KR20090031987A - Pigment dispersion composition, photocurable composition, color filter, liquid crystal display element, solid state image sensor and method for manufacturing color filter - Google Patents

Abstract

A pigment dispersion composition is provided to ensure high pigment dispersibility and dispersion stability and favorable color characteristics even when containing a high concentration of pigment, to improve development and surface smoothness of pixel and to obtain high contrast ratio. A pigment dispersion composition comprises a polymer containing a cyclic structure as a partial structure and having the average molecular weight of 1,000~100,000, and dyes. The polymer satisfies one or more of the condition (i) and (ii): (i) an alkali-liable group is bonded to a cyclic structure directly, and (ii) the cyclic structure is at least one selected from the group including lactone or acid anhydride structure, and the polymer has a block type, lactone type or terminal-modified type structure.

Description

Pigment dispersion composition, photocurable composition, color filter, liquid crystal display device, solid state image pickup device and color filter manufacturing method }

INDUSTRIAL APPLICABILITY The present invention is a pigment dispersion composition which can be used to form image materials such as color filters and color proofs, and photocurable materials such as inks and paints, and photocurable compositions suitable for forming color filters such as liquid crystal display devices and solid state image pickup devices. The present invention relates to a color filter using the curable composition, a manufacturing method thereof, a liquid crystal display device, and a solid state image pickup device.

Background Art In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) for liquid crystal display devices (LCDs), and high color characteristics are required in chromaticity, contrast, etc. in accordance with the tendency of expanding these uses. have. In addition, the use of an image sensor (solid-state image sensor) also requires high color characteristics such as reduction of color unevenness and improvement of color resolution.

In response to the above requirements, it is required to maintain the pigment in a stable dispersed state (good dispersion stability). If the dispersibility is insufficient, fringes (uneven edges) and surface irregularities are formed in the formed colored resist film, and the chromaticity and dimensional accuracy of the color filter produced are lowered, or the contrast is considerably deteriorated. A problem arises.

Moreover, when dispersion stability is inadequate, the uniformity of the film thickness in the manufacturing process of a color filter especially a coating process of a colored photocurable composition falls, the photosensitivity in an exposure process falls, or develops. The problem that the alkali solubility in a process falls or is easy to produce arises. Moreover, when the dispersion stability of a pigment is bad, there also exists a problem that the constituent component of a colored photocurable composition raise | generates a viscosity, raises a viscosity, and the photolife becomes very short over time.

In order to solve such a problem, the pigment dispersant of the polymer which combined the organic pigment | dye and the polymer, etc. are proposed (for example, Unexamined-Japanese-Patent No. 4-139262). Moreover, it is also proposed to use the copolymer containing acid groups, such as carboxylic acid, sulfonic acid, and methacrylic acid, and the polymer containing the maleimide substituted phenolic acid group (for example, Japanese Patent No. 3094403, Japanese Patent Laid-Open No. 2004-287409 and Japanese Patent Laid-Open No. 2000-56118).

However, when the particle diameter of the pigment is made smaller, the surface area of the pigment particles is increased, so that the cohesion force between the pigment particles is increased, and it is difficult to achieve both dispersibility and dispersion stability at a high level.

In addition, when manufacturing a color filter using the said pigment dispersion composition, a photocurable composition is apply | coated on a board | substrate or the board | substrate which previously formed the light shielding layer of a desired pattern, and after drying, a desired pattern is applied to a dry coating film. Various pixels are obtained by irradiating radiation (hereinafter referred to as "exposure") and developing so as to form.

However, the color filter manufactured in this way tends to cause residue or base contamination on the substrate or the light shielding layer of the unexposed portion in the developing step, and the surface smoothness of the postbaked pixel after development becomes poor. There was a problem of being poor. In addition, the degree of residue or base contamination on the substrate or the light shielding layer and deterioration of surface smoothness tends to become remarkable as the concentration of the pigment contained in the photocurable composition increases. Therefore, it was difficult to achieve sufficient color density with the conventional photocurable composition for color filters.

In addition, it is proposed to use a linear random polymer containing lactone (for example, Japanese Patent Application Laid-Open No. 2007-65155). However, in this case, when a lot of lactones effective for developability are contained, the molecular weight becomes too large, which causes a problem that solvent solubility and developability deteriorate. Therefore, sufficient amount of lactone cannot be introduced into the linear random polymer, and the effect of improving developability was not obtained satisfactorily. In addition, the linear random polymer containing lactone has a low effect of suppressing aggregation of pigments, and therefore, it is necessary to use other dispersants together in order to express dispersibility. As a result, a large amount of linear random polymer containing lactone can be added. There was a problem that I could not.

The present invention provides a pigment dispersion composition having high pigment dispersibility and dispersion stability after dispersion and good color characteristics even when the pigment is contained at a high concentration.

Moreover, this invention provides the photocurable composition which is excellent in developability and the surface smoothness of a pixel when a color filter is comprised, and can obtain a high contrast.

The present invention also provides a high contrast color filter having good color characteristics and a method of manufacturing the color filter.

That is, this invention provides the pigment dispersion composition which contains a <1> cyclic structure as a partial structure, and contains a high molecular compound and a pigment which are in the range of 1,000-100,000 in weight average molecular weight. Here, the polymer compound is characterized by satisfying at least one of the following conditions (i) and (ii).

(i) The group which decomposes | disassembles with alkali to the said cyclic structure directly bonds.

(ii) The cyclic structure is at least one selected from the group consisting of a lactone structure and an acid anhydride structure, and the polymer compound has a block, graft, or terminal modified structure.

Particularly, in the first aspect, the present invention provides a pigment-dispersion composition that satisfies the condition (i), that is, a weight average having a cyclic structure in which a group decomposed by (A-1) alkali is directly bonded to a partial structure. Provided is a pigment dispersion composition comprising a polymer compound having a molecular weight of 1,000 or more and 100,000 or less and a pigment (B).

The present invention also provides a pigment dispersion composition of <2>, wherein the polymer compound (A-1) is a compound having a monomer represented by the following General Formula (G-I).

In the formula, X represents a hydrogen atom or a methyl group; W represents a single bond or a linking group formed by arbitrarily combining two or more linking groups selected from an atomic group represented by the following; Q represents a cyclic structure which may have a substituent; In addition, n represents the integer of 1-3.

Z ¹ and Z ² here represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group or a hydroxy group; In addition, Z ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms.

The present invention also provides a pigment dispersion composition of <3>, wherein the polymer compound represented by <4> is represented by any one of the following general formulas (G-II) to (GV). to provide.

In formulas (G-II) to (G-V), X, Q and n have the same meaning as X, Q and n in the general formula (G-I).

In addition, the present invention is bonded directly to the cyclic structure in the polymer compound having a weight average molecular weight of 1,000 or more and 100,000 or less having a cyclic structure formed by directly bonding a group decomposed by the above-mentioned (A-1) alkali as a partial structure. Content of the repeating unit containing the group decomposed | disassembled by alkali is 5-50 mass%, The pigment dispersion composition in any one of said <2>-<4> is provided.

In addition, the present invention is characterized in that the acid value of the polymer compound having a weight average molecular weight of 1,000 or more and 100,000 or less and 300 mg or more of 300 mg having a cyclic structure formed by directly bonding groups decomposed by the above-mentioned (A-1) alkali as a partial structure is 50 mg KOH / g or more. The pigment dispersion composition in any one of said <2>-<5> which is KOH / g or less is provided.

Moreover, this invention provides the photocurable composition containing the pigment dispersion composition as described in any one of <7> said <2>-<6>, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator.

Furthermore, this invention provides the color filter characterized by having the coloring pattern which uses <8> the photocurable composition as described in said <7>.

Furthermore, this invention provides the liquid crystal display element using the color filter as described in <9> said <8>.

The present invention also provides a solid state image pickup device using the color filter described in < 10 >.

The present invention also provides a process for forming a photosensitive film by applying the photocurable composition as described in <7> above or directly through another layer to form a photosensitive film and subjecting the formed photosensitive film to patterning and developing a colored pattern. It provides a method for producing a color filter comprising the step of forming.

Moreover, especially as a 2nd aspect, this invention has the pigment dispersion composition which satisfy | fills the said condition (ii), ie, it has 1 or more types of partial structures chosen from (A-2) lactone structure and an acid anhydride structure, It provides a pigment dispersion composition which has a weight average molecular weight of 1,000-100,000, and contains the high molecular compound which has a block-like, graft-type, or terminal-modified structure, and (B) pigment.

The present invention is also characterized in that the polymer compound (A-2) has a repeating unit having a group having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-10). The pigment dispersion composition of <12> is provided.

Wherein the lactone structure moiety does or does not have a substituent (R ^b2 ); R ^b2 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group; when n ² is 2 or more, a plurality of R ^{b2 's} may be the same or different; In addition, a plurality of R ^{b2 's} may be bonded to each other to form a ring.

In addition, the present invention provides a pigment dispersion composition of <13>, wherein the repeating unit is represented by the following general formula (AI).

In the formula, R ^b0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent; A ^b represents a divalent linking group having an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group combining these; V represents a group represented by any one of General Formulas (LC1-1) to (LC1-10).

The present invention is also characterized in that the polymer compound (A-2) has a repeating unit containing a group having an acid anhydride structure represented by any one of the following general formulas (UA1-1) to (UA1-5). The pigment dispersion composition of <12> is provided.

In the formula, the acid anhydride structural moiety may or may not have a substituent (R ^b2 ); R ^b2 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group; when n ² is 2 or more, a plurality of R ^{b2 's} may be the same or different; In addition, a plurality of R ^{b2 's} may be bonded to each other to form a ring.

In addition, the present invention provides a pigment dispersion composition according to <15>, wherein the repeating unit is represented by the following general formula (AII).

In the formula, R ^b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a substituent; A ^b represents a divalent linking group having an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group combining these; V ² represents a group represented by one of General Formulas (UA1-1) to (UA1-5).

In addition, the present invention is the above-mentioned <12> polymer compound (A-2) is a block-type polymer compound having 5 to 80 mass% of repeating units having at least one partial structure selected from lactone structure and acid anhydride structure. The pigment dispersion composition as described in> is provided.

In addition, the present invention has a graft side chain in which the polymer compound (A-2) has at least one repeating unit having a partial structure selected from a lactone structure and an acid anhydride structure, and the repeating unit in the graft side chain. The pigment dispersion composition as described in said <12> which is the graft type high molecular compound whose ratio is 5-100 mass% is provided.

In addition, the present invention has a repeating unit having at least one partial structure in which the polymer compound (A-2) has a partial structure selected from a lactone structure and an acid anhydride structure, and at the same time, The pigment dispersion composition as described in said <12> which is a terminal side shaping high molecular compound whose ratio of a repeating unit is 5-100 mass% is provided.

Furthermore, this invention provides the pigment dispersion composition in any one of said <12> to <19> in which the <20> above-mentioned high molecular compound (A-2) contains an adsorption site | part.

The present invention also provides the pigment dispersion composition according to the above <20>, wherein the polymer compound (A-2) is a block-type polymer compound having 5 to 50 mass% of repeating units having the adsorption site.

The present invention also provides a graft type in which the polymer compound (A-2) has a repeating unit having the adsorption site in the graft backbone, and the proportion of the repeating unit in the graft backbone is 5 to 50% by mass. The pigment dispersion composition as described in said <20> which is a high molecular compound is provided.

The present invention also provides the pigment dispersion composition according to the above <20>, wherein the polymer compound (A-2) is a terminal-modified polymer compound whose terminal is modified with the adsorption site.

Moreover, this invention provides the photocurable composition containing the pigment dispersion composition in any one of said <12> to <23>, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator.

Furthermore, this invention provides the color filter which uses the photocurable composition as described in said <24>.

Furthermore, this invention provides the liquid crystal display element using the color filter as described in said <25>.

The present invention also provides a solid state image pickup device using the color filter described in the above <25>.

In addition, the present invention provides a process for forming a photosensitive film by applying the photocurable composition according to the above <24> directly or through another layer to form a photosensitive film and subjecting the formed photosensitive film to pattern exposure and development to produce a colored pattern. It provides a method for producing a color filter comprising the step of forming.

(Effects of the Invention)

In the development process of a curable composition, as a method of solving the problem which a residue and base contamination generate | occur | produce on the board | substrate or light shielding layer of an unexposed part, conventionally alkali-soluble resin which has acidic radicals, such as methacrylic acid, is added to a pigment dispersion composition. The method to say is known.

However, when a large amount of acid groups are introduced into the high molecular compound, alkali solubility is improved, so developability is certainly improved. On the contrary, there arises a problem that the pigment dispersion stability is deteriorated.

In general, when a basic pigment derivative is used, the acid groups in the polymer compound are adsorbed to the pigment and do not function as a developing group. Moreover, the pigment may generate | occur | produce adsorption.

In addition, in the case of using a basic polymeric dispersant for the purpose of improving dispersibility, when an acid group is introduced into the polymer compound in order to impart developability, the acid group and the basic group coexist in the dispersant, and the dispersant gels and consequently the pigment. We think that we adsorb each other.

In the polymer compound (A-1) according to the first aspect of the present invention, an acid group is introduced to a hydrophobic cycloalkyl group, an aromatic group, or the like, and an acidic group reaction that causes deterioration in dispersion stability and gelation due to an cyclic structure by a cyclic structure. It is thought that this is inhibited. Therefore, it is thought that the dispersion stability of the dispersion composition resulting from an acidic radical does not deteriorate. Moreover, since the said acidic radical contacts with a large amount of alkali and expresses developability which an acidic radical originally has, when the curable composition of this invention containing the dispersion composition which has such an acidic radical is used for a color filter, It is thought that good developability can be provided by this. In particular, when the polymer compound having an acid group bonded directly to the cyclic structure is used, the effect is considered to be large.

According to the first aspect of the present invention, even when a pigment is contained at a high concentration, it has a pigment dispersant having high pigment dispersibility and dispersion stability after dispersion, and has good color characteristics. It is possible to provide a pigment dispersion composition, a photocurable composition, a color filter having good color characteristics and high contrast, and a method for producing the same, which have excellent surface smoothness and can obtain high contrast.

In addition, the high molecular compound (A-2) in the 2nd aspect of this invention has a structure of block type, graft type, or terminal modification type, and is effective in adsorb | sucking on the surface of a pigment and inhibiting reaggregation of pigments. Since it has a stereoscopic repulsion, good dispersibility can be exhibited. In particular, when the partial structure selected from the lactone structure and the acid anhydride structure is introduced into the three-dimensional repellent group, it is inferred that the lactone and the acid anhydride are disposed outside as shown in Fig. 1A. As shown in Fig. 1B, the reaction (opening) with the developer becomes dull when disposed inside, but the reaction is rapidly developed (opening) with the developer due to the lactone or the acid anhydride being disposed outside, resulting in excellent developability. I think that can be obtained.

In addition, in particular, the colored photocurable composition using the pigment dispersion composition according to the second aspect of the present invention is difficult to adhere the polymer liquid to the piping portion or the coating head portion of the coating, so that the retention of the liquid in the piping is reduced. The effect of reducing adhesion of dried foreign matters and the like on the coating head can be exhibited. Accordingly, it is considered that a color filter having particularly excellent surface smoothness can be obtained. Moreover, in the pigment dispersion composition of this invention and the colored photocurable composition using the said pigment dispersion composition, it is thought that the thickening at time resulting from association of an alkali-soluble polymer, a dispersing agent, etc. can be prevented, and aggregation of a pigment can be prevented.

In addition, in the colored photocurable composition using the pigment dispersion composition of the present invention, since alkali development proceeds mildly, it is easy to perform discrimination of the exposed portion and the non-exposed portion, and a good developing pattern is obtained. It is estimated that contamination etc. become favorable.

According to the second aspect of the present invention, even when the pigment is contained at a high concentration, a pigment dispersion composition having high pigment dispersibility and dispersion stability and good color characteristics is obtained. Further, when constituting the color filter, a photocurable composition which is excellent in developability and surface smoothness of a pixel and can obtain high contrast, a color filter having good color characteristics and high contrast, and a method of manufacturing the color filter Can provide.

The color filter using the pigment dispersion composition of the 2nd aspect of this invention is especially excellent in voltage retention.

The decrease in the voltage retention occurs when the metal ions in the color filter easily move in the film. Usually, since a carboxylic acid can be used as a developing group, it was in the situation which metal ion is easy to move via a carboxylic acid. In the pigment dispersion composition according to the second aspect of the present invention, it is thought that the acid group is a latent acid group (lactone / acid anhydride) rather than a carboxylic acid to reduce the interaction with the basic group. As a result, excellent voltage retention is obtained. It is estimated to be lost.

Hereinafter, the pigment dispersion composition, the photocurable composition, the color filter, the liquid crystal display element, the solid-state image sensor, and the manufacturing method of the color filter of this invention are demonstrated in detail.

Pigment dispersion composition

The pigment dispersion composition of this invention contains the polymeric compound (A) and pigment (B) of the weight average molecular weights 1,000-100,000 which have a cyclic structure as a partial structure, and it comprises using other components, such as a resin component, as needed. can do.

In particular, the pigment dispersion composition in the first aspect of the present invention has a weight average molecular weight of 1,000 to 1 having a group decomposed by at least one alkali on a cyclic structure (hereinafter may be appropriately referred to as an "acid group"). It is characterized by containing 100,000 high molecular compound (A-1) and pigment (B).

Moreover, the pigment dispersion composition in the 2nd aspect of this invention has 1 or more types of partial structures chosen from a lactone structure and an acid anhydride structure, and has a weight average molecular weight of 1,000-100,000, and also a block type, a graft type, or a terminal edge. It is characterized by containing a high molecular compound (A-2) and a pigment (B) which have a shaping structure.

Polymer compound (A)

When the pigment dispersion composition of the present invention contains a high molecular compound (A), the dispersion state of the pigment in an organic solvent becomes good and, for example, when a color filter is formed using the pigment dispersion composition, the pigment is concentrated at a high concentration. Even when it contains, high developability and surface smoothness can be expressed.

Polymer compound (A-1)

The pigment dispersion composition in the first aspect of the present invention contains, as the polymer compound (A), a polymer compound (A-1) having a weight average molecular weight of 1,000 to 100,000 having an acid group bonded directly to the cyclic structure.

Examples of the acid group in the high molecular compound (A-1) include a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, (Alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris And (alkylcarbonyl) methylene groups, tris (alkylsulfonyl) methylene groups, groups having fluorinated alcohol groups and the like.

Among these acid groups, carboxylic acid groups are preferred from the viewpoints of developability, ease of introduction, and the like.

5-50 mass% is preferable in the total solid of a high molecular compound (A-1), and, as for the quantity of the repeating unit containing an acidic radical, 5-30 mass% is more preferable.

Here, it is preferable that a high molecular compound (A-1) is a compound which has a monomer represented with the following general formula (G-I).

In general formula (G-1), X represents a hydrogen atom or a methyl group. W represents a single bond or a linking group formed by arbitrarily combining two or more of a single linking group selected from an atomic group represented by the following. Q represents the cyclic structure which may have a substituent. n represents the integer of 1-3.

Z ¹ and Z ² represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group or a hydroxy group. Z ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

As substituents other than the acidic group which can be introduce | transduced into X in general formula (G-1), an alkyl group, a cycloalkyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group is mentioned, and an alkyl group, a halogen atom, and an alkoxy group are more preferable.

It is more preferable that general formula (G-I) is represented with the following general formula (G-II)-(G-V).

In General Formulas (G-II) to (G-V), X, Q and n have the same meanings as X, Q and n in the general formula (G-I).

Specific examples of the general formulas (G-I) to (G-V) are shown below.

Among the above embodiments, G-4, G-5, G-6, G-8, G-9, G-13, G-14, G-15, G-19, G-20, G-21, G- More preferred are monomers represented by 23, G-24, G-25, G-26, G-27, G-28, G-30, G-33, G-35, G-38, G-4, More preferred are monomers represented by G-5, G-6, G-9, G-14, G-20, G-25, G-26.

The high molecular compound (A-1) of this invention can be synthesize | combined even if it superposes | polymerizes the monomers mentioned above, and can also be synthesize | combined by making the high molecular compound of a precursor and the low molecular compound which has an acidic radical react.

As for the high molecular compound (A-1) of this invention, it is more preferable that it is at least 1 sort (s) chosen from a block type polymer, a graft type polymer, and a terminal modification type polymer.

It is thought that the high molecular compound (A-1) of this invention acts by adsorb | sucking to the surface of a pigment and preventing reaggregation in a dispersion process. Therefore, the high molecular compound (A-1) of the present invention may be a linear random copolymer, but a block polymer, a graft polymer, or a terminal modified polymer is more preferable because it is more effective.

Polymer compound (A-2)

In the second aspect of the present invention, the pigment dispersion composition is the polymer compound (A), and has a weight average molecular weight of 1,000 to 100,000 having a lactone structure or an acid anhydride structure, a graft type or a terminal modified polymer compound (A) -2).

By introducing a lactone structure or an acid anhydride structure, the dispersion state of the pigment in the organic solvent becomes good, and when a color filter is formed, for example, high developability and surface smoothness can be expressed even when the pigment is contained at a high concentration. have.

Lactone structure

As the lactone structure, any group can be used as long as it contains a lactone structure, but a group having a 5 to 7 membered ring lactone structure is preferable. Moreover, it is more preferable to have a repeating unit provided with the group which has a lactone structure represented by either of following general formula (LC1-1) (LC1-10). In addition, the group having a lactone structure may be directly bonded to the main chain. Among the general formulas (LC1-1) to (LC1-10) shown below, more preferable lactone structures include (LC1-1), (LC1-4), (LC1-8), and (LC1-9), and specific lactones. Developing becomes more favorable by using a structure.

The lactone structure moiety may or may not have a substituent (R ^b2 ). Preferred substituents (R ^b2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid decomposition. Genitals and the like. When n <^2> is two or more, two or more R <^b2> may be same or different, and two or more R <^b2> may combine and form a ring.

As a repeating unit containing the group which has a lactone structure represented by any of said general formula (LC1-1)-(LC1-10), the repeating unit represented by the following general formula (AI), etc. can be mentioned.

R <^b0> represents a hydrogen atom, a halogen atom, or a C1-C4 alkyl group in general formula (AI). As a preferable substituent which the alkyl group represented by R <^b0> may have, a hydroxyl group or a halogen atom is mentioned.

^Examples of the halogen atom represented by R ^b0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As R ^{b0, a} hydrogen atom or a methyl group is preferable.

A ^b represents a divalent linking group having a alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group or a divalent linking group combining these. It is preferably a single bond or a linking group represented by -A ^b1 -CO _2- .

A ^b1 is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, and preferably methylene group, ethylene group or propylene group.

V represents a group represented by any one of General Formulas (LC1-1) to (LC1-10).

Although the specific example of the repeating unit containing group which has a lactone structure is listed below, this invention is not limited to these. Further, according to (LC-1) ~ (LC -20), R x represents H or CH _3.

Acid anhydride structure

As the acid anhydride structure, any group can be used as long as it contains an acid anhydride structure, but a group having a 5 to 7 membered ring acid anhydride structure is preferable. Furthermore, it is more preferable to have a repeating unit containing the group which has an acid anhydride structure represented by either of following general formula (UA1-1) (UA1-5). In addition, the group having an acid anhydride structure may be directly bonded to the main chain.

The acid anhydride structural moiety may or may not have a substituent (R ^b2 ). Preferred substituents (R ^b2) are exemplified as the substituent is the same as the (R ^b2) in the lactone structure described above.

As a repeating unit containing the group which has an acid anhydride structure represented by either of general formula (UA1-1)-(UA1-5), the repeating unit etc. which are represented by the following general formula (AII) can be mentioned.

In the general formula (AII), R ^b0 A and ^b have the same meanings as R ^b0 A and ^b in the general formula (AI).

V ² represents a group represented by one of General Formulas (UA1-1) to (UA1-5).

Although the specific example of the repeating unit containing group which has an acid anhydride structure is listed below, this invention is not limited to these. In the following (UA-1) to (UA-4), R ^x represents H or CH ₃ .

In addition, the high molecular compound (A-2) which has a lactone structure or an acid anhydride structure in 2nd aspect of this invention can be synthesize | combined even if superposing | polymerizing the monomers mentioned above, and the precursor high molecular compound, lactone structure, or acid anhydride can be synthesize | combined. It can also synthesize | combine by reacting the low molecular weight compound which has a structure.

The lactone structure or the acid anhydride structure may be contained in one kind or in combination of two or more kinds. Moreover, a lactone structure is more preferable from a viewpoint of easy synthesis and easy handling.

As described above, the polymer compound (A) according to the present invention may have a block, graft, or terminal modified structure. Moreover, especially the high molecular compound (A-1) of this invention may take the structure of a linear random copolymer.

Block type polymer compound

As a block type polymer, the block type polymer compound which consists of an adsorption | suction site | part (pigment adsorption block) a1, the block (b1) which has a cyclic structure, and the block (c1) which does not adsorb | suck to a pigment is preferable.

It is preferable that the pigment adsorption block (a1) is 5-50 mass% of the whole high molecular compound, More preferably, it is 10-50 mass%.

It is preferable that the block (b1) which has a cyclic structure is 5-80 mass% of the whole high molecular compound, More preferably, it is 10-80 mass%.

It is preferable that the block (c1) which does not adsorb | suck to a pigment is 0-80 mass% of the whole high molecular compound.

Adsorption site (a1)

Although it does not restrict | limit especially as a monomer which comprises an adsorption site, For example, the monomer which has a functional group which can adsorb | suck to a pigment is mentioned. Specific examples include monomers having an organic dye structure or a heterocyclic structure, monomers having an acidic group, monomers having a basic nitrogen atom, monomers having an ionic functional group, and the like.

Monomer with organic pigment structure or heterocyclic structure

As a monomer which has the organic pigment | dye structure or heterocyclic structure used in the high molecular compound (A-1) of 1st aspect of this invention, it is a phthalocyanine type, an insoluble azo type, an azo lake type, an anthraquinone type, Quinacridone-based, dioxazine-based, diketopyrrolopyrrole-based, anthrapyridine-based, anthrone-based, indanthrone-based, flavantron-based, perinone-based, perylene-based, and thioindigo-based pigmented structures; for example, thiophene , Furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone, benzimazolone, benzothiazole, succinimide, phthalyl Mead, naphthalimide, hydantoin, indole, quinoline, carba , Acridine, acridine money, can be exemplified a monomer having a heterocyclic structure, such as anthraquinone. More specifically, although it does not restrict | limit, The monomer of the following structures can be enumerated.

As a monomer which has the organic pigment | dye structure or heterocyclic structure used in the high molecular compound (A-2) of the 2nd aspect of this invention, the monomer represented by following General formula (1), or maleimide, a maleimide derivative The monomer which consists of these is mentioned. Or it is especially preferable that it is a monomer represented by following General formula (1).

R <^1> in the said General formula (1) represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= 0) O-, -CONH-, -OC (= 0)-or a phenylene group. Z represents a group having a heterocyclic structure.

As an alkyl group represented by R <^1> , a C1-C12 alkyl group is preferable, A C1-C8 alkyl group is more preferable, A C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Cyclohexyloxy group etc. are mentioned.

Specifically as a preferable alkyl group represented by R <^1> , For example, a methyl group, an ethyl group, a propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-hydroxy Ethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group are mentioned.

As R ^{1, a} hydrogen atom or a methyl group is most preferred.

In General Formula (1), R ² represents a single bond or a divalent linking group. As said bivalent coupling group, a substituted or unsubstituted alkylene group is preferable. As said alkylene group, a C1-C12 alkylene group is preferable, A C1-C8 alkylene group is more preferable, A C1-C4 alkylene group is especially preferable.

^{Two or more} alkylene groups represented by R ² may be linked via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).

As a preferable alkylene group represented by R <^2> , a methylene group, an ethylene group, a propylene group, trimethylene group, tetramethylene group is mentioned specifically ,.

When the preferable alkylene group represented by R <^2> has a substituent, a hydroxyl group etc. are mentioned as said substituent, for example.

As a divalent linking group represented by R <^2> , -O-, -S-, -C (= O) O-, -CONH-, -C (= O) S-, -NHCONH at the terminal of said alkylene group Partial structure containing a hetero atom or a hetero atom selected from -NHC (= 0) O-, -NHC (= 0) S-, -OC (= 0)-, -OCONH-, and -NHCO-; It may have a heterostructure or a partial structure containing a hetero atom and may be connected to Z.

In General Formula (1), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthrone and indantron. Pigment structure, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, Imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, iso Indolin, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, nattalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone , Pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztria Cyclic amides, cyclic ureas, cyclic is already open a heterocyclic structure, such as DE. These heterocyclic structures may have a substituent, and examples of the substituent include alkyl groups, alkoxy groups, halogen atoms, aliphatic ester groups, aromatic ester groups, alkoxycarbonyl groups and the like.

Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms. As the nitrogen-containing heterocyclic structure having 6 or more carbon atoms, specifically, phenothiazine ring, phenoxazine ring, acridon ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic A urea structure and a cyclic imide structure are preferable, and it is especially preferable that it is a structure represented by following General formula (2), (3) or (4).

In the general formula (2), X is a single bond, an alkylene group (e.g., methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group and the ^{like), -O-, -S-, -NR A} - And -C (= 0)-. R ^A represents a hydrogen atom or an alkyl group here. The alkyl group in the case where R ^A represents an alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n -Butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group, etc. are mentioned.

Among the above-mentioned, as X in General formula (2), a single bond, a methylene group, -O-, or -C (= O)-is preferable, and -C (= O)-is especially preferable.

Formula (4), Y and Z are, each independently, -N =, -NH-, -N ( R B) -, represents a -S- or -O-. R ^B represents an alkyl group, and the alkyl group represented by R ^B is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, and i- A propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group, etc. are mentioned.

Among those described above general formula (4) Y and Z as -N =, -NH- and -N (R ^B) of the - is particularly preferred. Examples of the combination of Y and Z include a combination in which one of Y and Z is -N = and the other -NH-, and an imidazolyl group.

In General Formulas (2), (3) and (4), Ring A, Ring B, Ring C, and Ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an indene ring, an azlene ring, a fluorene ring, an anthracene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, an indole ring, a quinoline ring, Acridine ring, phenothiazine ring, phenoxazine ring, acridon ring, anthraquinone ring, etc. are mentioned. Especially, a benzene ring, a naphthalene ring, anthracene ring, a pyridine ring, a phenoxazine ring, an acridine ring, a phenothiazine ring, an acridon ring, an anthraquinone ring is preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are especially preferable.

Specifically, as ring A and ring B in General formula (2), a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, etc. are mentioned, for example. As ring C in General formula (3), a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, etc. are mentioned, for example. As ring D in General formula (4), a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, etc. are mentioned, for example.

Among the structures represented by the general formulas (2), (3) and (4), a benzene ring and a naphthalene ring are more preferable from the viewpoints of dispersibility and the aging stability of the dispersion. In general formula (2) or (4), a benzene ring is more preferable, and in formula (3), a naphthalene ring is more preferable.

In the high molecular compound (A-2) in this invention, about the monomer which has an organic pigment | dye structure or heterocyclic structure which can be used as a monomer which comprises an adsorption site | part, the monomer or maleimide represented by the said General formula (1) Although the specific example of the monomer which consists of a maleimide derivative is listed below, this invention is not limited to these.

Monomers with Acidic Groups

As a monomer which has an acidic group, you may contain the vinyl monomer which has a carboxyl group, the vinyl monomer which has a sulfonic acid group, or a phosphoric acid group.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimers. Furthermore, addition reactants of monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, and ω-carboxy-polycaprolactone mono ( Meth) acrylate etc. can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, a citraconic acid anhydride, as a precursor of a carboxyl group. Moreover, in these, (meth) acrylic acid is especially preferable from a viewpoint of copolymerizability, cost, and solubility.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamide-2-methylpropanesulfonic acid and the like, and examples of the vinyl monomer having a phosphate group include monophosphate (2-acryloyloxyethyl ester) and monophosphate (1-methyl-). 2-acryloyloxyethyl ester) etc. are mentioned.

In addition, the group (acid group) decomposed | disassembled by the said at least 1 sort (s) of alkali in the 1st aspect of this invention is introduce | transduced separately from said acidic group.

Monomers with basic nitrogen atoms

As a monomer which has a basic nitrogen atom, vinylpyridine, vinylimidazole, vinyltriazole, etc. are mentioned as a monomer which has a heterocyclic ring. As (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, (meth) acrylic acid 1- (N, N-dimethylamino) -1,1- Dimethylmethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N- (meth) acrylate Di-n-butylaminoethyl, (meth) acrylic acid N, N-di-i-butylaminoethyl, (meth) acrylate morpholinoethyl, (meth) acrylic acid piperidinoethyl, (meth) acrylic acid 1-pi Rollidinoethyl, N, N-methyl- 2-pyrrolidylaminoethyl (meth) acrylic acid, N, N-methylphenylaminoethyl (meth) acrylic acid, etc. are mentioned. As (meth) acrylamide, N- (N ', N'-dimethylaminoethyl) acrylamide, N- (N', N'-dimethylaminoethyl) methacrylamide, N- (N ', N'- Dimethylaminoethyl) acrylamide, N- (N ', N'-dimethylaminoethyl) methacrylamide, N- (N', N'-dimethylaminopropyl) acrylamide, N- (N ', N'-dimethyl Aminopropyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) acrylamide, N- (N', N'-diethylaminopropyl) methacrylamide, 2- (N, N-dimethylamino ) Ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N -Dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acryl Amide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) arc Rylamide and the like. Examples of the styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, and the like.

It is also possible to use a monomer having a urea group, a urethane group, a hydrocarbon group having 4 or more carbon atoms having a coordinating oxygen atom, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group. Specifically, the monomer of the following structure can be enumerated, for example.

Monomers Containing Ionic Functional Groups

Examples of the monomer containing an ionic functional group include anionic vinyl monomers or cationic vinyl monomers. Specific examples of the anionic vinyl monomer include salts of alkali metal salts and organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol) of the vinyl monomer having the acidic group. Moreover, as a cationic vinyl monomer, the said nitrogen-containing vinyl monomer is halogenated alkyl (alkyl group: C1-C18, halogen atom: chlorine atom, bromine atom, or iodine atom); Halogenated benzyl, such as benzyl chloride and benzyl bromide; Alkyl sulfonic acid esters such as methane sulfonic acid (alkyl group: 1 to 18 carbon atoms); aryl sulfonic acid alkyl esters (alkyl group: 1 to 18 carbon atoms) such as benzene sulfonic acid and toluene sulfonic acid; The dialkyl diallyl ammonium salt etc. which were quaternized by dialkyl sulfate (alkyl group: C1-C4) etc. are mentioned.

The monomer which has a functional group which can adsorb | suck to a pigment can be suitably selected according to the kind of pigment to be disperse | distributed, These may be used independently and may use 2 or more types together.

Block b1 having an annular structure

In the polymer compound (A-1) according to the first aspect of the present invention, the block (b1) having a cyclic structure in the block-type polymer compound has a block (b1-1) having a cyclic structure in which an acid group is directly bonded. In the polymer compound (A-2) according to the second aspect of the present invention, the block (b1) is a block (b1-2) having a lactone structure or an acid anhydride structure.

The monomer mentioned above is mentioned as a monomer which comprises the block (b1-1) which has a cyclic structure which an acidic radical bonds directly. Preferably, it consists of monomers represented by the said general formula (G-I)-(G-V).

The monomer which has an acidic radical can be suitably selected according to the kind of pigment to be disperse | distributed, These may be used independently and may use 2 or more types together.

As the lactone structure or the acid anhydride structure in the block (b1-2) having a lactone structure or an acid anhydride structure, the lactone structure and the acid anhydride structure described above can be adopted, respectively.

Block that does not adsorb to pigment (c1)

Although it does not restrict | limit especially as a monomer which comprises the block (c1) which does not adsorb | suck to a pigment, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, Itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, etc. can be mentioned. These monomers may be used independently and may use 2 or more types together.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, T-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) T-octyl acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxy (meth) acrylate, phenyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acrylate Methoxyethyl, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, vinyl (meth) acrylate, (meth) acrylic acid 2 -Phenylvinyl, (meth) acrylic acid 1-propenyl, (meth) acrylic acid allyl, (meth) acrylic acid 2- Aryloxyethyl, (meth) acrylic acid propargyl, (meth) acrylic acid benzyl, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl Ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β-phenoxyethoxyethyl, (meth) acrylic acid nonyl Phenoxypolyethylene glycol, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluoro (meth) acrylate Octylethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid tribromophenyl, (meth) acrylic acid tribromophenyloxyethyl, (meth) Methacrylate-butyrolactone, (meth) acrylic acid (2-hydroxyethyl), (meth) acrylic acid (2,3-dihydroxypropyl), (meth) acrylic acid glycidyl, (meth) acrylic acid 2-isocyanate Ethyl and the like.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate and the like.

Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, dibutyl maleate, and the like.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate, and the like.

Examples of itaconic acid diesters include dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid and the like.

As (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth Acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide , (Meth) acryloyl morpholine, diacetone acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, N -Allyl (meth) acrylamide, etc. are mentioned.

Examples of styrenes are styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromostyrene And chloromethylstyrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc, etc.), methyl vinyl benzoate, α-methylstyrene, and the like.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl Ethers and the like.

Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

Examples of the olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.

Examples of maleimide include maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide and the like.

Examples of the (meth) acrylonitrile include methacrylonitrile, acrylonitrile and the like.

As a method of obtaining the block-type high molecular compound which concerns on this invention, a conventionally well-known method can be used. For example, living polymerization, the initiator method, etc. are known, and as another method, thiol carboxylic acid or 2-acetylthioethyl ether when carrying out radical polymerization of the monomer which has a pigment adsorption group, or the monomer which does not have a pigment adsorption group is carried out. End polymer obtained by treating a polymer obtained by coexisting a polymer containing a thioester and a thiol group in a molecule such as 10-acetylthiodecanethiol and polymerizing with an alkali such as sodium hydroxide or ammonia and making a polymer having a thiol group at one end. The method of radically polymerizing the monomer component of the other block in the presence of the polymer which has a thiol group is also known. Among these, living polymerization is preferable.

The weight average molecular weight of the block-type high molecular compound of this invention needs to be 1,000-100,000, the range of 3,000-100,000 is preferable, and the range of 5,000-50,000 is more preferable. When the weight average molecular weight is less than 1,000, the stabilization effect is not obtained satisfactorily, and when the weight average molecular weight exceeds 100,000, good adsorption is not obtained and excellent dispersibility is not exhibited.

In addition, the said weight average molecular weight can be measured as a polystyrene conversion value by a gel permeation chromatography (GPC) method. In more detail, monodisperse PHS (polystyrene) is used as a standard (standard), and it measures by RI of GPC. Here, the detailed conditions of the said measurement in this invention are as follows.

Type of column: TSKgel GMH (XL), TSKgel G4000H (XL), TSKgel G3000H (XL) and TSKgel G2000H (XL) (all made by trade name TOSOH)

Developing Solvent: Tetrahydrofuran

Flow rate: 1μL / min

Temperature: 40 ℃

Sample concentration: 40 g / L

Sample injection volume: 100 μL

The measurement of the weight average molecular weight in this specification can be performed by the following method.

Grafted Polymer Compound

The graft polymer compound according to the present invention may have a cyclic structure in the graft side chain, in the main chain, or both.

As a method for synthesizing the graft polymer, a general method is (1) polymerizing a branched monomer from a main chain polymer, and (2) a branched polymer into a main chain polymer, as described in New Molecular Experiments Vol. 2 (Public Publication, 1995). (3) a method of copolymerizing the main chain monomer with the branched polymer, and the like.

In the first aspect of the present invention, the graft-type polymer compound includes one or more monomers containing an acid group represented by the general formulas (GI) to (G-III) in either or both of the main chain and the branched portion. Can be obtained by copolymerizing with another copolymerizable monomer.

As another copolymerizable monomer, (1) the monomer which has an organic pigment | dye structure or heterocyclic structure, (2) the monomer which has an acidic group, (3) the monomer which has a basic nitrogen atom, (4) a urea group, a urethane group, and coordination C4 or more hydrocarbon group having an oxygen atom, alkoxysilyl group, epoxy group, isocyanate group, monomer having hydroxyl group, (5) monomer containing ionic functional group, (6) (meth) acrylic acid ester, crotonic acid ester , Vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth One or more types of monomers, such as an acrylonitrile, can be selected arbitrarily.

The following aspect is mentioned as a preferable aspect in the said graft type high molecular compound in 1st aspect of this invention.

1. The monomer represented by the above-mentioned (1)-(6), the monomer containing the acid group shown by said general formula (GI)-(GV), and a polymeric oligomer (henceforth a macromonomer) are made into a copolymerization component. Graft polymer (particularly preferred to include (1))

2. Graft type which uses as a copolymerization component the polymerizable oligomer (henceforth a macromonomer) containing the monomer represented by said (1)-(6), and the acidic radical represented by said general formula (GI)-(GV). Polymer (particularly preferably comprising (1))

3. It contains the monomer represented by the above-mentioned (1)-(6), the monomer containing the acidic radical shown by the said general formula (GI)-(GV), and the acidic radical shown by the said general formula (GI)-(GV) Graft-type polymer which has a polymeric oligomer (henceforth a macromonomer) as a copolymerization component (it is especially preferable to contain (1)).

In the second aspect of the present invention, the graft polymer compound may have a lactone structure or an acid anhydride structure in the graft side chain or in the main chain, but it is particularly preferable to have the graft side chain.

As a graft type high molecular compound, the graft type high molecular compound formed by superposing | polymerizing the monomer which comprises the adsorption site | part (a2), the macromonomer (b2) shown below, and the monomer which comprises the site | part (c2) which does not adsorb | suck to a pigment are preferable. Thereby, the dispersibility and dispersion stability of a pigment improve.

In the graft polymer compound according to the present invention, it is preferable to include a repeating unit having an adsorption site (a2) in the graft backbone. Moreover, it is preferable that the ratio of the said repeating unit in a graft main chain is 5-50 mass%, More preferably, it is 10-50 mass%.

It is preferable that macromonomer (b2) is 20-90 mass% of the whole high molecular compound, More preferably, it is 40-90 mass%. Moreover, in a macromonomer, it is necessary to have a repeating unit which has a cyclic structure at least, and it is preferable that content of the repeating unit which has a cyclic structure is 5-100 mass%.

It is preferable that the site | part (c2) which does not adsorb | suck to a pigment is 0-70 mass% of the whole high molecular compound.

As for the monomer constituting the adsorption site (a2) and the monomer constituting the site (c2) that does not adsorb to the pigment, the monomer (a1) constituting the adsorption site described above and the block (c1) that do not adsorb to the above-mentioned pigment, respectively. The monomer which comprises () can be employ | adopted.

Macromonomer (b2)

In the graft polymer compound according to the present invention, it is preferable to have the macromonomer (b2) in the graft side chain or the main chain.

As the macromonomer (b2) in the graft polymer compound, polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, and the like are preferably listed, and represented by the following general formula (5) The graft polymer compound having a structural unit at least in the graft side chain is more preferable.

In General Formula (5), R ⁷⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Q is a cyano group, an aryl group having 6 to 30 carbon atoms, -COOR ⁷⁵ (where R ⁷⁵ is a hydrogen source Now, an alkyl group having 1 to 22 carbon atoms, or an aryl group having 6 to 30 carbon atoms) or a group having a cyclic structure.

However, in the whole macromonomer contained in a graft type high molecular compound, it is necessary to contain the group which has the said cyclic structure at least, or it is preferable that content of the group which has a cyclic structure is 5-100 mass%.

In General Formula (5), the alkyl group represented by R ⁷⁴ may have a substituent, preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group. Examples of the substituent for the alkyl group include a halogen atom, a carboxyl group, an alkoxycarbonyl group, an alkoxy group, and the like. Specific examples of the alkyl group include methyl group, ethyl group, hexyl group, octyl group, trifluoromethyl group, carboxymethyl group, methoxycarbonylmethyl group and the like. do.

Among these R ⁷⁴ , a hydrogen atom and a methyl group are preferable.

In General Formula (5), the aryl group represented by Q may have a substituent, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is particularly preferable. As a substituent of an aryl group, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, etc. are mentioned. Specific examples of such aryl groups include phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, Dichlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group and the like. Among these aryl groups, an unsubstituted aryl group or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group is preferable, and an aryl group substituted with an unsubstituted aryl group or an alkyl group is particularly preferable.

The alkyl group represented by R ⁷⁵ in —COOR ⁷⁵ represented by Q in General Formula (5) may have a substituent, preferably an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 8 carbon atoms. Is preferred. As a substituent of an alkyl group, a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, a carbamoyl group, etc. are mentioned. Specific examples of such alkyl groups include methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and 2-chloroethyl groups. , 2-bromoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 2-bromopropyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 2-hex Senyl, 4-methyl-2-hexenyl, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methylbenzyl, ethylbenzyl Group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, bicyclo [3.2.1] octo-2-yl group, 1-adamantyl group , Dimethylaminopropyl group, acetylaminoethyl group, N, N-dibutylaminocarbamoylmethyl group and the like. Of these alkyl groups, unsubstituted alkyl groups or alkyl groups substituted with halogen atoms, aryl groups, or hydroxyl groups are preferred, and unsubstituted alkyl groups are particularly preferred.

The aryl group represented by R ⁷⁵ in —COOR ⁷⁵ represented by Q in General Formula (5) may have a substituent, preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably having 6 to 12 carbon atoms. Aryl groups are preferred. As a substituent of an aryl group, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acylamino group, etc. are mentioned. As a specific example of such an aryl group, a phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group And dichlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidephenyl group, propioamidophenyl group, dodecylylamidophenyl group and the like. Of these aryl groups, unsubstituted aryl groups or aryl groups substituted with halogen atoms, alkyl groups or alkoxy groups are preferred, and aryl groups substituted with alkyl groups are particularly preferred.

Among these R ⁷⁵ , a hydrogen atom and an alkyl group having 1 to 22 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 12 carbon atoms are particularly preferable.

In 1st aspect, the cyclic structure represented by Q in General formula (5) has an acidic radical, Specifically, group represented by the above-mentioned general formula (G-I)-(G-V) is preferable.

In the second aspect, the cyclic structure represented by Q in General Formula (5) is a group having a lactone structure or an acid anhydride structure, and specifically, the general formulas (LC1-1) to (LC1-10) and (UA1) described above. Groups represented by -1) to (UA1-5) are preferable.

As a specific example of the branched part (graft side chain) of the graft-type high molecular compound which has at least a structural unit represented by such general formula (5) in a branched part (graft side chain), polymethyl (meth) acrylate and poly-n-butyl (Meth) acrylate, poly-i-butyl (meth) acrylate, poly (methyl (meth) acrylate-co-benzyl (meth) acrylate), poly (methyl (meth) acrylate-co-styrene), Poly (methyl (meth) acrylate-co- (meth) acrylic acid), poly (methyl (meth) acrylate-co-acrylonitrile) and the like.

You may use any well-known method for the synthesis | combination of the graft type polymer compound which has a structural unit represented by General formula (5) at least in a branch part (graft side chain).

Specifically, copolymerization of the macromonomer which has at least the structural unit represented by General formula (5), and the ethylenically unsaturated monomer copolymerizable with the said macromonomer is mentioned.

Among the macromonomers having at least the structural unit represented by the general formula (5), preferred ones are represented by the following general formula (6).

In General Formula (6), R ⁷⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W has the same meaning as W in General Formula (GI). A represents group which has at least a structural unit represented by the said General formula (5).

Although the specific example of the macromonomer represented by the said General formula (6) is listed below, this invention is not limited to these.

In the said specific example, A is synonymous with A in the said General formula (6).

As said macromonomer which can be obtained as a commercial item, single-terminal methacrylylated polymethylmethacrylate oligomer (Mn = 6000, brand name: AA-6, Toagosei Co., LTD.) And single-terminal methacryloylated poly- n-butylacrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toagosei Co., Ltd.), single-ended methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, Toagosei Co., LTD. Production).

As molecular weight of the said macromonomer, it is preferable that the number average molecular weights (Mn) of polystyrene conversion are 1,000-20,000, and it is more preferable that it is 2,000-15,000. When the number average molecular weight is within the above range, the steric repulsion effect as the pigment dispersant can be more effectively obtained.

In addition, the said number average molecular weight can be measured according to the measuring method of the above-mentioned weight average molecular weight, and the measurement of the number average molecular weight in this specification can be performed by the following methods.

The weight average molecular weight of the graft type high molecular compound which concerns on the 1st aspect of this invention needs to be in the range of 1,000-100,000, and the range of 5,000-50,000 is preferable.

In particular, the range of 300-30,000 is preferable and, as for the weight average molecular weight of a branch part, the range of 1,000-20,000 is more preferable. If there is a molecular weight of the branched portion in the above range, the developability is particularly good, and the developing latitude is widened.

Moreover, the weight average molecular weight of the graft-type high molecular compound which concerns on the 2nd aspect of this invention needs to be 1,000-100,000, or it is preferable that it is the range of 3,000-100,000, and the range of 5,000-50,000 is more preferable. If the weight average molecular weight is less than 1,000, the stabilization effect may not be obtained satisfactorily, and if the weight average molecular weight exceeds 100,000, good adsorption may not be obtained and excellent dispersibility may not be exhibited.

Terminally modified polymer compound

The terminally modified polymer compound according to the present invention has a cyclic structure in the stem polymer portion (ie, a portion other than the end of the polymer) and a functional group at the end of the polymer.

Although the method of synthesizing the polymer having a functional group at the terminal of the polymer is not particularly limited, for example, the following method, a method of combining them, and the like can be enumerated.

1. Synthesis by polymerization (eg, radical polymerization, anionic polymerization, cationic polymerization, etc.) using a functional group-containing polymerization initiator (polymerization initiator capable of introducing a functional group at the polymer terminal).

2. Synthesis by radical polymerization using a functional group-containing chain transfer agent (chain transfer agent capable of introducing a functional group at the polymer end)

Here, the functional group to be introduced includes an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, The group selected from an epoxy group, an isocyanate group, a hydroxyl group, and an ionic functional group etc. are mentioned.

As a functional group introduce | transduced into a terminal here, an adsorption site | part (a3) is preferable, and the functional group which can introduce | transduce into the said adsorption site | part (a3) may be sufficient. As the monomer constituting the adsorption site (a3), the above adsorption site (a1) can be adopted.

As a chain transfer agent which can introduce a functional group to a polymer terminal, for example, a mercapto compound (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercapto) Butyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl ) Amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1 , 2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3- Pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or disulfide which is an oxidized compound of these mercapto compounds Feed compounds and halogen compounds (for example, 2-iodineethanesulfonic acid, 3-iodine propanesulfonic acid, etc.) are listed.

Moreover, as a polymerization initiator which can introduce a functional group in a polymer terminal, 2,2'- azobis (2-cyanopropanol), 2,2'- azobis (2-cyanopentanol), 4 , 4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis [2- (5-methyl-2-imi Dazolin-2-yl) propane], 2,2'-azobis [2- (imidazolin-2-yl) propane], 2,2'-azobis [2- (3,4,5,6 -Tetrahydropyrimidin-2-yl) propane], 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2 '-Azobis [2-methyl-n- (2-hydroxyethyl) -propionamide] and the like or derivatives thereof.

As a stem polymer part, the polymer which consists of a site | part (b3) which has a cyclic structure, and the site | part (c3) which does not adsorb | suck to a pigment is preferable.

Moreover, as a monomer which comprises the site | part (b3) which has the said cyclic structure, and the monomer which comprises the site | part (c3) which does not adsorb | suck to a pigment, for example, as a radically polymerizable monomer, the block (b1) which has the above-mentioned cyclic structure is mentioned. And the monomer constituting the block (c1) which does not adsorb to the pigment described above can be employed.

It is preferable that 5-100 mass% of repeating units which have a cyclic structure are contained in a stem polymer part.

As a molecular weight of the terminal modification type polymer which concerns on the 1st aspect of this invention, it is preferable that it is a weight average molecular weight 1,000-50,000. If the number average molecular weight is 1,000 or more, the steric repulsion effect as the pigment dispersant can be more effectively obtained, and if it is 50,000 or less, the steric effect can be more effectively suppressed, and the adsorption time to the pigment can be shortened more.

The weight average molecular weight of the terminal modification type polymer compound which concerns on the 2nd aspect of this invention needs to be 1,000-100,000, or it is preferable that it is 1,000-50,000, and it is especially preferable that it is 1,000-30,000. If the weight average molecular weight is less than 1,000, the steric repulsion effect as a pigment dispersant is not obtained satisfactorily, and when the weight average molecular weight exceeds 100,000, an effective steric effect is not obtained and a shortening of the adsorption time to the pigment can be realized. Can't.

Straight random copolymer

The high molecular compound (A-1) which concerns on the 1st aspect of this invention may have a structure of a linear random copolymer. A linear random copolymer can obtain the monomer containing the acidic radical shown by the said general formula (G-I)-(G-V) by arbitrary polymerization methods, such as another copolymerizable monomer and radical polymerization. Other copolymerizable monomers include, but are not limited to (1) monomers having an organic pigment structure or heterocyclic structure, (2) monomers having an acid group, (3) monomers having a basic nitrogen atom, and (4) urea Baby, urethane, C4 or more hydrocarbon group having a coordinating oxygen atom, an alkoxysilyl group, an epoxy group, an isocyanate group, a monomer having a hydroxyl group, (5) a monomer containing an ionic functional group, (6) (meta) Acrylic esters, crotonic esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, and olefins One or more types of monomers, such as maleimide and (meth) acrylonitrile, can be selected arbitrarily.

Moreover, it is preferable to contain 1 or more types chosen from the monomer group of (1)-(3).

Although the preferable weight average molecular weight of a linear random copolymer is not specifically limited, The range of 1,000-100,000 is preferable, and the range of 3,000-50,000 is more preferable. If the weight average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and if the weight average molecular weight is 100,000 or less, it can adsorb | suck more effectively and can exhibit favorable dispersibility.

The above-mentioned high molecular compound (A) may be used independently, and may mix and use 2 or more types.

It is preferable to add the addition amount of a high molecular compound (A) so that it may become 0.3-100 mass% with respect to the pigment (B) mentioned later, and 0.5-80 mass% is more preferable. When these high molecular compounds (A) are used within the said range as a pigment dispersant, sufficient pigment dispersion effect will be obtained. However, the optimum addition amount of the high molecular compound (A) is appropriately adjusted by the combination of the kind of the pigment (B) to be used, the kind of the solvent, and the like.

As an acid value of the high molecular compound (A) which has a cyclic structure by which the acidic radical in the 1st aspect of this invention directly bonds, 50-300 mg KOH / g is preferable, More preferably, it is 50-200 mg KOH / g.

An acid value is by measuring the amount (mg) of potassium hydroxide required to neutralize a compound. Desired acid value resin can be obtained by adjusting the number of acid groups which a monomer has, the molecular weight of a monomer, the composition ratio of a monomer, etc., and controlling the number of acid groups which resin has.

(B) pigment

The pigment dispersion composition of the present invention has at least one pigment (B). As the pigment (B), conventionally known various inorganic pigments or organic pigments can be appropriately selected and used. As the particle size of the pigment (B), considering that the color filter in which the pigment dispersion composition of the present invention is preferably used has a high transmittance, etc., it is preferable that the organic pigment is preferred, and that the particle size of the pigment (B) is preferably used. desirable. Considering the handleability of the pigment dispersion composition and the photocurable composition containing the same, the average primary particle diameter of the pigment is preferably 10 to 300 nm, more preferably 10 to 150 nm, and more preferably 10 to 150 nm. 10-100 nm is more preferable, and 10-30 nm is the most preferable. When the particle diameter is in the above range, the transmittance is high, the color characteristics are good, and it is effective to form a high contrast color filter.

The average primary particle diameter is observed by SEM or TEM, and can be calculated | required by measuring 100 particle sizes in the part which particle | grains do not aggregate, and calculating an average value.

Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and The complex oxide of the said metal can be enumerated.

As said organic pigment, for example,

CIPigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 , 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

CIPigment Yelloｗ 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36 , 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139 , 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C.I.Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73

C.I.Pigment Green 7, 10, 36, 37

Cl substituents of CIPigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Thing, 80

C.I.Pigment Violet 1, 19, 23, 27, 32, 37, 42

C.I.Pigment Broｗn 25, 28

C.I. Pigment Black 1, 7, and the like.

Among these, the following can be mentioned as a pigment which can be used preferably. However, in this invention, it is not limited to these.

C.I.Pigment Yelloｗ 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C.I. Pigment Orange 36, 71,

C.I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C.I. Pigment Violet 19, 23, 32,

C.I.Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C.I. Pigment Green 7, 36, 37;

C.I.Pigment Black 1, 7

Process pigment

In the present invention, a fine and well-defined organic pigment can be used as necessary. Pigment refinement is a process of grinding a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt together into a high viscosity liquid composition.

In this process, you may add the high molecular compound which coat | covers a pigment and the high molecular compound (A) of this invention as needed. The polymeric compound which coats the pigment (B) which may be added is preferably solid at room temperature, water insoluble, and at least partially soluble in water-soluble organic solvents used for the wetting agent in salt milling, Natural resins, synthetic resins and synthetic resins modified from natural resins are used. When using a dry process pigment, it is preferable that the compound used is solid at room temperature.

Rosin is typical as a natural resin, and rosin derivative, a cellulose derivative, a rubber derivative, a protein derivative, and those oligomers are mentioned as a modified natural resin. Examples of the synthetic resins include epoxy resins, acrylic resins, maleic acid resins, butyral resins, polyester resins, melamine resins, phenol resins and polyurethane resins. Examples of the synthetic resin modified from natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.

Examples of the synthetic resins include polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, polyurethanes, polyesters, poly (meth) acrylates, (meth) acrylic copolymers, and naphthalene sulfonic acid formalin condensates. do.

It is preferable that it is a synthetic resin which has a functional group which can adsorb | suck to a pigment, and it is preferable that it is a high molecular compound which has an organic pigment | dye structure or a heterocyclic structure. Specifically, the poly (meth) acrylate which has a monomer represented by (M-1)-(M-27) is mentioned. By having a functional group which can adsorb | suck to a pigment in a high molecular compound, a polymeric compound can coat | cover a pigment efficiently and can suppress aggregation of pigments.

The timing of adding these resins may all be added at the beginning of a salt milling process, and may be divided and added.

The water-soluble organic solvent used for the grinding of the pigment (B) is not particularly limited as long as it functions to wet organic pigments and inorganic salts, and dissolves (mixes) in water and does not substantially dissolve the inorganic salts used. Do not. However, since a temperature rises at the time of salt milling and a solvent becomes easy to evaporate, the high boiling point solvent of 120 degreeC or more of boiling points is preferable from a safety point. As a water-soluble organic solvent, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl, for example Ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol , Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like are used. As the water-soluble organic solvent, methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Propylene glycol, propylene glycol monomethyl ether acetate, and the like.

However, if it is adsorbed to the pigment by using a small amount and is not lost in the waste water, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, Butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl Sulfoxide, N-methylpyrrolidone, etc. may be used, and 2 or more types of solvents may be mixed and used as needed.

In the present invention, water-soluble inorganic salts include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.

It is preferable that it is 1-50 times (mass ratio) of pigment (B), as for the usage-amount of water-soluble inorganic salt, it is more preferable that it is 1-30 times (mass ratio), and it is especially preferable that it is 5-25 times (mass ratio). Although the usage-amount of water-soluble inorganic salt has many grinding effects, 1-10 times (mass ratio) are preferable at the point of productivity, and it is preferable that moisture is 1 mass% or less.

As addition amount of the water-soluble organic solvent in the 1st aspect of this invention, 5-50 mass% is preferable with respect to an inorganic salt. More preferably, it is 10-40 mass%, and it is 15-35 mass% optimally. If the added amount is less than 5% by mass, uniform kneading may be difficult and the particle size may not be uniform. When the addition amount is 50 mass% or more, the kneading composition becomes too soft and it becomes difficult to shear the kneading composition, so that a sufficient refinement effect may not be obtained.

It is preferable that the usage-amount of the water-soluble organic solvent in the 2nd aspect of this invention is 50-300 mass% with respect to a pigment, More preferably, it is 100-200 mass%. When the amount of use is at least 50 mass%, uniform kneading can be performed, and the particle size can be more neatly trimmed. When the amount used is 300% by mass or less, the kneading composition does not become too soft, the shearing to the kneading composition is satisfactorily achieved, and a sufficient refinement effect is obtained.

The water-soluble organic solvent may be added all at the initial stage of salt milling, or may be added separately. A water-soluble organic solvent may be used independently and may use 2 or more types together.

In the present invention, when the wet grinding apparatus is used, the operating conditions thereof are not particularly limited. However, when the apparatus is a kneader, in order to effectively advance the grinding by the grinding media, the operating conditions are 10 to 10 rotational speed of the blades in the apparatus. 200 rpm is preferable, and since the rotation ratio of two axes is relatively large, a grinding effect is large, it is preferable. The operation time is preferably 1 hour to 8 hours in addition to the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Moreover, the water-soluble inorganic salt which is a grinding | pulverization medium is 5-50 micrometers in particle size, sharp distribution of a particle diameter, and spherical shape is preferable.

After the grinding, the water-soluble organic solvent and the water-soluble inorganic salts are dissolved in hot water, filtered, washed with water and dried in an oven to obtain a fine pigment.

These organic pigments can be used alone or in combination in various ways to improve color purity. The specific example of the said combination is shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindolin yellow pigment, and a quinophthalone yellow pigment Or a mixture of a perylene red pigment, an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like. For example, CI pigment red 177 is listed as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are listed as a perylene pigment, and CI pigment red 254 is a diketopyrrolopyrrole pigment. The mixing with CI pigment yellow 83, CI pigment yellow 139, or CI pigment red 177 is preferable at the point of color reproducibility. Moreover, as for the mass ratio of a red pigment and another pigment, 100: 5-100: 80 are preferable. By more than 100: 5, the light transmittance of 400 nm to 500 nm can be suppressed favorably, and color purity can be raised. Moreover, favorable color development power can be obtained by being 100: 80 or less. Especially as said mass ratio, the range of 100: 10-100: 65 is optimal. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

In addition, as a green pigment, the halogenated phthalocyanine type pigment can be used individually by 1 type or in combination with this and a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine type yellow pigment, or an isoindolin type yellow pigment. have. For example, CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Mixing of yellow 185 is preferred. As for mass ratio of a green pigment and a yellow pigment, 100: 5-100: 200 are preferable. When the said mass ratio is 100: 5 or more, the light transmittance of 400 nm to 500 nm can be suppressed favorably, and color purity can be improved. Further, by being 100: 200 or less, the dominant wavelength does not become too close to the long wavelength, and the deviation from the NTSC target color can be satisfactorily suppressed. As said mass ratio, the range of 100: 20-100: 150 is especially preferable.

As a blue pigment, a phthalocyanine type pigment can be used individually by 1 type, or the mixture of this and a dioxazine type purple pigment can be used. As a particularly preferred example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 can be enumerated.

As for mass ratio of a blue pigment and a purple pigment, 100: 0-100: 100 are preferable, More preferably, it is 100: 70 or less.

Moreover, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture can be used as a pigment suitable for a black matrix use, and the combination of carbon black and titanium black is preferable.

In addition, the mass ratio of carbon black and titanium black is preferably in the range of 100: 0 to 100: 60. By 100 or less than 60, the fall of dispersion stability can be suppressed favorably.

In this invention, when using dye as a coloring agent, the photocurable composition melt | dissolved uniformly is obtained.

There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. Hei 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Registration 2592207, U.S. Patent No. 4,808,501, U.S. Patent 5,667,920, U.S. Patent 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115 JP-A-6-194828, JP-A-8-211599, JP-A 4-249549, JP-A-10-123316, JP-A-11-302283 Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215, Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open No. 8-62416, Japanese Patent Laid-Open No. 2002-14220, Japanese Patent Laid-Open No. 2002-14221, Japanese Patent Laid-Open No. 2002-14222, Japanese Patent Laid-Open No. 2002-14223, Japanese Patent Laid-Open No. 8-302224, Japanese Patent Laid-Open No. 8-73758, Japanese Patent Laid-Open It is a pigment | dye as described in Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531.

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine and pyrrolo. Dyestuffs, such as a pyrazole azomethine type, a xanthene type, a phthalocyanine type, a benzopyran type, an indigo type, can be used.

As content in the pigment dispersion composition of a pigment, 1-30 mass% is preferable with respect to the total solid (mass) of the said composition, and 3-20 mass% is more preferable. If content of a pigment is in the said range, color Sufficient density is also effective for securing excellent color characteristics.

Pigment derivative (C)

The pigment derivative (C) is added to the pigment dispersion composition of this invention as needed. The pigment derivative (C) having affinity with the dispersant or the polar group introduced therein is adsorbed on the surface of the pigment and used as the adsorption point of the dispersant, thereby dispersing the pigment as fine particles in the composition, thereby preventing reaggregation. It is effective in forming a color filter having high contrast and excellent transparency.

The pigment derivative (C) is a compound in which an organic pigment is specifically used as a mother skeleton and an acidic group, a basic group, and an aromatic group are introduced into the side chain as a substituent. Specific examples of the organic pigment include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments and benzimidazolones. Pigments and the like. Generally, pale yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine and quinoline, which are not called dyes, are also included. As a pigment derivative (C), Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Unexamined-Japanese-Patent No. 8 What is described in -295810, Unexamined-Japanese-Patent No. 11-199796, Unexamined-Japanese-Patent No. 2005-234478, Unexamined-Japanese-Patent No. 2003-240938, Unexamined-Japanese-Patent No. 2001-356210, etc. can be used.

As content in the pigment dispersion composition of the pigment derivative (C) which concerns on this invention, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is in the above range, the dispersion can be performed satisfactorily while the viscosity is kept low, and the dispersion stability after dispersion can be improved, and excellent color characteristics can be obtained with high transmittance, and a good color can be obtained when producing a color filter. It can comprise with high contrast which has a characteristic.

Timing to which a pigment derivative (C) is added may be added at the time of salt milling, and may be added at the time of dispersion.

The dispersion method is, for example, a microdispersion using a bead disperser (eg, dispermat manufactured by GETZMANN Co., Ltd.) using zirconia beads or the like, in which a pigment and a dispersant are mixed in advance and dispersed in a homogenizer or the like. By doing so. The dispersion time is preferably about 3 to 6 hours.

Dispersant (D)

The high molecular compound (A) mentioned above can be used as a dispersing agent (D). Thereby, while the dispersion state of the pigment (B) in an organic solvent becomes favorable, for example, when a color filter is comprised, even if it contains a pigment (B) in high concentration, high developability and surface smoothness can be expressed.

When using as a dispersing agent (D), it is preferable that a high molecular compound (A) is a graft type high molecular compound or a terminal modified | denatured high molecular compound, The graft which contains the copolymerization unit derived from the monomer which has an organic pigment | dye structure or a heterocyclic structure is the above-mentioned. Particularly preferred is a type polymer compound or a terminal modified polymer compound having an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, or a urethane group as the terminal group.

Moreover, as needed, dispersing agents, such as a pigment dispersing agent and surfactant conventionally known other than a high molecular compound (A), can be added.

Known dispersants (pigment dispersants) include polymer dispersants [e.g., polyamideamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acryl Latex, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure.

Although the ratio (mass ratio) of the high molecular compound (A) and a well-known dispersing agent in the case of using a well-known dispersing agent together is not restrict | limited, 10 / 90-90 / 10 is preferable and 20 / 80-80 / 20 is especially preferable. .

A preferred embodiment of the present invention is obtained by dispersing the above-described pigment (processing pigment) (B), pigment derivative (C) and dispersant (D) coated with a polymer compound (A) having a weight average molecular weight of 1,000 to 100,000 in an organic solvent. Pigment dispersion composition. A high molecular compound (A) may be used as a pigment coating high molecular compound added at the time of pigment processing, and may be used as a dispersing agent (D). In addition, it is preferable to use a high molecular compound (A) as a dispersing agent (D).

Although the high molecular compound (A) which concerns on this invention may be used for any of a salt milling process and a dispersion process, it is preferable to use for a dispersion process. Moreover, it can also be used for both a salt milling process and a dispersion process. Moreover, it can also use in addition to the process of preparing a photocurable composition using the pigment dispersion composition which has a high molecular compound (A) concerning this invention.

When the said dispersing agent is a polymeric dispersing agent, it is preferable to add the addition amount of the dispersing agent in this invention so that it may become 0.5-100 mass%, 3-100 mass% is more preferable, and 5-80 mass% Particularly preferred. If the amount of the pigment dispersant is within the above range, sufficient pigment dispersion effect is obtained. However, the optimal addition amount of a dispersing agent is suitably adjusted with combinations, such as the kind of pigment to be used, the kind of solvent, etc.

Preparation of Pigment Dispersion Compositions

Although the preparation form of the pigment dispersion composition of this invention is not restrict | limited, For example, a pigment, a dispersing agent, and a solvent are 0.01-1 mm of a vertical or horizontal sand mill, a pin mill, a slit mill, an ultrasonic disperser, etc. It can obtain by performing a microdispersion process with the beads of glass, zirconia, etc. of a particle diameter.

Before the bead dispersion, kneading and dispersing with strong shearing force, using two rolls, three rolls, ball mill, tronn mill, disper, kneader, cornider, homogenizer, blender, single screw or twin screw extruder It is also possible to do this.

In addition, the details about kneading | mixing and dispersion are T.C. Patton Flont and Pigment Dispersion (published by John Wiley and Sons, 1964).

The pigment dispersion composition of this invention is used suitably for the coloring photocurable composition used for manufacture of a color filter.

Photocurable composition

The photocurable composition of this invention contains the pigment dispersion composition, alkali-soluble resin, photopolymerizable compound, and photoinitiator of the above-mentioned this invention, and may contain another component as needed. Moreover, the detail of the pigment dispersion composition of this invention is as above-mentioned. Hereinafter, each component is explained in full detail.

Alkali soluble resin

As alkali-soluble resin, it is a linear organic high molecular polymer, group which promotes at least 1 alkali solubility in a molecule | numerator (preferably an acryl-type copolymer and a molecule | numerator which has a styrene type copolymer as a main chain) (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group) Etc. can be suitably selected from alkali-soluble resin which has. Among these, More preferably, it is soluble in the organic solvent and can be developed by weak alkaline aqueous solution.

For the production of alkali-soluble resin, for example, a method by a known radical polymerization method can be applied. The polymerization conditions such as the temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be determined experimentally. .

As said linear organic high polymer, the polymer which has a carboxylic acid in a side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836, Japan Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like as described in the respective publications of Patent Publication No. 59-71048; and The acid cellulose derivative which has a carboxylic acid in a side chain, the acid anhydride was added to the polymer which has a hydroxyl group, etc. Moreover, the high molecular polymer which has a (meth) acryloyl group in a side chain is also mentioned as a preferable thing.

Among these, in particular, a multipart copolymer composed of a benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomers is preferable.

In addition, those copolymerized with 2-hydroxyethyl methacrylate are also listed as useful. The said polymer can be mixed and used in arbitrary quantity.

2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and 2-hydroxy-3-phenoxypropylacrylic acid described in Japanese Patent Application Laid-Open No. 7-140654. Latex / polymethylmethacrylate macromonomer / benzylmethacrylate / methacrylic acid copolymer, 2-hydroxyethylmethacrylate / polystyrene macromonomer / methylmethacrylate / methacrylic acid copolymer, 2-hydroxyethyl meta Acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like.

About the specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and another monomer copolymerizable with this is especially preferable. Here, (meth) acrylic acid is a general term which combined acrylic acid and methacrylic acid, and (meth) acrylate is a general term of acrylate and methacrylate similarly below.

As another monomer copolymerizable with the said (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atom of an alkyl group and an aryl group may be substituted by the substituent.

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) Acrylate, cyclohexyl (meth) acrylate, etc. can be mentioned.

Moreover, as said vinyl compound, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene, for example Macromonomer, polymethylmethacrylate macromonomer, CH ₂ = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.], And the like can be mentioned.

These copolymerizable other monomers can be used individually by 1 type or in combination of 2 or more types. Preferred copolymerizable other monomers are at least one selected from CH ₂ = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. , Particularly preferably CH ₂ = CR ¹ R ² and / or CH ₂ = C (R ¹ ) (COOR ³ ).

As for content in the photocurable composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 2-12 mass%, Especially preferably, it is 3-10 mass%. .

Photopolymerizable compound

The photopolymerizable compound has at least one addition-polymerizable ethylenically unsaturated group, preferably a compound having a boiling point of 100 ° C. or higher at atmospheric pressure, and particularly preferably a tetrafunctional or higher acrylate compound.

As a compound which has the said at least 1 addition-polymerizable ethylenically unsaturated group, and whose boiling point is 100 degreeC or more at normal pressure, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) Monofunctional acrylates and methacrylates such as acrylate; Polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acrylic oiloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane (Meth) acrylated addition of ethylene oxide or propylene oxide to polyfunctional alcohols, poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Urethane acrylates described in Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43 Polyfunctional acrylates and methacrylates, such as the polyester acrylates of 191 and Unexamined-Japanese-Patent No. 52-30490, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned.

Moreover, the thing introduce | transduced as a photocurable monomer and an oligomer can be used by Japanese adhesive association Vol.20, No.7, pages 300-308.

Further, (meth) acrylated is added after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-open No. Hei 10-62986 together with the specific examples as general formulas (1) and (2). Compounds can also be used.

Especially, the structure where dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types can also be used.

Furthermore, urethane acrylates and Japanese patent publications such as those described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. Hei 2-16765. Also preferred are urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Application Laid-Open No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Furthermore, by using addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238. It is possible to obtain a photopolymerizable composition having a very good photosensitive speed. As a commercial item, urethane oligomer UAS-10, UAB-140 (all are brand name: Nippon Paper Industries Co., Ltd. product), UA-7200 (brand name: Shin-nakamura Chemical Co. Ltd. product), DPHA-40H (brand name: Nippon Manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

Moreover, ethylenically unsaturated compounds which have an acid group are also preferable, As a commercial item, Toagosei Co., Ltd., for example. TO-756 which is a carboxyl group-containing trifunctional acrylate of preparation, TO-1382 which is a carboxyl group-containing 5-functional acrylate, etc. are mentioned.

A photopolymerizable compound can be used in combination of 2 or more type other than using individually by 1 type.

As content in the photocurable composition of a photopolymerizable compound, 20-200 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 50-120 mass%. If content of a photopolymerizable compound is in the said range, hardening reaction will fully be performed.

Photopolymerization initiator

The photocurable composition of this invention may contain a photoinitiator. As a photoinitiator, halomethyl-sadiazole described in Unexamined-Japanese-Patent No. 57-6096, halomethyl-s described in Unexamined-Japanese-Patent No. 59-1281, 53-133428, etc., for example. Active halogen compounds such as triazine, aromatic carbonyl compounds such as ketal, acetal, or benzoin alkyl ethers described in each specification such as US Patent USP-4318791, European Patent Publication EP-88050A, and US Patent USP-4199420 Aromatic ketone compounds such as benzophenones described in the above, (thio) xanthone-based or acridine-based compounds described in the Fr-2456741 specification, coumarin-based or biimidazole-based compounds described in JP-A-10-62986; Sulfonium organoboron complexes, such as Unexamined-Japanese-Patent No. 8-015521, etc. are mentioned.

Examples of the photopolymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, active halogen compounds (triazine series, halomethyloxadiazole series, coumarin series) acridines, biimidazole series, An oxime ester system etc. are preferable.

As said acetophenone type photoinitiator, 2, 2- diethoxy acetophenone, p-dimethylamino acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylamino, for example Acetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino propanone-1, etc. can be mentioned preferably.

As said ketal type photoinitiator, benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl acetal, etc. can be mentioned preferably, for example.

Examples of the benzophenone photopolymerization initiators include benzophenone, 4,4 '-(bisdimethylamino) benzophenone, 4,4'-(bisdiethylamino) benzophenone, 4,4'-dichlorobenzophenone, and the like. It may be enumerated preferably.

As said benzoin type or benzoyl type photoinitiator, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, etc. can be mentioned preferably, for example.

As said xanthone type photoinitiator, diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chloro thioxanthone, etc. can be mentioned preferably, for example.

As said active halogen photoinitiator (triazine type, oxadiazole type, coumarin type), for example, 2, 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2, 4-bis (Trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl -s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s- Triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3, 4-dimethoxystyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o- Bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 2-trichloro Tyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl-5- ( Naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 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 can be preferably listed.

As said acridine type photoinitiator, 9-phenyl acridine, 1, 7-bis (9-acridinyl) heptane, etc. can be mentioned preferably, for example.

As said biimidazole type photoinitiator, 2- (o-chlorophenyl) -4,5-diphenyl imidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenyl are mentioned, for example. Midazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, etc. can be mentioned preferably.

In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6 -Trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, and the like.

In this invention, it is not limited to the above photoinitiator, Another well-known thing can also be used. For example, the bisinal polyketolaldonyl compounds described in US Pat. No. 2,367,660, the α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670, and the acyloinethers described in US Pat. No. 2,448,828. , Aromatic acyloin compounds substituted with α-hydrocarbons as described in US Pat. No. 2,722,512, polynuclear quinone compounds as described in US Pat. Nos. 3,046,127 and 2,951,758, and triallylimidazole as described in US Pat. Combination of Emer / p-aminophenylketone, Benzothiazole compound / Trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, JCSPerkin II (1979) 1653-1660, JCSPerkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in Japanese Patent Application Laid-Open No. 2000-66385.

Moreover, these photoinitiators can also be used together.

As for content in the photocurable composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 0.5-5.0 mass%. When content of a photoinitiator is in the said range, a polymerization reaction can be advanced favorably and film formation with favorable intensity | strength is possible.

Sensitizer

It is preferable to add a sensitizer (sensitizing dye) to the photocurable composition of this invention as needed. By exposing this sensitizing dye to the wavelength which can be absorbed, the radical generation reaction of the said polymerization initiator component and the polymerization reaction of the polymeric compound by it are accelerated | stimulated. Examples of such sensitizing dyes include known spectroscopic sensitizing dyes or dyes, or dyes or pigments that absorb light and interact with a photopolymerization initiator.

Spectral sensitizing dyes or dyes

Preferred sensitizing dyes or dyes as the sensitizing dyes used in the present invention are polynuclear aromatics (e.g., pyrene, perylene, triphenylene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhoda). Min B, Rose Bengal), Cyanines (e.g., thiacarbocyanine, oxacarbocyanine), Melocyanines (e.g., melocyanine, carbomelocyanine), Thiazines (e.g. For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acrylflavin), phthalocyanines (for example, phthalocyanine, metal phthalocyanine), porphyrins ( For example, tetraphenylporphyrin, central metal substituted porphyrin), chlorophylls (for example, chlorophyll, chloropyrine, central metal substituted chlorophyll), metal complexes (for example, the following compounds), anthraquinones (for example , Anthraquinone), squaaryl The acids (e.g., squarylium), and the like are listed.

Examples of more preferable spectral sensitizing dyes or dyes are illustrated below.

Styryl pigments described in Japanese Patent Application Laid-Open No. 37-13034; Cationic dyes described in Japanese Patent Application Laid-Open No. 62-143044; Quinoxalinium salts described in Japanese Patent Application Laid-Open No. 59-24147; Trimethylene blue compounds disclosed in Japanese Patent Application Laid-Open No. 64-33104; Anthraquinones described in JP-A-64-56767; Benzoxanthene dye of Unexamined-Japanese-Patent No. 2-1714; Acridines disclosed in Japanese Patent Laid-Open No. 2-226148 and Japanese Patent Laid-Open No. 2-226149; Pyryl salts of Japanese Patent Application Laid-open No. 40-28499; Cyanines described in Japanese Patent Application Laid-Open No. 46-42363; Benzo furan pigment of Unexamined-Japanese-Patent No. 2-63053; Conjugated ketone dyes of Japanese Patent Application Laid-Open No. 2-85858 and Japanese Patent Laid-Open No. 2-216154; Pigment | dye of Unexamined-Japanese-Patent No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent Application Laid-Open No. 2-30321; Cyanine-based dyes described in Japanese Patent Application Laid-Open No. H1-287105; Xanthene-based pigments described in JP-A-62-31844, JP-A-62-31848 and JP-A-62-143043; Amino styryl ketones disclosed in Japanese Patent Application Laid-Open No. 59-28325; Pigments described in JP-A 2-179643; Melocyanine pigment | dye of Unexamined-Japanese-Patent No. 2-244050; Melocyanine pigment | dye of Unexamined-Japanese-Patent No. 59-28326; Melocyanine pigment | dye of Unexamined-Japanese-Patent No. 59-89303; Melocyanine pigment | dye of Unexamined-Japanese-Patent No. 8-129257; The benzopyran pigment | dye of Unexamined-Japanese-Patent No. 8-334897 is mentioned.

Pigment with maximum absorption wavelength from 350 to 450 nm

As another preferable form of a sensitizing dye, the pigment | dye which belongs to the following compound groups and has a maximum absorption wavelength in 350-450 nm is mentioned.

For example, polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), and cyanines (for example For example, thiacarbocyanine, oxacarbocyanine), melocyanines (e.g. melocyanine, carbomelocyanine), thiazines (e.g. thionine, methylene blue, toluidine blue) , Acridines (e.g., acridine orange, chloroflavin, acrylflavin), anthraquinones (e.g., anthraquinones), squaryliums (e.g., squaryliums) are listed. .

As an example of a more preferable sensitizing dye, the compound represented by following General formula (7)-(11) is mentioned.

(In General Formula (7), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² is a nonmetallic atom group that forms a basic nucleus of a dye in combination with adjacent A ¹ and adjacent carbon atoms. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atom group, and R ⁵¹ and R ⁵² may combine with each other to form an acidic nucleus of a dye, where W represents an oxygen atom or a sulfur atom. )

Below, the preferable specific example [(F-1)-(F-5)] of the compound represented by General formula (7) is shown.

(In Formula (8), Ar ¹ and Ar ² each independently represent an aryl group and are linked through a bond by -L ^3- , where L ³ represents -O- or -S-.) W Is the same meaning as shown in the general formula (7).)

Preferred examples of the compound represented by the general formula (8) include the following [(F-6) to (F-8)].

(In the general formula (9), A ² is sulfur represents the atom or NR ^59, L ⁴ denotes a non-metallic atomic group forming a basic nucleus of the cavity by the dye and A ² and carbon atom which are adjacent, R ^53, R ^54, R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a group of a monovalent nonmetallic atom group, and R ⁵⁹ represents an alkyl group or an aryl group.)

Preferred examples of the compound represented by the general formula (9) include the following [(F-9) to (F-11)].

(In General Formula (10), A ³ and A ⁴ each independently represent -S- or -NR ⁶³ , R ⁶³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁵ and L ⁶ each represent Independently represent a non-metallic atom group which, together with adjacent A ³ , A ⁴ and adjacent carbon atoms, form a basic nucleus of the pigment, each of R ⁶¹ , R ⁶² independently is a monovalent non-metallic atom group or combine with each other to form an aliphatic or aromatic group You can form a ring of sex.)

Preferred examples of the compound represented by the general formula (10) include the following [(F-12) to (F-15)].

In addition, what is represented by following formula (11) is mentioned as a preferable sensitizing dye used for this invention.

(In General Formula (11), A represents an aromatic ring or heterocyclic ring which may have a substituent, X represents an oxygen atom, a sulfur atom or -N (R ¹ )-, and Y represents an oxygen atom or -N (R). ¹⁾ - represents the R ^1, R ^2, R ³ are, each independently, a hydrogen atom or a monovalent non-metallic atomic group, a and R ^1, R ^2, R ³ are aliphatic or aromatic rings, castle to respectively bonded to each other Can form.)

Here, when R <^1> , R <^2> , R <^3> represents monovalent nonmetallic atom group, Preferably it represents a substituted or unsubstituted alkyl group or an aryl group.

Next, the preferable example of R <^1> , R <^2> , R <^3> is demonstrated concretely. Examples of preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl and hep. Methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t-butyl, Isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group are mentioned. Among these, linear alkyl groups having 1 to 12 carbon atoms, branched groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a group of monovalent nonmetallic atom groups except hydrogen is used, and as a preferred example, a halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkyl Thio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-aryl Amino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N -Alkyl-N-arylcarbamoyloxy group, alkyl sulfoxy group, aryl sulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N-alkylureido group , N, N-dialkyl ureido group, N-aryl ureido group, N, N- diaryl ureido group, N-alkyl-N-aryl ureido group, N-alkylureido group, N-arylureido group, N-alkyl-N-alkylureido group, N-alkyl-N-arylureido group, N, N-dialkyl-N-alkylureido group, N, N-di Alkyl-N-arylureido group, N-aryl-N-alkylureido group, N-aryl-N-arylureido group, N, N-diaryl-N-alkylureido group, N, N-diaryl-N -Aryl ureido group, N-alkyl-N-aryl-N-alkyl ureido group, N-alkyl-N-aryl-N-aryl ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N- Alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group , Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-aryl Carbamoyl group, alkylsulfinyl group, aryl Blood group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugated salts device (hereinafter referred to as alcohol Estepona earthenware), alkoxy sulfonyl group, aryloxy procedure Four group, sulfinyl cinnamoyl group, N- Alkyl sulfinamoyl group, N, N-dialkyl sulfinamoyl group, N-aryl sulfinamoyl group, N, N- diaryl sulfinamoyl group, N-alkyl-N-aryl sulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂ ) And its conjugated base group (hereinafter referred to as phosphonato group), dialkyl phosphono group (-PO ₃ (alkyl) ₂ ), diaryl phosphono group (-PO ₃ (aryl) ₂ ), alkylaryl phosphono Group (-PO ₃ (alkyl) (aryl)), monoalkylphosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group (- PO ₃ H (aryl)) and its conjugated salts device (hereinafter, called as ah reel force Estepona earthenware ), Phosphono oxy group (-OPO ₃ H ₂₎ and its conjugated salts device (hereinafter referred to as after, Nato phosphonate group), dialkyl phosphono oxy group _{(-OPO 3 (alkyl) 2)} , diaryl phosphono Oxy group (-OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (-OPO ₃ (alkyl) (aryl)), monoalkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (Hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as arylphosphonatooxy group), cyano group, nitro Group, aryl group, heteroaryl group, alkenyl group, alkynyl group, silyl group.

Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group and ethoxyphenyl group. , Phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbono And a phenyl group, an N-phenylcarbamoyl phenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, a phosphonatophenyl group, and the like.

As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen, and sulfur atoms is used. Examples of the heteroaryl ring in the particularly preferred heteroaryl group include, for example, thiophene, styrene, Furan, pyran, isobenzofuran, chroman, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizin, isoindoligin, indoyl, indazole, Purine, quinolysine, isoquinoline, phthalazine, naphthylazine, quinazoline, cynoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine , Phenalzazin, phenoxazine, furazane, phenoxazine and the like are listed, and these may be benzo-substituted or may have a substituent.

Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamil group, 2-chloro-1-ethenyl group and the like, and examples of the alkynyl group include ethynyl group, 1-propynyl group and 1-butynyl group. , Trimethylsilylethynyl group and the like. An acyl group as G ¹ in the (G ¹ CO-) can be exemplified hydrogen, and the alkyl group, an aryl group. As more preferable of these substituents, a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, N-alkylamino group, N, N-dialkylamino group , Acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N- Dialkyl sulfamoyl group, N-aryl sulfamoyl group, N-alkyl-N-aryl sulfamoyl group, phosphono group, phosphonato group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, Alkyl phosphonate group, monoaryl phosphono group, aryl phosphonato group, phosphonooxy group, phosphonatooxy group, aryl group, alkenyl group, alkylie Den groups (methylene group etc.) are mentioned.

On the other hand, as an alkylene group in a substituted alkyl group, what was used as the divalent organic residue except any of the hydrogen atoms on the C1-C20 alkyl group mentioned above is mentioned, Preferably it is a C1-C atom To cyclic straight chains, branched groups having 3 to 12 carbon atoms and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of the substituted alkyl group as R ¹ , R ² or R ³ obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group and methoxyethoxyethyl group. , Allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group , N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N -Methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatepropyl group, sulfonatebutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropyl sulfamoylpropyl group , N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyl octyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methyl Phosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamil group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. can be mentioned.

Specific examples of the aryl group preferred as R ¹ , R ² or R ³ include those in which one to three benzene rings form a condensed ring, and those in which the benzene ring and the five-membered unsaturated ring form a condensed ring, and specific examples thereof include a phenyl group, Naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, and fluorenyl group are mentioned, Among these, a phenyl group and a naphthyl group are more preferable.

As a specific example of a substituted aryl group which is preferable as R <^1> , R <^2> or R <^3> , what has a group of monovalent nonmetallic atom group (other than a hydrogen atom) is used as a substituent on the ring-forming carbon atom of the aryl group mentioned above. As an example of a preferable substituent, what was shown as a substituent in the above-mentioned alkyl group, substituted alkyl group, and above-mentioned substituted alkyl group is mentioned. As a specific example of such a substituted aryl group, a biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group, Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N -Cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group , Carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- Phenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (force Phonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethyl phosphonophenyl group, diphenyl phosphonophenyl group, methyl phosphonophenyl group, methyl phosphonatophenyl group, tolyl phosphonophenyl group, tolyl phosphonatophenyl group, Allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, etc. are mentioned. Can be.

Moreover, as a more preferable example of R <^2> and R <^3> , a substituted or unsubstituted alkyl group is mentioned. Furthermore, as a more preferable example of R ¹ , a substituted or unsubstituted aryl group is listed. The reason for this is not certain, but it is presumed that having such a substituent increases the interaction between the electron excitation state generated by light absorption and the initiator compound, and the efficiency of generating radicals, acids or bases of the initiator compound is improved. do.

Next, A in General formula (11) is demonstrated. A represents an aromatic ring or hetero ring which may have a substituent, and as a specific example of the aromatic ring or hetero ring which may have a substituent, in the above-mentioned description about R <^1> , R <^2> or R <^3> in General formula (11) The same as exemplified is listed.

Especially, as A, the aryl group which has an alkoxy group, a thioalkyl group, and an amino group is mentioned, As an especially preferable A, the aryl group which has an amino group is mentioned.

Next, Y in Formula (11) is demonstrated. Y cavities with A and adjacent carbon atoms described above and represents a nonmetallic atom group necessary to form a heterocycle. As such a heterocyclic ring, the 5, 6, or 7-membered nitrogen containing or sulfur containing heterocycle which may have a condensed ring is mentioned, Preferably a 5 or 6-membered heterocycle is preferable.

Examples of nitrogen-containing heterocycles include, for example, the melrose described by LGBrookers, J. Am. Chem. Soc, Vol. 73 (1951), p. 5326-5358 and references. What is known as what comprises the basic nucleus in pigment | dye which is not can be used preferably.

Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-di Phenylthiazole, 4,5-di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (eg For example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6 -Methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole Sol, 5-iodinebenzothiazole, 6-iodinebenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5, 6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonyl benzothiazole, etc.), naphtho thiazoles (e.g., naphtho [1,2] thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2, 1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole, etc.), thia Naphtheno-7,6,4,5-thiazoles (eg, 4-methoxythianaphtheno-7,6,4,5-thiazole, etc.), oxazoles (eg, 4-methyloxa Sol, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazoles (benzo Oxazole, 5-chlorobenzoxazole, 5-methylbenzooxazole, 5-phenylbenzoxazole, 6-methylbenzooxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzooxazole, 6 -Methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxy Benzoxazole, etc.),

Naphtho oxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methyl selenazole, 4-phenyl selenazole, etc.) ), Benzo selenazoles (for example, benzo selenazole, 5-chlorobenzo selenazole, 5-methoxy benzo selenazole, 5-hydroxy benzo selenazole, tetrahydrobenzo selenazole, etc.), naphtho selenazole ( For example, naphtho [1,2] selenazole, naphtho [2,1] selenazole, etc., thiazolins (for example, thiazolin, 4-methylthiazoline, 4,5-dimethylthiazoline , 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5-diphenylthiazoline, 4,5-di (p-methoxyphenyl) thiazoline, etc.), 2-quinolines (E.g., quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxy quinoline, etc., 4-quinolines (eg quinoline, 6-metholone) Cyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (for example, isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (for example, iso Quinoline, etc.), benzimidazoles (for example, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-di Alkylindolenins (eg 3,3-dimethylindolenin, 3,3,5-trimethylindolenin, 3,3,7-trimethylindolenin, etc.), 2-pyridine (eg, pyridine, 5) -Methylpyridine etc.), 4-pyridine (for example, pyridine etc.), etc. can be mentioned. In addition, substituents of these rings may be bonded to each other to form a ring.

Moreover, as an example of a sulfur-containing heterocycle, the dithiol partial structure in the pigment | dye of Unexamined-Japanese-Patent No. 3-296759 can be mentioned, for example.

Specific examples include benzodithiols (eg, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (eg, naphtho [1,2] dithiol). , Naphtho [2,1] dithiol and the like), dithiols (for example, 4,5-dimethyldithiol, 4-phenyldithiol, 4-methoxycarbonyldithiol, 4,5-dimethoxycar Bonyldithiols, 4,5-diethoxycarbonyldithiols, 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyl Dithiol etc.) etc. can be mentioned.

In the examples of the nitrogen-containing or sulfur-containing heterocycle in which Y in the general formula (11) described above is formed jointly with A and the adjacent carbon atoms described above, a partial structural formula of the following general formula (11-2) Since the pigment | dye which has a structure shown has high sensitization capability, since it gives the photocurable composition which is also very excellent in storage stability, it is especially preferable. The pigment | dye which has a structure represented by General formula (11-2) is a compound described in detail in Japanese Patent Application No. 2003-311253 as a novel compound.

(In General Formula (11-2), A represents an aromatic ring or hetero ring which may have a substituent, and X represents an oxygen atom or a sulfur atom or -N (R ¹ )-. R ¹ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent nonmetallic atom group, and A and R ¹ , R ⁴ , R ⁵ , and R ⁶ may be bonded to each other to form an aliphatic or aromatic ring.)

In formula (11-2), A and R ¹ are as defined as in formula (11), R ⁴ is and R ^2, R ⁵ is represented by the general formula (11) in the formula (11) of the R <^3> and R <^6> in the same meaning are the same as R <^1> in General formula (11), respectively.

Next, the compound represented by general formula (11-3) which is a preferable form of the compound represented by general formula (11) used for this invention is demonstrated.

In the above general formula (11-3) A denotes an import good aromatic ring or heterocyclic ring substituents, X represents an oxygen atom or a sulfur atom to -N (R ¹⁾ - represents a. R ¹ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent nonmetallic atom group, and A and R ¹ , R ⁴ and R ⁵ may be bonded to each other to form an aliphatic or aromatic ring. Ar represents an aromatic ring or a hetero ring having a substituent. However, the substituent on Ar skeleton requires that the sum total of the Hammet values is larger than zero. Herein, the sum of the Hammett values is greater than 0, which has one substituent, and the Hammett value of the substituents may be greater than 0, the plurality of substituents, and the sum of the Hammett values in those substituents is greater than 0. It may be.

In Formula (11-3), A and R ¹ have the same meanings as those in Formula (11), R ⁴ is R ² in Formula (11), and R ⁵ is Formula (11). It is synonymous with R <^3> in. In addition, Ar represents the aromatic ring or heterocyclic ring which has a substituent, and the specific example according to the aromatic ring or heterocyclic ring which has a substituent is mentioned similarly as what was described in description of A in General formula (11) mentioned above as a specific example. . However, as a substituent which can be introduce | transduced into Ar in General formula (11-3), it is essential that the sum total of Hammet values is 0 or more, As an example of such a substituent, a trifluoromethyl group, a carbonyl group, an ester group, a halogen atom, a nitro group, and a cyan A no group, a sulfoxide group, an amide group, a carboxyl group, etc. can be mentioned. Hammett values of these substituents are shown below. Trifluoromethyl group (-CF ₃ , m: 0.43, p: 0.54), carbonyl group (for example -COHm: 0.36, p: 0.43), ester group (-COOCH ₃ , m: 0.37, p: 0.45), halogen Atoms (e.g. Cl, m: 0.37, p: 0.23), cyano groups (-CN, m: 0.56, p: 0.66), sulfoxide groups (e.g. -SOCH ₃ , m: 0.52, p: 0.45) , Amide groups (eg -NHCOCH ₃ , m: 0.21, p: 0.00), carboxyl groups (-COOH, m: 0.37, p: 0.45) and the like. The parenthesis shows the introduction position in the aryl skeleton of the substituent, and its Hammet value, and (m: 0.50) indicates that the Hammet value when the substituent is introduced at the meta position is 0.50. Among these, as a preferable example of Ar, the phenyl group which has a substituent is mentioned, As a preferable substituent on Ar skeleton, ester group and cyano group are mentioned. It is especially preferable that it is located in the ortho position on Ar skeleton as a substitution position.

Although the preferable specific example (Example compound (F1)-Example compound (F56)) of the sensitizing dye represented by General formula (11) which concerns on this invention below is shown, this invention is not limited to these.

Among the sensitizing dyes applicable to the present invention, the compound represented by the general formula (11) is preferable from the viewpoint of core hardenability.

About the said sensitizing dye, it is possible to perform the following various chemical formulas for the purpose of improving the characteristic of the photocurable composition of this invention. For example, by combining a sensitizing dye and a polymerizable compound structure (for example, acryloyl group or methacryloyl group) by a method such as a covalent bond, an ionic bond, a hydrogen bond, etc. Unnecessary precipitation suppression effect improvement of the pigment | dye of can be obtained.

As for content of a sensitizing dye, 0.01-20 mass% is preferable with respect to the total solid of the photocurable composition for color filters of this invention, More preferably, it is 0.01-10 mass%, More preferably, it is 0.1-5 mass%. .

When content of a sensitizing dye is this range, it is high sensitivity with respect to the exposure wavelength of ultra-high pressure mercury lamp, and it is preferable at the point of image development hardening and pattern formation property while obtaining film | membrane part hardenability.

solvent

In general, the pigment dispersion composition and the photocurable composition of the present invention can be preferably prepared using a solvent together with the above components.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetic acid, oxyacetic acid butyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid, methyl 3-oxypropionate, 3 3-oxypropionic acid alkyl esters such as ethyl oxypropionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate , 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetacetic acid, ethyl acetate, methyl 2-oxobutanoate, 2-oxo Ethyl butane and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxy propionate, 2-heptanone, and cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferable.

You may use a solvent in combination of 2 or more type other than using independently.

Other ingredients available

In the photocurable composition of the present invention, if necessary, a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a coloring agent, a photopolymerization initiator, other fillers, polymer compounds other than the above-mentioned alkali-soluble resins, surfactants And various additives such as adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors.

Chain transfer agent

As a chain transfer agent which can be added to the colored photocurable composition of this invention, N, N- dialkylamino benzoic acid alkyl esters, such as N, N- dimethylamino benzoic acid ethyl ester, 2-mercaptobenzothiazole, for example And mercapto compounds having heterocycles such as 2-mercaptobenzoxazole and 2-mercaptobenzoimidazole, and aliphatic polyfunctional mercapto compounds.

A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

Fluorinated Organic Compound

By containing a fluorine-type organic compound, the liquid characteristic (particularly fluidity) at the time of using a coating liquid can be improved, and the uniformity and liquid saving property of application thickness can be improved. That is, since the interfacial tension between the substrate and the coating liquid is lowered, the wettability to the substrate is improved, and the coating property to the substrate is improved, so that even when a thin film having a thickness of several micrometers is formed with a small amount of liquid, a uniform thickness with a small thickness unevenness is obtained. This is effective in that a film can be formed.

3-40 mass% is preferable, as for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Especially preferably, it is 7-25 mass%. If the fluorine content is in the above range, it is effective in terms of coating thickness uniformity and liquid saving property, and the solubility in the composition is also good.

As a fluorine-type organic compound, the compound which has a fluoroalkyl or a fluoroalkylene group in at least one site | part of a terminal, a main chain, and a side chain can be used preferably. As a specific commercial item, Mega pack F142D, F172, F173, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R-61 , Copper R-90 (all manufactured by Dainippon Inc Co., Ltd.), Floroid FC-135, Copper FC-170C, Copper FC-430, Copper FC-431, Novec FC-4430 (All trade names: Sumitomo 3M Co., Ltd.), Asahi Guard AG 7105, 7000, 950, 7600, Supron S-112, S-113, S-131, S-141, S-145, S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (all manufactured by Asahi Glass Co., Ltd.), F-Top EF351, East 352, 801 and 802 (both manufactured by JEMCO Corporation).

The fluorine-based organic compound is particularly effective for preventing coating stains and thickness irregularities when the coating film is thinned. Moreover, it is effective also in the application | coating of the slit which is easy to produce liquid dripping.

As for the addition amount of a fluorine-type organic compound, 0.001-2.0 mass% is preferable with respect to the total mass of a photocurable composition, More preferably, it is 0.005-1.0 mass%.

Thermal polymerization initiator

It is also effective to include a thermal polymerization initiator in the photocurable composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds, and examples of the azo compounds include azobis compounds. As the peroxide compound, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxy carbonate and the like can be mentioned.

Thermal polymerization component

It is also effective to contain a thermal-polymerization component in the photocurable composition of this invention. An epoxy compound can be added as needed in order to raise the intensity | strength of a coating film. As an epoxy compound, it is a compound which has two or more epoxy rings in a molecule | numerator, such as bisphenol-A, cresol novolak-type, a biphenyl type, and an alicyclic epoxy compound. For example, as bisphenol A, Efototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF- 170 etc. (all made by Tohto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103, etc. (all made by Nagase Kasei Co., Ltd.), Fraxel GL-61, GL In addition to -62, G101, G102 (all manufactured by Daicel Chemical Industries, Ltd.), these similar bisphenol F type and bisphenol S type can also be listed. Moreover, epoxy acrylates, such as Ebecryl 3700, 3701, 600 (all are brand name: Daicel UCB Co., Ltd.), can also be used. As a cresol novolak type, Efototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (all are brand name: Tohto Kasei Co., Ltd. make), Denacol EM-125, etc. ( Brand name: produced by Nagase Kasei Co., Ltd.) and the biphenyl type, as an alicyclic epoxy compound, such as 3,5,3 ', 5'- tetramethyl-4,4' diglycidyl biphenyl, Celoxide 2021 , 2081, 2083, 2085, Eporide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (all manufactured by Daicel Chemical Industries, Ltd.), Santoto ST-3000, ST-4000 , ST-5080, ST-5100, and the like (all are manufactured by Tohto Kasei Co., Ltd.). 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o- Phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and other amine epoxy resins, efototo YH-434 and YH-434L (all manufactured by Tohto Kasei Co., Ltd.), bisphenol A epoxy resin Glycidyl ester etc. which modified | denatured the dimer acid in the skeleton of can also be used.

Surfactants

It is preferable that the photocurable composition of this invention is comprised using various surfactant from a viewpoint of improving applicability | paintability, In addition to the fluorine-type surfactant mentioned above, nonionic, cationic, and anionic surfactant can be used. have. Especially, said fluorine-type organic compound (surfactant) and nonionic surfactant are preferable.

As an example of nonionic surfactant, Nonionic system, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, monoglyceride alkyl ester, etc., for example Surfactants are particularly preferred. Specifically, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene polythiylated ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polytyryl ether and polyoxyethylene nonylphenyl ether; Ratios such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and ethylenediamine polyoxyethylene-polyoxypropylene condensates Ionic surfactants, which include Kao Corporation, NOF Corporation, Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Chemical Industries, Ltd. What is marketed from the back etc. can be used suitably. In addition to the above, the above-described dispersant may be used.

In addition to the above, various additives may be added to the photocurable composition. Specific examples of the additive include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, anti-agglomerating agents such as sodium polyacrylate, glass and alumina. Fillers such as; Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, acid anhydride added to a polymer having a hydroxyl group, alcohol soluble nylon, bisphenol A and epichlorohydrin Alkali-soluble resins such as phenoxy resins formed from

In addition, when promoting alkali solubility of the uncured portion and further improving the developability of the pigment dispersion composition, it is possible to add an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, to the pigment dispersion composition. have. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sublinic acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid; Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, telephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamildeacetic acid, coumalic acid and umbelic acid Listed.

Thermal polymerization inhibitor

It is preferable to further add a thermal polymerization inhibitor to the photocurable composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl Catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercapto Benzoimidazole and the like are useful.

Photocurable composition and manufacturing method of color filter using same

The photocurable composition of this invention contains alkali-soluble resin, a photopolymerizable compound, and a photoinitiator (preferably with a solvent) in the pigment dispersion composition of this invention mentioned above, and adds additives, such as surfactant, as needed to this. It can mix and prepare through the mixing-dispersion process which mix-disperses using various mixers and a disperser.

Moreover, although it is preferable that a mixing-dispersion process consists of kneading dispersion | distribution and the microdispersion process performed subsequently, it is also possible to omit kneading dispersion.

The photocurable composition of this invention is apply | coated to a board | substrate directly or through another layer by the apply | coating methods, such as rotation coating, slit coating, casting coating, roll coating, and bar coating, a photocurable coating film is formed and a predetermined | prescribed mask pattern By exposing through, and developing and removing the uncured part with a developing solution after exposure, the pattern shape film which consists of pixels of various colors (3 or 4 colors) can be formed and it can be set as a color filter.

At this time, as radiation to be used, ultraviolet rays such as g-rays, h-rays, i-rays, and j-rays are particularly preferable. As a color filter for a liquid crystal display device, a proximity exposure machine and a mirror projection exposure machine are used, and exposure using the h line | wire and i line | wire is mainly preferable, and the color filter for solid-state image sensors uses a stepper exposure machine, and mainly uses i line | wire. It is preferable to use.

The color filter of the present invention is formed on a substrate such as glass using the photocurable composition of the present invention described above, and the photocurable composition of the present invention is applied to a substrate, for example, slit coating directly or through another layer. By forming a coating film by this, this coating film is dried, pattern exposure is carried out, and it can produce suitably by performing the image development process using a developing solution sequentially. As a result, color filters used in liquid crystal display devices and solid-state image pickup devices can be produced with little process difficulty, high quality, and low cost.

Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto, and photoelectric conversion element substrates used in solid state imaging devices and the like. Examples thereof include silicon substrates and plastic substrates. On these board | substrates, the black matrix which isolate | separates each pixel is normally formed, or the transparent resin layer is provided for adhesion promotion etc.

It is preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface. In addition, the photocurable composition of the present invention is also formed on a driving substrate (hereinafter referred to as a "TFT type liquid crystal driving substrate") in which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed. A patterned film can be formed and a color filter can be created. In addition to the pattern for forming a pixel, the photomask used at that time is also formed with a pattern for forming a through hole or a U-shaped recess. As a board | substrate in a TFT system liquid crystal drive board | substrate, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. can be mentioned, for example. If desired, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like. For example, the board | substrate etc. which provided the passivation film, such as a silicon nitride film, on the surface of a TFT system liquid crystal drive substrate or the surface of the said drive substrate are mentioned.

Although it does not specifically limit as a method of apply | coating the photocurable composition of this invention to a board | substrate, The method of using slit nozzles, such as a slit and spin method and a spinless coating method (henceforth a slit nozzle coating method), desirable. In the slit nozzle coating method, the slit and spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate, but for example, the fifth generation glass substrate (1100 mm x 1250 mm) by the spinless coating method. When apply | coating, the discharge amount of the photocurable composition from a slit nozzle is normally 500-2000 microliters / sec is preferable, or 800-1500 microliters / second is preferable, and the application | coating speed is 50-300 mm / sec is preferable normally, 100 200 mm / sec is more preferable. As solid content of a photocurable composition, 10 to 20% is preferable normally, and 13 to 18% is more preferable. When forming the coating film by the photocurable composition of this invention on a board | substrate, as thickness (after prebaking process) of the said coating film, generally 0.3-5.0 micrometers is preferable, 0.5-4.0 micrometers is more preferable, 0.8- 3.0 mu m is most preferred.

Usually, a prebaking process is performed after application | coating. If necessary, vacuum treatment may be performed before prebaking. As for conditions of vacuum drying, a degree of vacuum is normally 0.1-1.0 torr is preferable, or 0.2-0.5 torr is more preferable.

The temperature range of 50-140 degreeC is preferable using a hotplate, oven, etc., or 70-110 degreeC is preferable, and prebaking process can be performed on conditions of 10 to 300 second preferably. You may use a high frequency process etc. together. High frequency treatment can be used alone.

In the developing treatment, the uncured portion after exposure is eluted to the developing solution, so that only the hardened powder remains. As image development temperature, it is 20-30 degreeC normally, and as image development time, it is 20 to 90 second.

As a developing solution, as long as it melt | dissolves the coating film of the photocurable photocurable composition in an uncured part, and does not melt a hardened part, any can be used. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

As said organic solvent, the above-mentioned solvent which can be used when preparing the pigment dispersion composition or photocurable composition of this invention is mentioned.

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl The concentration of the alkaline compounds such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene is preferably 0.001 to 10% by mass, more Preferably, the alkaline aqueous solution melt | dissolved so that it may become 0.01-1 mass% is mentioned. A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can also be added to alkaline aqueous solution.

The developing method may be any of a dip method, a shower method, a spray method, and the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith. Before the contact with the developer, the surface to be developed may be wetted with water or the like in advance to prevent development stains. Moreover, it can also develop by tilting a board | substrate.

In the case of a solid state image pickup device, a paddle phenomenon is also used.

After the development treatment, drying is carried out through a rinse step of washing and removing excess developer, and then heat treatment (post-baking) is performed to complete the curing.

The rinse step is usually performed in pure water, but pure water is used in final cleaning for liquid saving, and the clean start can be performed using pure water of finished use, cleaning by tilting the substrate, or using ultrasonic irradiation in combination.

After rinsing off the water and drying, heat treatment is usually performed at about 200 ° C to 250 ° C. This heat treatment (post-baking) can be performed continuously or batchwise by using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high frequency heater, or the like so that the coated film after development is in the above condition.

By repeatedly performing the above operation for each color according to a desired number of colors, a color filter in which a plurality of colored cured films are formed can be produced.

Although the use of the pigment dispersion composition and the photocurable composition of the present invention is mainly described as a color filter, the present invention can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter.

The said black matrix can be formed by exposing and developing the pigment dispersion composition of this invention using black pigments, such as carbon black and titanium black, as a pigment, and then postbaking as needed, and further promoting hardening of a film | membrane.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "part" and "%" are mass references | standards unless there is particular notice.

(1) Preparation and Evaluation of Pigment Dispersion Composition of First Embodiment

Synthesis Example of Polymer Compound (A-1)

Linear synthesis

Synthesis of Polymer 1-1

27.0 g of BzMA, 126.0 g of MMA, 27.0 g of the compound (G-4), and 420.0 g of 1-methoxy-2-propanol were introduced into a three-necked flask with nitrogen substitution, followed by a stirrer (trade name: Three-One Motor, Shinto Scientific Co.). Co., Ltd.) was heated, heated to 90 ° C while flowing nitrogen into the flask. To this, 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by heating and stirring at 90 ° C for 2 hours. After 2 hours, 1.69 g of V-65 was further added, followed by heating and stirring for 3 hours to obtain a 30% solution of polymer 1-1.

It was 2.00,000 when the weight average molecular weight of the obtained high molecular compound was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material.

In addition, the repeating unit composition ratio (mass ratio) of the acid value per solid content of 98 mg KOH / g and ¹ H-NMR was 15/70/15 from the titration using sodium hydroxide.

In the same manner, polymers 1-2 to 1-6 of the compositions shown in Table 1 were synthesized.

Synthesis of Polymer 1-7

21.0 g of the compound (a-3), 98.0 g of MMA, 14.0 g of the compound (G-20), 7.0 g of MAA, and 420.0 g of 1-methoxy-2-propanol were introduced into a three-necked flask with nitrogen substitution, followed by stirring. It was stirred with (trade name: Three One Motor, manufactured by Shinto Scientific Co., Ltd.), heated to 90 ° C while flowing nitrogen into the flask. To this, 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by heating and stirring at 90 ° C for 2 hours. After 2 hours, 1.69 g of V-65 was further added, followed by heating and stirring for 3 hours to obtain a 30% solution of polymer 1-7.

It was 1.5 million when the weight average molecular weight of the obtained high molecular compound was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material.

Moreover, the repeating unit composition ratio (mass ratio) calculated | required from 98 mg KOH / g and ¹ H-NMR of the acid value of solid content from the titration using sodium hydroxide was 15/70/10/5.

Graft Type Synthesis

Synthesis of Polymer 1-8

BzMA 28.0 g, polymethyl methacrylate having a methacryloyl group at the end (brand name: AA-6, manufactured by Toagosei Co., Ltd.) 91.0 g, 21.0 g of the compound (G-4), n-dodecyl 2.9 g of mercaptan and 327 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (trade name: Three-One Motor, manufactured by Shinto Scientific Co., Ltd.), and heated while flowing nitrogen into the flask. It heated up to 78 degreeC. 0.8 g of 2,2-azobis (dimethyl 2-propionate) (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and heating and stirring were performed at 78 ° C for 2 hours. After 2 hours, 0.8 part of V-601 was further added, followed by heating and stirring for 3 hours to obtain a 30% solution of Polymer 1-8.

It was 2.00,000 when the weight average molecular weight of the obtained high molecular compound was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material.

In addition, the acid value per solid content of the repeating unit composition ratio (mass ratio) calculated | required from 98 mg KOH / g and ¹ H-NMR from the titration using sodium hydroxide was 20/65/15. In the same manner, polymers 1-9 to 1-12 having the compositions shown in Table 1 were synthesized.

Synthesis of Terminal Denatured Forms

Synthesis of Precursor TM-1 of Polymer 1-13

7.83 parts of dipentaerythritol hexakis (3-mercaptopropionate) (trade name: DPMP, manufactured by Sakai Chemical Industry Co., Ltd.) and 4.55 parts of itaconic acid are dissolved in 28.90 parts of 1-methoxy-2-propanol. It heated at 70 degreeC under nitrogen stream. To this was added 0.04 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (trade name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) and heated for 3 hours. Furthermore, 0.04 part of V-65 was added and it was made to react at 70 degreeC under nitrogen stream for 3 hours. By cooling to room temperature, a 30% solution of the mercaptan compound (TM-1) according to the present invention shown below was obtained.

Synthesis of Polymer 1-13

5.03 parts of the 30% solution of TM-1, 90.0 g of methyl methacrylate, and 10.0 g of the compound (G-26), and 23.3 g of 1-methoxy-2-propanol were mixed at 90 ° C. under a nitrogen stream. Heated. While stirring this mixed solution, 0.7 g of 2,2'- azobisisobutyrates (brand name: V-601, a Wako Pure Chemical Industries, Ltd. make), 26.8 g of 1-methoxy- 2-propanol, 1-meth A mixed solution of 47 g of oxy-2-propyl acetate was added dropwise over 2.5 hours. After completion of the dropwise reaction, the mixture was reacted at 90 ° C. for 2.5 hours, and then 0.23 g of 2,2′-azobisisobutyrate dimethyl and 1-methoxy-2 -A mixed solution of 20.0 g of propyl acetate was added and reacted for another 2 hours. 7.5g of 1-methoxy-2-propanol and 105.0g of 1-methoxy-2-propyl acetate were added to the reaction liquid, and it cooled to room temperature, and obtained the 30% solution of the polymer 1-13.

It was 1.80,000 when the weight average molecular weight of the obtained high molecular compound was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material.

In addition, the repeating unit composition ratio (mass ratio) of the acid value per solid content of 100 mg KOH / g and ¹ H-NMR was 90/10 from the titration using sodium hydroxide.

In the same manner, polymers 1-14 of the composition of Table 1 were synthesized.

The compound in Table 1 is shown below.

MAA: methacrylic acid

MMA: Methyl methacrylate

BzMA: benzyl methacrylate

CHMA: cyclohexyl methacrylate

DMAEMA: 2-dimethylaminoethyl methacrylate

AA-6: single-ended methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toagosei Co., Ltd.)

Example 1-1

Preparation of Process Pigments

3650 g of pigment C.I. Pigment Green, 500 g of sodium chloride, and 100 g of diethylene glycol were placed in a stainless gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded for 9 hours. Next, the mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and a solvent, and dried to obtain a processed pigment coated with a high molecular compound.

Preparation of Pigment Dispersion Compositions

The components of the following composition (1) were mixed, the mixture was stirred and stirred at a rotational speed of 3,000 rpm for 3 hours using a homogenizer, and a mixed solution containing a pigment was prepared.

Composition (1)

95 parts of processing pigment (particle diameter: 30 nm)

Pigment derivative A (formula below) 5 parts

100 parts of a dispersant (30% 1-methoxy-2-propyl acetate solution of polymer 1-1)

1-methoxy-2-propyl acetate 750 parts

Subsequently, the mixed solution obtained above was dispersed for 6 hours using a bead disperser dispermat (manufactured by GETZMANN Co., Ltd.) using 0.3 mmφ zirconia beads, and thereafter, a high-pressure disperser NANO-3000-10 with a decompression mechanism (Japan Biei Co., Ltd.) )), The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

Examples 1-2-1-11, Comparative Examples 1-1-1-2

Except for replacing the composition of the pigment dispersion composition obtained in Example 1-1 as described in Table 2, and in the same manner as in Example 1-1, Examples 1-2 to 1-13 and Comparative Examples 1-1 to 1- The pigment dispersion composition of 2 was obtained.

Examples 1-14 to 1-18 and Comparative Examples 1-3 to 1-4

It adjusted like Example 1-1 except adding 25g of the high molecular compound (polymer) solutions of Table 2 with 3650g of pigment C.I. pigment green, 500g of sodium chloride, and 100g of diethylene glycol.

Evaluation of Pigment Dispersion Compositions

The following evaluation was performed about the obtained pigment dispersion composition. The results are shown in Table 2.

(1) Measurement and evaluation of viscosity

About the obtained pigment dispersion composition, after using E-type viscosity meter (brand name: RE550L, Toki Sangyo Co., Ltd.), the viscosity (eta) ¹ of the pigment dispersion composition immediately after dispersion, and 1 week after dispersion (at room temperature), The viscosity (eta) ² of the pigment dispersion composition was measured, and the grade of thickening was evaluated. The evaluation results are shown in Table 2 below. Here, the thing with a low viscosity shows that the raise of the viscosity resulting from a dispersing agent is suppressed, and the dispersibility and dispersion stability of a pigment are favorable.

(2) Measurement and evaluation of contrast

The obtained pigment dispersion composition was apply | coated on a glass substrate, and the sample was produced so that the thickness of the coating film after drying might be set to 1 micrometer. This sample was placed between two polarizing plates, and the polarizing plate measured the brightness at the time of parallel and the brightness at the time of direct with BM-5 (made by Topcon Corporation), and calculated | required the contrast (luminance at the time of parallel / luminance at the time of direct). The results of the measurement evaluation are shown in Table 2 below. Here, high contrast indicates high transmittance, that is, high coloring power, since the pigment is uniformly dispersed in a highly refined state.

(3) evaluation of developability

The pigment dispersion composition was apply | coated so that a film thickness might be set to 2.0 micrometers on the glass substrate of 100 mm x 100 mm (brand name: 1737, Corning Co., Ltd. product), and it dried for 60 second in 70 degreeC oven. The membrane is immersed in a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by FUJIFILM Electronics Materials Co., Ltd.), and the extraction is repeated 20 times. Visual determination of the solubility of the membrane and the presence or absence of the suspension in the developer is performed. did. The higher the score, the better the developability.

Judgment method

Up and down movement 1 to 20 times, developer coloration: 4

After 20 times of up and down movement, it is left to stand for 1 minute to color the developer: 3

After 20 movements up and down, the solution is left for 5 minutes to color: 2

After 20 times of vertical movement, the developer does not color even if left for 5 minutes: 1

P-1: Methyl methacrylate / methacrylic acid = 85/15 mass% copolymer, 20,000 weight average molecular weight, acid value 98 mg KOH / g

P-2: hydrogenated rosin ester (trade name: ester gum HP, manufactured by Arakawa Chemical Co., Ltd.)

D-1: a-1 / AA-6 / MAA = 20/65/15 mass% of copolymer, weight average molecular weight 2.30,000, acid value 100 mg KOH / g

D-2: methacrylic acid / mono succinate mono (2-acryloyloxyethyl) / styrene 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide = 15/10 / 11.2 / 10/35 /18.8 mass% copolymer, weight average molecular weight 2.5

From the result of Table 2, in Examples 1-1 to 1-18 using the pigment dispersion composition of this invention, it is confirmed that pigment dispersion property and dispersion stability after dispersion are excellent, contrast is high, and developability is favorable.

Moreover, in Comparative Examples 1-1 to 1-4 which do not contain the (A) polymer compound, it is confirmed that contrast is low, and dispersion stability and developability are also inferior.

Example 2-1

Pigment dispersion composition

The pigment dispersion composition (red) was adjusted in the same manner as in Example 1-1 except that the pigment was changed to C.I. Pigment Red 254.

Preparation of colored photocurable composition

The components of the following composition (2) were mixed, the mixture was stirred and stirred at a rotational speed of 3,000 rpm for 3 hours using a homogenizer, and a mixed solution containing a pigment was prepared.

Composition (2)

110 parts of processed pigments listed in Table 3.

250 parts of dispersant as listed in Table 3

(30% 1-methoxy-2-propylacetate solution)

20 parts of dispersant pigment derivatives described in Table 3.

1-methoxy-2-propyl acetate 750 parts

Subsequently, the mixed solution obtained above was disperse | distributed for 6 hours by the bead disperser dispermat (made by GETZMANN company) using 0.3 mm diameter zirconia bead, and the high pressure disperser NANO-3000-10 with a pressure reduction mechanism after that (Japan Biei ( Note) produced) was further subjected to dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

Preparation of color filter using photocurable composition

The obtained photocurable composition (color resist liquid) is apply | coated so that the x value and y value which become an index of color density may be set to 0.650, respectively, on a glass substrate (brand name: 1737, Corning Co., Ltd.) of 100 mm x 100 mm, Dry in an oven at 90 ° C. for 60 seconds (prebaked). Thereafter, the entire surface of the coating film was exposed at 200mJ / cm ² (roughness 20mW / cm ² ), and the coated film after exposure was coated with a 1% aqueous solution of alkaline developer CDK-1 (trade name, manufactured by FUJIFILM Electronics Materials Co., Ltd.). Was stopped for 60 seconds. After stopping, the pure water was sprayed in the shower shape, and the developing solution was wash | cleaned. Then, the coating film subjected to the exposure and development as described above was heated in an oven at 220 ° C. for 1 hour (post-baking), and a colored pattern (colored resin film) for a color filter was formed on the glass substrate, thereby forming a colored filter. A substrate (color filter) was produced.

Examples 2-2 to 2-4, and comparison in the same manner as in Example 2-1 except for changing the pigment, pigment derivative, polymer compound, and dispersant used in Example 2-1 to the compound shown in Table 3 The pigment dispersion compositions of Examples 2-1 to 2-2 were obtained. Using this, the photocurable composition was obtained like Example 2-1, and the color filter was produced.

Pigment Pigment derivatives Polymer used in the dispersing process evaluation Pigment Polymers for Processed Pigments Contrast Phenomenon residue Surface smoothness Example 2-1 PR254 A none 1-9 5000 A A Example 2-2 PR254 A P-1 1-8 7500 A A Example 2-3 PG36 A P-1 1-8 / 1-14 (mass ratio 3: 7) 8000 A A Example 2-4 PG36 B none 1-10 6000 A A Comparative Example 2-1 PR254 A P-1 D-1 3000 X X Comparative Example 2-2 PG36 A none D-1 2000 X X

The compound of Table 3 is shown below.

P-1: Methyl methacrylate / methacrylic acid = 85/15 mass% copolymer, 20,000 weight average molecular weight, acid value 98 mgKOH / g

D-1: a-1 / AA-6 / MAA = 20/65/15 mass% of copolymer, weight average molecular weight 2.30,000, acid value 100 mgKOH / g

Evaluation of Color Filter

The produced colored filter substrate (color filter) was evaluated as follows. The results are shown in Table 3.

(1) contrast

The colored resin film for color filters was put on a polarizing plate on a glass substrate, and the brightness at the time of parallel polarization and the brightness at the time of linear measurement were measured by BM-5 (made by Topcon Corporation), and the contrast (at the time of parallel / brightness at the time of parallelism) was measured. Luminance). The results of the measurement evaluation are shown in Table 3. Here, high contrast indicates that the transmittance, that is, the coloring power, is high because the pigment is uniformly dispersed in a highly refined state.

(2) developing residue

The case where the board | substrate after image development remained in the glass substrate of an unexposed part with an optical microscope was observed. A was confirmed that there was no residue in the unexposed part at all, but the residue was confirmed in the unexposed part slightly, but it was X that the residue was remarkably confirmed in B and the unexposed part in the case where there was no problem practically.

(3) surface smoothness

Slit coating aptitude was evaluated using the slit coating apparatus provided with the slit head of 100 micrometers of slit spaces, and 500 mm of coating effective widths. After apply | coating on 10 sheets of glass substrates (550 mm in width, 650 mm in length, 0.7 mm in thickness) by a conventional method, the said slit head was made to air hold for 5 minutes, and it forcedly dried. The dummy dispense was dispensed for 3 seconds after waiting, and 10 sheet slits were applied to the glass substrate as it was intermittently. The space | interval between a slit and a glass substrate was adjusted so that the coating film thickness after post baking might be set to 2 micrometers, and the curable composition was apply | coated at the application | coating speed | rate 100 mm / sec. After application, after prebaking at 90 ° C. for 60 seconds on a hot plate, the number of lines on the coating surface was visually counted using a sodium light source, and the following criteria were evaluated.

Evaluation standard

A: No smudge on the coated surface at all

B: 1 to 5 spots on the line were observed

X: 6 or more stains on a line were observed

From the result of Table 3, in Examples 2-1 to 2-4 using the color filter of this invention, high contrast is shown, the residue in an unexposed part is suppressed, and it is confirmed that surface smoothness was excellent.

Moreover, in Comparative Examples 2-1 to 2-2 which do not contain the (A) polymer compound, it is confirmed that contrast is low, a residue is seen in an unexposed part, and surface smoothness is also inferior.

Next, the example which prepared the curable composition containing a pigment for color filter formation for a solid-state image sensor use is demonstrated.

Example 3-1

B1. Preparation of resist liquid

The components of the following composition were mixed and dissolved to prepare a resist liquid.

Composition of resist liquid

Propylene glycol monomethyl ether acetate 19.20 parts

30.51 parts of a 40% propylene glycol monomethyl ether acetate (PGMEA) solution of benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate (molar ratio = 60/22/18) copolymer

Dipentaerythritol hexaacrylate

 (Photopolymerizable compound containing ethylenically unsaturated double bond) 12.20 parts

Polymerization inhibitor (p-methoxyphenol) 0.0061 parts

Fluorine-based surfactant

 (Product name: F-475, produced by Dainippon Ink and Chemicals, Inc.) 0.83

TAZ-107 (brand name, Midori Kagaku Co., Ltd. production)

(Trihalomethyl triazine photopolymerization initiator) 0.586 parts

B2. Fabrication of Silicon Wafers with Undercoat Layers

The 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes, and then the resist liquid was applied onto the silicon wafer so as to have a dry film thickness of 1.5 μm, and further dried in an oven at 220 ° C. for 1 hour to undercoat. Was formed to obtain a silicon wafer substrate having an undercoat layer.

Preparation of Pigment Dispersion

95 parts of C.I. pigment green 36 (average primary particle diameter 30nm)

35.5 parts of the dispersing agent (30% of solid content concentration) described in Table 4

Propylene glycol monomethyl ether acetate (solvent) 830 parts

The mixed liquid which mixed the said component was mixed and disperse | distributed by the bead mill for 15 hours, and the pigment dispersion liquid (P2) was prepared.

Preparation of curable composition (coating liquid)

Using the pigment dispersion liquid (P2) obtained above, it stirred and mixed so that it might become the following composition, and prepared the solution of curable composition.

<Composition>

600 parts of pigment composition (P2)

Ilgacure 907 (trade name, produced by Ciba Specialty Chemicals K.K.)

(Acetophenone-based strong polymerization initiator) 5 parts

15 parts dipentaerythritol hexaacrylate (photopolymerizable compound)

280 parts of propylene glycol monomethyl ether acetate

Preparation and Evaluation of Color Filter by Curable Composition

Pattern formation and evaluation of sensitivity

The curable composition prepared as mentioned above was apply | coated so that the dry film thickness of a foam film (colored layer) might be set to 0.7 micrometer on the undercoat layer of the silicon wafer with an undercoat layer obtained by said B2. Then, heat processing (prebaking) was performed for 120 second using the 100 degreeC hotplate.

Subsequently, using an i-line stepper exposure apparatus FPA-3000 i5 + (manufactured by Canon Co., Ltd.), various exposure doses in a range of 50 to 1200 mJ / cm ² were obtained at a wavelength of 365 nm through a 1.5-μm square island pattern mask. Exposure was performed.

Thereafter, the silicon wafer substrate on which the coated film after exposure is formed is placed on a horizontal rotating table of a spin shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and mounted on CD-2000 (FUJIFILM Electronics Materials Co., Ltd.). Ltd.) was used for 60 seconds at 23 ° C. to form a colored pattern on the silicon wafer.

The silicon wafer on which the coloring pattern is formed is fixed to the horizontal rotating table by a vacuum chuck method, and the pure water is flowed from the jet nozzle to the shower image while the silicon wafer is rotated at a rotational speed of 50 r.pm by a rotating device, rather than above the center of rotation. It was supplied and rinsed, and then spray dried.

The storage stability of the solution (coating solution) of the curable composition prepared above and the developability of the curable composition layer formed on the glass substrate were evaluated using the curable composition. The evaluation results are shown in Table 4 below.

Developability

In exposure and image development, the presence or absence of the residue of the area | region (non-exposed part) to which light was not irradiated was confirmed by optical microscope and SEM photograph observation after post-baking, and developability was evaluated according to the following evaluation criteria.

Evaluation standard

A: No residue was confirmed at all in the unexposed part.

B: Although the residue was slightly confirmed by the unexposed part, it was the degree which is satisfactory practically.

X: The residue was remarkably confirmed by the unexposed part.

Evaluation of Dispersibility

About the obtained pigment dispersion composition, after using the E-type viscosity meter (brand name: RE550L, Toki Sangyo Co., Ltd. make), after 1 week at room temperature after viscosity and dispersion of the pigment dispersion composition immediately after dispersion, it is a pigment dispersion composition. The viscosity of was measured and the degree of thickening was evaluated. Here, the thing with a low viscosity shows that the raise of the viscosity resulting from a dispersing agent is suppressed, and the dispersibility and dispersion stability of a pigment are favorable.

Examples 3-2 to 3-4 and Comparative Examples 3-1 to 3-2

Except having changed the dispersing agent used in Example 3-1 to the compound of Table 4, it carried out similarly to Example 3-1, Example 3-2-3-4 and Comparative Examples 3-1-3-3 Curable composition was obtained. In addition, evaluation was performed similarly to Example 3-1. The results are shown in Table 4.

Example Polymer used in the dispersing process Developability Initial viscosity (mPas) Viscosity over time (mPas) Example 3-1 1-1 A 30 50 Example 3-2 1-6 A 25 50 Example 3-3 1-9 A 25 60 Example 3-4 1-13 A 20 30 Comparative Example 3-1 D-1 X 80 Gel Comparative Example 3-2 D-2 X 80 Gel

The compound of Table 4 is shown below.

D-1: a-1 / AA-6 / MAA = 20/65/15 mass% of copolymer, weight average molecular weight 2.30,000, acid value 100 mg KOH / g

D-2: methacrylic acid / mono succinate mono (2-acryloyloxyethyl) / styrene 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide = 15/10 / 11.2 / 10/35 /18.8 mass% copolymer, weight average molecular weight 2.5

It was found from Table 4 that the pigment dispersion composition of the present invention has good dispersion stability, and that the photocurable composition has good developability for use in a solid state imaging device.

(2) Preparation and evaluation of the pigment dispersion composition of the second aspect

Synthesis of Grafted Polymer

Synthesis of Polymer 2-1

BzMA 27.0 g, polymethyl methacrylate having a methacryloyl group at the end (trade name: AA-6, manufactured by Toagosei Co., Ltd.) 126.0 g, monomers inducing LC-1 (R ^x is CH ₃ ) 27.0 g, n-dodecyl mercaptan 2.9 g and 327 g methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (trade name: Three-One Motor, Shinto Scientific Co., Ltd.), and nitrogen was added to the flask. It heated and let it heat up to 78 degreeC, flowing in the inside. 0.8 g of 2,2-azobis (dimethyl 2-propionate) (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and heating and stirring were performed at 78 ° C for 2 hours. After 2 hours, 0.8 g of V-601 was further added, followed by heating and stirring for 3 hours to obtain a 30% solution of Polymer 2-1.

It was 2.00,000 when the weight average molecular weight of the obtained polymer 2-1 was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material. In addition, the repeating unit composition ratio (mass ratio of BzMA / AA-6 / LC-1) determined from ¹ H-NMR was 15/70/15.

Synthesis of Polymer 2-4

In the synthesis of polymer 2-1, polymer 2-4 was synthesized by the method described in polymer 2-1 except that BzMA, AA-6, and LC-1 were changed as described in Table 5 below. In addition, UA-7 shown in Table 5 represents the monomer which induces UA-7.

Synthesis of Grafted Polymers with Lactones in the Side Chains

Synthesis of Macromonomer AL-1

50.0 g of 1-methoxy-2-propanol was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (trade name: Three-One Motor, Shinto Scientific Co., Ltd.), and heated while flowing nitrogen into the flask. It heated up to ° C. To this, MMA 170.0 g, LC-1 inducing monomer (R ^x is CH ₃ ) 30.0 g, mercaptopropionic acid 4.1 g, 1-methoxy-2-propanol 50.0 g, 2,2-azobis (2,4 -Dimethylvaleronitrile) (brand name: V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g was added dropwise at 90 占 폚 over 2 hours. After 4 hours, the mixture was diluted with 104.1 g of 1-methoxy-2-propanol. Next, after filling the flask with air, 6.0 g of glycidyl methacrylate, 0.06 g of methylhydroquinone and 4.0 g of tetraethylammonium bromide were added thereto, and the mixture was stirred at 90 ° C for 5 hours. After the completion of the reaction, the white powder obtained by reprecipitation in a 12L water / 3L methanol mixed solution was dried to obtain macromonomer AL-1.

Synthesis of Macromonomer AL-9

In the synthesis of the macromonomer AL-1, the macromolecule is synthesized by the method described in the macromonomer AL-1 except that the monomer inducing LC-1 is changed to the monomer inducing LC-9 (R ^x is CH ₃ ). Monomer AL-9 was synthesized.

Synthesis of Polymers 2-2, 2-3 and 2-5

In the synthesis of the polymer 2-1, the polymer 2-2, 2-3 and by the method described in the polymer 2-1 except that BzMA, AA-6, LC-1 was changed as shown in Table 5, respectively 2-5 was synthesized.

Determination of the ratio of the repeating unit having a lactone structure in the side chain of the graft polymer from 2-2 ¹ H-NMR, was 10% by mass. In addition, the ratio of the polymer 2-3 was 10 mass%, and the ratio of the polymer 2-5 was 10 mass% similarly.

Synthesis of Blocky Polymers

Synthesis of Polymer 2-6

The degassed solution of 140 g of benzyl methacrylate, 2 g of following compound (P), and 100.0 g of cyclohexanone was stirred at 80 degreeC for 2 hours, and then heated at 120 degreeC for 0.5 hour, and the polymer of Mn = 6500 was obtained. 20 g of MAA was added thereto, and the degassed solution was heated at 120 ° C. for 1 hour to obtain a polymer having Mn = 7200. In addition, 40 g of monomers (R ^x is CH ₃ ) for inducing LC-1 were added, and the degassed solution was heated at 120 ° C. for 1 hour. After completion of the reaction, the mixture was diluted with 392.0 g of 1-methoxy-2-propyl acetate to obtain a 30% solution of polymer 2-6.

It was 0.9 million when the weight average molecular weight of the obtained polymer 2-6 was measured by the gel permeation chromatography method (GPC) which made polystyrene the reference material. In addition, the repeating unit composition ratio (mass ratio of BzMA / MAA / LC-1) determined from ¹ H-NMR was 70/10/20.

Synthesis of Polymers 2-7, 2-8 and 2-9

In the synthesis of polymers 2-6, polymers 2-7, 2-8, and 2- by the method described in polymers 2-6, except that BzMA, MAA, and LC-1 were each changed as shown in Table 5 below. 9 was synthesized. In addition, LC-9 and LC-20 shown in Table 5 represent monomers which induce LC-9 (R ^x is CH ₃ ) and monomers which induce LC-20 (R ^x is CH ₃ ), respectively.

Synthesis of Polymer 2-10

4.4 g of a 30% solution of TM-1, a mixed solution of 24.8 g of monomers (R ^x is CH ₃ ) for inducing LC-20 and 14.0 g of 1-methoxy-2-propyl acetate were heated at 90 ° C. under a stream of nitrogen. did. A mixed solution of 0.1 g of 2,2'-azobisisobutyric acid (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 12.0 g of 1-methoxy-2-propyl acetate while stirring this mixed solution Was dripped over 2.5 hours. After completion | finish of dripping, after making it react at 90 degreeC for 2.5 hours, the mixed solution of 0.1 g of 2,2'- azobisisobutyric acid dimethyl, and 1.0 g of 1-methoxy- 2-propyl acetate was thrown in, and it was made to react further for 2 hours. . 13.9 g of 1-methoxy-2-propyl acetate was added to the reaction solution, and a 30% solution of Polymer 2-10 was obtained by cooling to room temperature.

Synthesis of Polymer 2-11

In the synthesis of polymer 2-10, polymer 2-11 was synthesized by the method described in polymer 2-10, except that the monomer inducing LC-20 was changed as described in Table 5 below. In addition, LC-9 described in Table 5 represents a monomer (R ^x is CH ₃ ) that induces LC-9.

It was 100 mass% when the ratio of the repeating unit which has a lactone structure in the stem polymer part (parts other than the terminal of a polymer) of the polymer 2-10 was calculated | required by ¹ H-NMR. In addition, the ratio of the polymer 2-11 was 20 mass% similarly.

Synthesis of Comparative Resin 2-2

Comparative resin 2-2 was synthesize | combined by the method similar to "synthesis example 6" described in Unexamined-Japanese-Patent No. 2007-65155.

Synthesis of Comparative Resins 2-1 and 2-3

In the synthesis of Comparative Resin 2-2, Comparative Resins 2-1 and 2 were prepared by the method described in Comparative Resin 2-2, except that BzMA, MMA, LC-13, and MAA were each changed as shown in Table 5 below. -3 was synthesized.

In addition, description in the said Table 5 is as follows.

MAA: methacrylic acid

MMA: Methyl methacrylate

BzMA: benzyl methacrylate

PhMI: Phenylmaleimide

DMAEMA: 2-dimethylaminoethyl methacrylate

AL-1: MMA / LC-1 = 85/15 (mass ratio)

AL-9: MMA / LC-9 = 85/15 (mass ratio)

AA-6: Polymethylmethacrylate Having Methacryloyl Group at Terminal

M-6: above-mentioned compound (specific example) M-6

M-13: the above-mentioned compound (specific example) M-13

Preparation of Processed Pigments and Pigment Dispersion Compositions

When using a polymer (polymer compound) in the preparation process of a process pigment, except having made the change which adds 25 g of 30% 1-methoxy- 2-propyl acetate solutions of the polymer of Table 6 to the preparation material further, In the same manner as in Example 1-1, the processed pigments of Examples 4-1 to 4-14 and Comparative Examples 4-1 to 4-3 were prepared. Furthermore, it changed into 100 parts of 30% 1-methoxy- 2-propyl acetate solution of the polymer 1-1, and changed using the dispersing agent (polymer) of Table 6 of the usage-amount (unit: mass part) of Table 6 A pigment dispersion composition of Examples 4-1 to 4-14 and Comparative Examples 4-1 to 4-3 was prepared in the same manner as in Example 1-1.

Evaluation of Pigment Dispersion Compositions

The viscosity and contrast of the obtained pigment dispersion composition were evaluated in the same manner as in Example 1-1.

In addition, in evaluation of precipitation property, the obtained pigment dispersion composition was apply | coated so that it might become a film thickness of 2.0 micrometer on the glass substrate (brand name: 1737, Corning Co., Ltd. product) of 100 mm x 100 mm, and it dried for 60 second in 90 degreeC oven. . Then, the coating film was heat-processed (post-baking) for 30 minutes in 230 degreeC oven, and the presence or absence of pattern shape precipitation was confirmed with the optical microscope. Post-baking process was repeated and it observed every time. The higher the score, the better the hard to be precipitated.

4: Precipitation in the fourth post-baking

3: Precipitation in the third time post-baking

2: Precipitate in the second post-baking

1: Precipitation at the first time of post-baking

In addition, description in the said Table 6 is as follows.

P-1: copolymer of methyl methacrylate / methacrylic acid = 85/15 (mass ratio), weight average molecular weight 20,000, acid value 98 mg KOH / g

P-2: hydrogenated rosin ester (brand name: ester rosin HP, Arakawa Chemicals Co., Ltd. product)

Preparation of colored photocurable composition

Examples 4-15 to 4-18 and Comparative Example 4 were carried out in the same manner as in Example 2-1 except that the composition (processing pigment, dispersant, dispersant pigment derivative) of the mixed solution was changed as shown in Table 7 below. A pigment dispersion composition of -4 to 4-5 was obtained. Using this, the photocurable composition was obtained like Example 2-1, and the colored filter substrate (color filter) was produced.

Evaluation of Color Filter

The produced colored filter substrate (color filter) was evaluated as follows. The results are shown in Table 7 below.

Pigment Pigment derivatives Polymer used in the dispersing process evaluation Pigment Polymers for Processed Pigments Contrast Phenomenon residue Surface smoothness Example 3-15 PR254 none A 2-1 5500 A A Example 3-16 PR254 P-3 A 2-3 7000 A A Example 3-17 PG36 P-1 A 2-8 / 2-5 (mass ratio 3: 7) 6500 A A Example 3-18 PG36 none B 2-9 5000 A A Comparative Example 3-4 PR254 P-1 A D-1 3000 X X Comparative Example 3-5 PG36 none A D-2 2000 X X

In addition, description in the said Table 7 is as follows.

PR 254: C.I.Pigment Red 254

PG36: C.I.Pigment Green 36

P-1: copolymer of methyl methacrylate / methacrylic acid = 85/15 (mass ratio), weight average molecular weight 20,000, acid value 98 mg KOH / g

P-3: a-10 / MMA / MAA = 20/30/30 (mass ratio) copolymer, weight average molecular weight 20,000

D-1: Solsperth 24000 (trade name, produced by Lubrizol Corporation)

1 (A) is an explanatory diagram showing the reactivity with the developer of the high molecular compound (A-2) according to the second aspect of the present invention.

1 (B) is an explanatory diagram showing the reactivity with a developer of a polymer compound in the prior art.

Claims (23)

As a pigment dispersion composition which contains a cyclic structure as a partial structure and contains a high molecular compound and dye which have a weight average molecular weight in the range of 1,000-100,000: The polymer compound is a pigment dispersion composition characterized in that at least one of the following conditions (i) and (ii). (i) a group which is decomposed by alkali to the cyclic structure is directly bonded; And (ii) the cyclic structure is at least one selected from the group consisting of a lactone structure and an acid anhydride structure, and the polymer compound has a structure of block type, lactone type or terminal modification type. The method of claim 1, The pigment dispersion composition which satisfy | fills said condition (i). The method of claim 2, The polymer compound is a pigment dispersion composition, characterized in that the compound having a monomer represented by the following general formula (G-1).

[Wherein X represents a hydrogen atom or a methyl group; W represents a single bond or a linking group formed by arbitrarily combining two or more linking groups selected from an atomic group represented by the following; Q represents a cyclic structure which may have a substituent; In addition, n represents an integer of 1 to 3:

Here, Z ¹ and Z ² represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group or a hydroxy group; In addition, Z ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms.] The method of claim 3, wherein The said polymeric compound represented by said general formula (G-1) is represented by either of the following general formula (G-1)-(G-V), The pigment dispersion composition characterized by the above-mentioned.

[In General Formulas (G-II) to (G-V), X represents a hydrogen atom or a methyl group; Q represents a cyclic structure which may have a substituent; And n represents an integer of 1 to 3.] The method of claim 2, The said polymeric compound contains 5-50 mass% of repeating units which have the said cyclic structure, The pigment dispersion composition characterized by the above-mentioned. The method of claim 2, The acid value of the said high molecular compound is 50 mg KOH / g-300 mg KOH / g, The pigment dispersion composition characterized by the above-mentioned. The method of claim 1, The pigment dispersion composition which satisfy | fills said condition (ii). The method of claim 7, wherein The said high molecular compound has a repeating unit provided with the group which has a lactone structure represented by any of the following general formula (LC1-1)-(LC1-10), The pigment dispersion composition characterized by the above-mentioned.

[Wherein, the lactone structure moiety may or may not have a substituent (R ^b2 ); R ^b2 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group or an acid-decomposable group; when n ² is 2 or more, a plurality of R ^{b2 's} may be the same or different; A plurality of R ^{b2 's} may be bonded to each other to form a ring.] The method of claim 8, The said repeating unit is represented by the following general formula (A1), The pigment dispersion composition characterized by the above-mentioned.

[Wherein, R ^b0 represents a hydrogen atom, a halogen atom or a C1-4 alkyl group which may have a substituent; A ^b represents a divalent linking group having an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group or a divalent linking group combining these; V represents a group represented by any one of General Formulas (LC1-1) to (LC1-10).] The method of claim 7, wherein The polymer compound has a repeating unit comprising a group having an acid anhydride structure represented by any one of the following general formula (UA1-1) to (UA1-5).

[Wherein, the acid anhydride structural moiety may or may not have a substituent (R ^b2 ); R ^b2 represents an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group; when n ² is 2 or more, a plurality of R ^{b2 's} may be the same or different; A plurality of R ^{b2 's} may be bonded to each other to form a ring.] The method of claim 10, The said repeating unit is represented by the following general formula (AII), The pigment dispersion composition characterized by the above-mentioned.

[In formula, R <^b0> represents the C1-C4 alkyl group which may have a hydrogen atom, a halogen atom, or a substituent; A ^b represents a divalent linking group having an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group combining these; V ² represents a group represented by one of General Formulas (UA1-1) to (UA1-5).] The method of claim 7, wherein Said high molecular compound is a block-type high molecular compound containing 5-80 mass% of repeating units which have the said cyclic structure as a partial structure, The pigment dispersion composition characterized by the above-mentioned. The method of claim 7, wherein The polymer compound is a pigment having a repeating unit having the cyclic structure as a partial structure in the graft side chain, and a lactone polymer compound having a ratio of 5 to 100% by mass of the repeating unit in the lactone side chain. Dispersion composition. The method of claim 7, wherein The polymer compound is a terminal-modified polymer compound having a repeating unit having a cyclic structure as a partial structure and having a ratio of 5 to 100% by mass of the repeating unit in the stem polymer part. Dispersion composition. The method of claim 7, wherein The polymer compound is a pigment dispersion composition, characterized in that it further contains an adsorption site. The method of claim 15, The polymer compound is a pigment dispersion composition, characterized in that the block-type polymer compound having 5 to 50% by mass of the repeating unit having the adsorption site. The method of claim 15, The said polymeric compound is a graft type polymeric compound which has a repeating unit which has the said adsorption site in a graft backbone, and the ratio of the said repeating unit in the said lactone backbone is 5-50 mass%. The method of claim 15, The polymer compound is a pigment dispersion composition, characterized in that the terminal-modified high-molecular compound modified terminal to the adsorption site. The photocurable composition containing the pigment dispersion composition as described in any one of Claims 1-18, alkali-soluble resin, a photopolymerizable compound, and a photoinitiator. It uses the photocurable composition of Claim 19, The color filter characterized by the above-mentioned. The color filter of Claim 20 was used, The liquid crystal display element characterized by the above-mentioned. A solid state image pickup device comprising the color filter according to claim 20. Providing a photosensitive film by applying the photocurable composition according to claim 19 on a substrate directly or through another layer, and And forming a colored pattern by subjecting the formed photosensitive film to pattern exposure and development.

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