toagosei Co., Ltd.)
・ Dipentaerythritol hexaacrylate 30 parts ・ Solvent (propylene glycol monomethyl ether acetate) 200 parts ・ Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part

  Using the colored polymerizable composition R-1 for red (R) on the light-shielding filter wafer having the black matrix prepared in Example 1, 1.6 × 1.6 μm red (R) A colored pattern was formed. Further, using the colored polymerizable composition G-1 for green (G) in the same manner, the colored polymerizable composition B-1 for 1.6 × 1.6 μm green (G) and blue (B) is used. A blue (B) chromatic coloring pattern was sequentially formed to produce a color filter for a solid-state imaging device.

-Evaluation-
When a full-color color filter was incorporated in a solid-state image sensor, it was confirmed that the solid-state image sensor has a high black matrix light-shielding property, high resolution, and excellent color separation.

<Production of liquid crystal display device>
-Preparation of chromatic coloring polymerizable composition-
The red and blue prepared for the production of the color filter for a solid-state imaging device described above were stirred and mixed using the pigment dispersion liquid for each color subjected to the dispersion treatment so that the composition ratio was as follows, and a coating liquid for the polymerizable composition of each color was prepared. Prepared.
Colorant (pigment dispersion) 200 parts Propylene glycol monomethyl ether acetate (solvent) 19.20 parts Ethyl lactate (solvent) 36.67 parts Resin (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) 40% propylene glycol monomethyl ether acetate solution of copolymer (molar ratio = 60/22/18) 33.51 parts dipentaerythritol hexaacrylate (polymerizable compound) 12.20 parts p-methoxyphenol (polymerization prohibited) Agent) 0.0061 parts Fluorosurfactant (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
0.83 parts, photopolymerization initiator (trihalomethyltriazine photopolymerization initiator) 0.586 parts

-Production of color filters for liquid crystal display devices-
Using the light-shielding filter produced in Example 1 as a black matrix and using the colored polymerizable composition R-1 for red (R) on the black matrix, in the same manner as in the method described in Example 1. A red (R) coloring pattern of 80 μm × 80 μm was formed. Further, similarly, the chromatic color of green (G) using the colored polymerizable composition G-1 for green (G) and blue (B) using the colored polymerizable composition B-1 for blue (B). A color filter having a black matrix for a liquid crystal display device was formed by sequentially forming a colored pattern.

-Evaluation-
The obtained color filter was processed with an ITO transparent electrode, an alignment film, and the like to provide a liquid crystal display device. The color filter using the polymerizable composition of the present invention had good uniformity of the coated surface, the liquid crystal display device had no display unevenness, and the image quality was good.

Black matrix top view Cross section of black matrix 1: Pattern edge 2: Step 10: Black matrix

Claims (12)

  A dispersion composition comprising (A) a light-shielding pigment, (B) a dispersant having at least one terminal capable of radical polymerization and a group adsorbing to the light-shielding pigment at the other terminal, and (C) a solvent. .   (B) A dispersant having at least one terminal capable of radical polymerization and a group adsorbing to the light-shielding pigment at the other terminal is a radical at at least one terminal of the polyether linking group and the polyester linking group. The dispersion composition according to claim 1, which is a dispersant having a polymerizable group. (B) The dispersant having at least one terminal capable of radical polymerization and having a group adsorbing to the light-shielding pigment at the other terminal is a compound represented by the following general formula (1): Or the dispersion composition of Claim 2.

In General Formula (1), B represents an allyl group or a (meth) acryloyl group, Q ¹ and Q ³ each independently represent a single bond or a divalent linking group, Q ² represents an alkylene group, M represents an organic group having at least one selected from a phosphoric acid group, a carboxylic acid group, a urethane group, a urea group, an amide group, and an imino group. a represents an integer of 0 to 20, b represents an integer of 0 to 100, and (a + b) is in the range of 5 to 100. n represents an integer of 1 to 4, and p represents an integer of 2 to 8, respectively. (B) A dispersant having at least one terminal capable of radical polymerization and a group adsorbing to the light-shielding pigment at the other terminal is represented by the following general formula (2) or general formula (3). The dispersion composition according to any one of claims 1 to 3, wherein the dispersion composition is a compound.

In General Formula (2) and General Formula (3), B ¹ and B ² each independently represent an allyl group or a (meth) acryloyl group, and Q ⁴ , Q ⁶ , Q ⁷ , and Q ⁹ are Each independently represents a single bond or a divalent linking group, Q ⁵ and Q ⁸ each independently represent an alkylene group, M ¹ represents an (n1 + m1) -valent organic group, M ² represents a single bond, or (n2 + m2) ) Represents a valent organic group. a1 and a2 each independently represent an integer of 0 to 20, b1 and b2 each independently represent an integer of 0 to 100, and (a1 + b1) is 5 to 100, and (a2 + b2) is 5 to 100. Range. m1, m2, n1, and n2 each independently represents an integer of 1 to 4, and q and r each independently represents an integer of 2 to 8. (B) A dispersant having at least one terminal capable of radical polymerization and a group adsorbing to the light-shielding pigment at the other terminal is represented by the following general formula (4) or general formula (5). It is a compound, The dispersion composition of any one of Claims 1-3.

In General Formula (4) and General Formula (5), B ³ and B ⁴ each independently represent an allyl group or a (meth) acryloyl group, and Q ¹⁰ and Q ¹⁴ each independently represent a single bond, or It represents a divalent linking group, Q ¹¹ and Q ¹⁵ each independently represent an alkylene group, and Q ¹² , Q ¹⁶ and Q ¹⁷ each independently represent a divalent linking group. Q ¹³ represents an n3 valent linking group, and Q ¹⁸ represents an n4 valent linking group. a3 and a4 each independently represents an integer of 0 to 20, b3 and b4 each independently represents an integer of 0 to 100, and (a3 + b3) is in the range of 5 to 100, and (a4 + b4) is in the range of 5 to 100 It is. n3 and n4 each independently represents an integer of 2 to 6, m4 represents an integer of 0 to 10, and s and t each independently represents an integer of 2 to 8.   The dispersion composition according to any one of claims 1 to 5, wherein (A) the light-shielding pigment is titanium black.   A polymerizable composition comprising the dispersion composition according to any one of claims 1 to 6 and (D) a polymerization initiator.   The polymerizable composition according to claim 7, wherein (D) the polymerization initiator is an oxime polymerization initiator.   The light-shielding color filter which has a coloring pattern which uses the polymeric composition of Claim 7 or Claim 8 on a board | substrate.   A solid-state imaging device comprising the light-shielding color filter according to claim 9.   A liquid crystal display device comprising the light-shielding color filter according to claim 9. A dispersant represented by the following general formula (2), general formula (4), or general formula (5).

In General Formula (2), General Formula (4), and General Formula (5), B ¹ , B ³ , and B ⁴ each independently represent an allyl group or a (meth) acryloyl group. Q ⁴ , Q ⁶ , Q ¹⁰ , and Q ¹⁴ each independently represent a single bond or a divalent linking group, Q ⁵ , Q ¹¹ , and Q ¹⁵ represent an alkylene group, Q ¹² , Q ¹⁶ , and Q ¹⁷ each independently represents a divalent linking group. Q ¹³ represents an n3 valent linking group, and Q ¹⁸ represents an n4 valent linking group. M ¹ represents an (n1 + m1) -valent organic group, a1 represents an integer of 1 to 20, and a3 and a4 each independently represents an integer of 0 to 20. b1, b3, and b4 each independently represents an integer of 0-100, (a1 + b1) is in the range of 5-100, (a3 + b3) is in the range of 5-100, and (a4 + b4) is in the range of 5-100. Range. m1 is an integer of 1 to 4, n1 is an integer of 1 to 4, m4 is an integer of 0 to 10, n3 and n4 are each independently an integer of 2 to 6, q, s, and t are each independently 2 Each represents an integer of 8.

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