JP2006225431A - Carbodiimide-based compound and method for producing pigment dispersed composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a carbodiimide-based compound in which a compound completely different from an objective molecular design does not occur at all, a polyacrylic side chain is introduced into a carbodiimide compound as the objective molecular design and excellent fluidity and dispersion stability are actualized in a high concentration of pigment and in a finely dispersed state, a pigment dispersed composition suitably useful in a wide range of ink-jet ink, a photosensitive resist composition, etc., by using the compound and a pigment dispersed resist composition containing the pigment dispersed composition. <P>SOLUTION: The method for producing a carbodiimide-based compound comprises polymerizing an acid group-free radically polymerizable unsaturated monomer containing at least one kind of an acid group-free (meth)acrylic monomer in the presence of an acid group-containing chain transfer agent to give a polyacrylic compound containing an acid group at one terminal of the molecule and introducing a polyacrylic chain to the carbodiimide compound by a reaction between the acid group at one terminal of the molecule of the obtained polyacrylic compound and the carbodiimide group of the carbodiimide compound having 100-50,000 carbodiimide equivalent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a carbodiimide compound and a method for producing a pigment dispersion composition using the carbodiimide compound. More specifically, the present invention relates to a carbodiimide that achieves good fluidity and dispersion stability in a state where a pigment is highly dispersed and finely dispersed. A method for producing a pigment-based compound, an intermediate composition, a method for producing a pigment-dispersed composition that contains the compound and can be suitably used in a wide range such as a photosensitive resist composition and inkjet recording, and a photosensitive composition as a final composition The present invention relates to a resist composition.

In addition to various printing inks and paints, pigments have recently begun to be used as colorants in fields where a clearer hue is required, such as color filters and inkjet inks.
These pigment dispersion techniques have made significant progress in recent years, and furthermore, a method of dispersing the pigment concentration as high as possible for rationalization of production has been carried out. However, when the pigment concentration is increased, fluidity, It has a basic problem that the dispersion stability is lowered.
In addition, in the field of color filters and ink jet recording, since high fastness is required, it is necessary to use high-grade pigments and to further reduce the particle diameter in order to obtain a clear hue. However, high-grade pigments originally have poor dispersion stability compared to other pigments, and the finer the particles, the more likely they are to aggregate and the more difficult it is to obtain a stable dispersion.

On the other hand, carbon black is widely used as a pigment with high blackness, but it is difficult to achieve high concentration and dispersion stability due to its small primary particle size, porosity and large specific surface area. There is a problem of lacking. Recently, attempts have been made to use carbon black as a black matrix light-shielding material. However, it is difficult to obtain a highly insulating black matrix from carbon black having high conductivity.
Therefore, in order to solve such problems, the applicant of the present application aims to increase the functionality of the carbodiimide compound used as a pigment dispersant, to disperse the hard-dispersible pigment more finely, and to maintain the state stably. The following proposals have already been made as a result of promoting the development of possible methods.
A method using a compound having a carbodiimide group as a method of utilizing a functional group and a covalent bond existing on the pigment surface (see, for example, Patent Document 1)
As a method of utilizing the adsorptive power with the pigment surface, a method of utilizing an acid-base affinity using a carbodiimide compound as a starting material (see, for example, Patent Document 2)
Method utilizing affinity resulting from similarity in molecular structure (for example, see Patent Document 3)
Such a pigment dispersant proposed by the applicant of the present application provides excellent effects in that dispersion stability and fluidity are very good even at high pigment concentrations, corresponding to higher pigment concentrations. Is.
In the carbodiimide compounds using the above methods (1) to (3) for obtaining a chemical binding force or adsorption force on the pigment surface, a domain is formed in a dispersion medium to form steric hindrance. At least one side chain selected from the group consisting of a polyester side chain, a polyether side chain and a polyacryl side chain is introduced so that the pigment can be stably dispersed in the dispersion medium. Propose to do.
International Publication WO 03/075527 Pamphlet International Publication WO04 / 000950 Pamphlet International Publication WO04 / 003085 Pamphlet

As a method for introducing a side chain into the above carbodiimide compound, a functional group capable of reacting with a carbodiimide group is used, but a polymer compound that does not have such a functional group in the molecule of the side chain is used. When many are included, the amount of the unreacted carbodiimide compound and the polymer compound is increased. On the other hand, when many compounds having a plurality of functional groups are included, there is a problem that the possibility of gelation increases. Such a problem has conventionally been liable to occur in the introduction of polyacryl side chains.

Usually, a polyacryl compound is obtained by polymerizing an acrylic monomer and, if necessary, another radical polymerizable unsaturated monomer, but when introduced as a side chain of a carbodiimide compound, a carbodiimide group and A method using a monomer having a reactive functional group, or a method of introducing such a functional group later (for example, a method of synthesizing a polyacryl compound having a hydroxyl group in a molecule and reacting an acid anhydride) ) Is common. However, in all polyacryl compound molecules, it is virtually impossible to control the reaction having only one such functional group, and in fact, one having no functional group in the molecule, one It is thought that what has and what has more is obtained. Here, when gelation occurs when the side chain is introduced, it cannot be used as a pigment dispersant or the like, resulting in a larger problem that the basic performance intended in the present invention is impaired. In order to avoid this problem, the use of a monomer having a functional group capable of reacting with a carbodiimide group (a functional group that becomes a base group when introduced later, and a hydroxyl group in the above example) is minimized. Naturally, many polyacrylic compounds having no functional group in the molecule are inevitably synthesized, and the synthesis of polyacrylic compounds having a plurality of functional groups cannot be completely prevented.

As a result, when trying to introduce a polyacrylic compound into the side chain of a carbodiimide compound, there are compounds that are completely different from the target molecular design, such as a carbodiimide compound without a side chain or a gelled carbodiimide compound. There was a high possibility that many would be obtained.
Therefore, the problem of the present invention is that no compound completely different from the target molecule design is generated, and the polyacryl side chain is introduced into the carbodiimide compound as in the target molecule design, and the pigment is increased. A method for producing a carbodiimide compound that achieves good fluidity and dispersion stability in a state of being finely dispersed in a concentration, suitable for a wide range of ink jet inks, photosensitive resist compositions, etc. using the compound It is to provide a method for producing a pigment dispersion composition that can be used, and a pigment dispersion resist composition containing the pigment dispersion composition.

Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors obtained by polymerizing an acid group-free (meth) acrylic monomer in the presence of a chain transfer agent having an acid group. The present invention has been completed by finding that a polyacryl side chain can be introduced without causing gelation in the reaction with a carbodiimide compound by using the polyacryl compound obtained.
That is, the present invention provides (1) an acid group-free radical polymerizable unsaturated monomer containing at least one acid group-free (meth) acrylic monomer in the presence of an acid group-containing chain transfer agent. Polymerization yields a polyacrylic compound containing an acid group at one end of the molecule, and the resulting polyacrylic compound reacts with an acid group at one end of the molecule and a carbodiimide group of a carbodiimide compound having a carbodiimide equivalent of 100 to 50,000. It is related with the manufacturing method of the carbodiimide type compound which consists of introduce | transducing a polyacryl chain | strand by making it.

The present invention also provides (2) an acid group-free radically polymerizable unsaturated monomer containing at least one acid group-free (meth) acrylic monomer in the presence of an acid group-containing chain transfer agent. Polymerization yields a polyacrylic compound containing an acid group at one end of the molecule, and the resulting polyacrylic compound reacts with an acid group at one end of the molecule and a carbodiimide group of a carbodiimide compound having a carbodiimide equivalent of 100 to 50,000. It is related with the manufacturing method of the pigment dispersion composition which introduce | transduces a polyacryl chain | strand and obtains a carbodiimide type compound, and disperses a pigment using the said carbodiimide type compound.
The present invention also relates to (3) the production method according to (1) or (2) above, wherein the acid group-containing chain transfer agent is a thiol-based acid group-containing chain transfer agent.
Further, the present invention provides (4) at least selected from the group consisting of a basic nitrogen-containing chain, a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain in the molecule of the carbodiimide compound. The present invention relates to the production method according to any one of (1) to (3) above, wherein one kind of chain is introduced.
Moreover, this invention relates to the carbodiimide type compound obtained by the manufacturing method of any one of (5) said (1) and (3)-(4).
Moreover, this invention relates to the pigment dispersion composition obtained by the manufacturing method of any one of (6) said (2)-(4).
The present invention also relates to (7) a pigment dispersion resist composition containing the pigment dispersion composition described in (6) above.

Hereinafter, the present invention will be described in more detail.
<About the manufacturing method of a carbodiimide type compound>
The method for producing a carbodiimide compound of the present invention comprises reacting an acid group at one end of a polyacryl compound obtained by using an acid group-containing chain transfer agent with a carbodiimide group of a carbodiimide compound having a carbodiimide equivalent of 100 to 50000. Thus, a polyacryl chain is introduced into the molecule of the carbodiimide compound.
The polyacryl compound is synthesized from a material having no functional group capable of reacting with the carbodiimide group except for the acid group-containing chain transfer agent. As a result, the functional group capable of reacting with the carbodiimide group is synthesized at one end of the molecule. Therefore, a gelled product is not generated in the reaction with the carbodiimide compound, and a polyacryl chain can be introduced into the carbodiimide compound as designed for the target molecule. The carbodiimide compound obtained from such a material has a polyacryl side chain in the side chain, and can be used in various applications where pigment dispersion stability is required.

As used herein, “side chain” refers to a chain that is branched from a portion derived from a carbodiimide compound, which is formed by reacting a carbodiimide group of a carbodiimide compound with a compound having a group that reacts with a carbodiimide group. Say. Hereinafter, in the present invention, regardless of the size of the chain structure, a portion derived from a carbodiimide compound is referred to as a “main chain”, and all chains branched from the main chain are referred to as “side chains”.

1) Material for synthesizing a carbodiimide compound First, in the method for producing a carbodiimide compound of the present invention, a carbodiimide compound which is an essential constituent material and a starting material, and a polyacryl for introduction as a side chain The compound will be described.
1-1) Carbodiimide compound In order to obtain a carbodiimide compound by the production method of the present invention, a carbodiimide compound used as a starting material is represented by a carbodiimide group in the molecule, i.e., -N = C = N-. This compound is a compound having at least one group, and will be described more specifically with the following preferred embodiments (a) to (d). It is appropriately selected and used depending on the form.
(A) A carbodiimide compound having an isocyanate group obtained by decarboxylation of a diisocyanate compound.
A carbodiimide compound can be produced by carbodiimidizing an isocyanate compound by a decarboxylation reaction in an organic solvent in the presence of a carbodiimidization catalyst, and when the material is a diisocyanate compound, an isocyanate is present at both ends of the molecule. A carbodiimide compound having a group will be obtained.
In the above production method, the diisocyanate compound to be decarboxylated includes, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, tetramethylxylylene diisocyanate. And aliphatic, alicyclic, aromatic or araliphatic diisocyanate compounds.

As said organic solvent, it is preferable to use what has a high boiling point and does not have active hydrogen which reacts with an isocyanate compound and the carbodiimide compound to produce | generate, For example, aromatic hydrocarbons, such as toluene, xylene, diethylbenzene; Glycol ether esters such as diethylene glycol diacetate, dipropylene glycol dibutyrate, hexylene glycol diacetate, glycol diacetate, methyl glycol acetate, ethyl glycol acetate, butyl glycol acetate, ethyl diglycol acetate, butyl diglycol acetate; Ketones such as ketones, acetophenone, propiophenone, diisobutylketone, cyclohexanone; amyl acetate, propyl propionate, ethyl butyrate Fatty acid esters and the like can be mentioned.

As the carbodiimidization catalyst, phospholenes and phospholene oxides are preferably used. For example, 1-ethyl-3-methyl-3-phospholene oxide, 1-phenyl-3-methyl-3-phospholene oxide 1-phenyl-3-methyl-2-phospholene oxide and the like.

As a method of performing a decarboxylation reaction of an isocyanate group using these materials, a known method can be used. For example, the reaction can be performed at a reaction temperature of 100 to 200 ° C. in a nitrogen atmosphere. Examples of other methods for obtaining the above compound having a carbodiimide group include methods such as US Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, Japanese Patent Application Laid-Open No. 5-178954, and Japanese Patent Application Laid-Open No. 6-56950. Is mentioned.

Regarding a carbodiimide compound having an isocyanate group obtained by using such a production method, for example, a compound obtained by decarboxylation of K mole (however, an integer of K ≧ 2) a diisocyanate compound is represented by the following general formula (1) Shown in
OCN- (A-N = C = N) _K-1- A-NCO (1)
In the general formula (1), A represents a residue excluding the isocyanate group of the diisocyanate compound used for the synthesis of the carbodiimide compound having an isocyanate group.
Examples of commercially available carbodiimide compounds having an isocyanate group represented by the general formula (1) include, for example, carbodiimide compounds using tetramethylxylylene diisocyanate as a raw material, carbodilite V-03, V-05, etc. Name, manufactured by Nisshinbo Co., Ltd.).

(B) A carbodiimide compound obtained by further chain-extending the carbodiimide compound of (a) with a chain extender.
The carbodiimide compound of the above (a) is made high in molecular weight using a chain extender capable of reacting with an isocyanate group, and can be a compound containing more carbodiimide groups in the molecule. The chain extender that can be used at this time is preferably a compound that has low reactivity with a carbodiimide group and that selectively reacts with an isocyanate group first, and examples thereof include a diol compound, a diamine compound, and hydrazine. .

(C) A compound obtained by decarboxylation of 2 mol of a monoisocyanate compound and K mol (where K is an integer of 1).
The carbodiimide compounds (a) and (b) are compounds having an isocyanate group at both ends of the molecule, and there is an advantage that various molecular chains can be added using the isocyanate group. When the material to be reacted with is also reacted with an isocyanate group, there is a problem that it is difficult to introduce as a side chain. On the other hand, it can be said that the above problem does not occur in a carbodiimide compound in which both ends of the molecule are stopped with a monoisocyanate compound. A carbodiimide compound in which both ends of the molecule are stopped with a monoisocyanate compound can be represented by the following general formula (2).
B−N = C = N− (A−N = C = N) _k −B (2)

In the general formula (2), B represents a residue other than the isocyanate group of the monoisocyanate compound used for the synthesis of the carbodiimide compound having an isocyanate group. A is as described above.
Here, examples of the diisocyanate compound that can be used include the same synthetic materials as in the above (a), and examples of the monoisocyanate compound include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, and octadecyl. Examples thereof include aliphatic, alicyclic, aromatic or araliphatic monoisocyanate compounds such as isocyanate and phenyl isocyanate.

(D) A compound obtained by decarboxylation of 1 mol of a monoisocyanate compound and K mol (provided that an integer of K ≧ 1) of a diisocyanate compound.
As an intermediate compound between those having an isocyanate group at both ends of the molecule and those having no isocyanate group, the reaction is stopped with a monoisocyanate compound at only one end, and a carbodiimide compound having an isocyanate group at the other end is also obtained. Can do. A carbodiimide compound in which one end of such a molecule is stopped with a monoisocyanate compound can be represented by the following general formula (3).
OCN- (A-N = CN) _k- B (3)
In the general formula (3), B represents a residue excluding the isocyanate group of the monoisocyanate compound used for the synthesis of the carbodiimide compound having an isocyanate group. A is as described above.

Here, the diisocyanate compound which can be utilized can mention the same thing as the synthetic material of said (a), and can mention the same thing as the synthetic material of said (c) as a monoisocyanate compound.

As mentioned above, the said carbodiimide compound (a)-(d) may be used independently as a starting material of a carbodiimide type compound, and may use 2 or more types together.
And in said carbodiimide compound, the thing of carbodiimide equivalent is 100-50000 is utilized. Here, the carbodiimide equivalent means a number represented by (molecular weight of carbodiimide compound) / (number of carbodiimide groups in carbodiimide compound molecule). If the carbodiimide equivalent of the compound is too high, the weight ratio of the polyacryl side chain to the whole molecule of the carbodiimide compound obtained will be small, and the dispersion stability of the pigment may be reduced. On the other hand, a compound having a low carbodiimide equivalent is advantageous in that it can increase the weight ratio of the polyacryl side chain and the side chain having each functionality described later to the whole molecule of the carbodiimide compound. Therefore, it becomes difficult to synthesize the carbodiimide compound itself and to control the reaction for introducing a side chain. Therefore, a more preferable carbodiimide equivalent is 200 or more and 10,000 or less.

1-2) Polyacryl compound Next, the polyacryl compound used for introduction as a side chain of the carbodiimide compound will be described.
As a method for producing the carbodiimide compound of the present invention, a method of introducing a polyacryl side chain by a reaction between a carbodiimide group and an acid group that reacts with the carbodiimide group is used.
A feature of the present invention is that, as a polyacryl compound that reacts with a carbodiimide group, in the presence of an acid group-containing chain transfer agent, at least one acid group-free (meth) acrylic monomer is used. It is to use a polyacryl compound having an acid group at one end, obtained by polymerizing the containing radical polymerizable unsaturated monomer.

Examples of the acid group-containing chain transfer agent include chain transfer agents having a carboxyl group such as mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, O-mercaptobenzoic acid; 2-chloroethanesulfonic acid, 2-chloroethanesulfone Contains sulfonic acid groups such as sodium acid, 4-chlorophenyl sulfoxide, 4-chlorobenzenesulfonamide, p-chlorobenzenesulfonic acid, sodium p-chlorobenzenesulfonate, sodium 2-bromoethanesulfonate, sodium 4- (bromomethyl) benzenesulfonate A chain transfer agent etc. are mentioned. Among these acid group-containing chain transfer agents, thiol-based acid group-containing chain transfer agents are preferable, and mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and O-mercaptobenzoic acid are more preferable.

Examples of the acid group-free (meth) acrylic monomer include alkyl (meth) acrylate compounds (for example, methyl methacrylate), (meth) acrylate compounds having an aromatic ring (for example, allyl acrylate, allyl methacrylate, Acrylic acid ester compounds such as benzyl acrylate and benzyl methacrylate). Examples of the non-acrylic acid group-containing radical-polymerizable unsaturated monomer other than acrylic are styrene monomers such as styrene and α-methylstyrene. Can be mentioned.

When polymerizing a polyacryl compound using such a monomer component, a commonly used initiator, for example, azo-nitrile compound: 2,2′-azo-bis-isobutyronitrile, 1,1′- Azo-bis-1-cyclobutanenitrile, 2,2′-azo-bis-2methylbutyronitrile, etc., azo compounds: 2,3-diaza-bicyclo [2,2,1] heptene, 2,2,2 ′ -Azo-bis-propane, 1,1'-azo-bis-1-phenylethane, peroxide compounds: t-butyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. it can.

The polyacrylic compound having an acid group at one end is obtained by using a polymerization method such as bulk polymerization, solution polymerization, and suspension polymerization if necessary, and using a total charge method, an initiator dropping method or a monomer dropping method as an initiator. It can be synthesized by reacting for 1 to 8 hours at a reaction temperature of 70 to 170 ° C. or higher. In this polymerization, a polyacrylic compound having an acid group at one end can be obtained by using an acid group-containing chain transfer agent as the chain transfer agent.
The polyacryl chain introduced as the side chain is not particularly limited as long as it has an effect of improving the dispersion stability of the pigment in the dispersion medium, but preferably has a number average molecular weight of 200 or more, and 10,000 It is as follows. More preferably, it is 300 or more and 6000 or less.
In the synthesis of the polyacrylic compound, the amount of the acid group-containing chain transfer agent is such that the amount of the monomer to be used and the amount of the acid group-containing chain transfer agent are the desired number average molecular weight. To be determined as appropriate.

1-3) Material for introducing other functional chain In the method for producing a carbodiimide compound of the present invention, the following (A) is further selected depending on the performance required for the obtained carbodiimide compound. A compound having a plurality of functions can be obtained by introducing one or two or more kinds of molecular chains and functional groups having various functions such as) to (e) into the molecule of the carbodiimide compound. And the carbodiimide type compound which has these several functions is a preferable form in this invention at the point that the field | area which can be utilized may become wider.
(A) a carbodiimide group (a) a basic nitrogen-containing chain (c) at least one chain (e) polyester selected from the group consisting of a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain At least one chain selected from the group consisting of a chain and a polyether chain (e) a chain having an ultraviolet sensitizing ability and / or a chain having a radical initiating ability

The carbodiimide compound of the present invention includes at least one selected from the group consisting of a carbodiimide group, a basic nitrogen-containing chain, a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain in the molecule. Those containing chains are more preferred.

Here, in order to introduce the carbodiimide group of (a), at the time of introducing the polyacryl side chain in the production of the carbodiimide compound, at least one carbodiimide group in the molecule of the carbodiimide compound is left unreacted as it is. For the introduction of the functional chain described in (a), for example, the material described in International Publication WO 04/000950, and the introduction of the functional chain described in (c) For example, for the introduction of the functional chain described in International Publication WO 04/003085 and the functional chain described in (d), for example, the material described in International Publication WO 03/075527 may be used. it can.
In addition, for the introduction of the functional chain described in (e), for example, when the carbodiimide group can react with a functional group or when the carbodiimide compound also has an isocyanate group, for example, a hydroxyl group, an amino group, etc. A compound having a functional group that easily reacts with an isocyanate group and having an ultraviolet sensitizing ability and / or a radical initiating ability can be used as a material.

Specific examples of such compounds include benzoylbenzoic acid, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1 Examples include N-alkyl dialkanolamines such as -hydroxy-cyclohexyl phenyl ketone, dimethylaminobenzoic acid, diethylaminobenzoic acid, N-ethyldiethanolamine, and N-methyldiethanolamine.

2) Molecular structure and effect of carbodiimide compound The carbodiimide compound obtained by the production method of the present invention is obtained by using the above-mentioned materials, and for that purpose, the carbodiimide compound which is a starting compound. In addition, the polyacryl compound having an acid group at one end is introduced through a reaction with a cardiimide group.
As such a carbodiimide compound, for example, when a compound having the structure of the above formula (1) is used as a carbodiimide compound as a starting compound, it can be schematically expressed as the following general formula (4).
OCN-X _(L) -(N = C = N) _(N-L) -OCN (4)
[Wherein X is each independently a structural unit containing a polyacryl side chain bonded via a linking group obtained by reaction of a carbodiimide group and a functional group capable of reacting with it, and L is X in the molecule. Represents the number of structural units, and is an integer of 1 or more. N represents the number of carbodiimide groups in the carbodiimide compound as a starting material, and is an integer of 1 or more. (N−L) represents an integer of 0 or more. ]

Moreover, about the chain | strands (a)-(e) which have other functions utilized arbitrarily, the method of introduce | transducing through reaction with either a carbodiimide group or an isocyanate group can be utilized. As such a carbodiimide compound, for example, when a compound having the structure of the above formula (1) is used as a carbodiimide compound as a starting compound, it can be schematically expressed as the following general formula (5).
YX _(L) -Z _(M) -(N = C = N) ₍ NLM ₎ -Y (5)
[Wherein X, L, and N have the same definitions as above, and Y independently represents an unreacted isocyanate group or a linking group obtained by reacting an isocyanate group with a functional group capable of reacting with it. Is a structural unit containing the functional chains of (a) to (e) above, and Z is independently bonded via a linking group formed by a reaction between a carbodiimide group and a functional group capable of reacting with it. It is a structural unit containing the functional chains of (i) to (e). M represents the number of Z constituent units in the molecule and represents an integer of 0 or more. In addition, (NLM) represents an integer of 0 or more. ]

In addition, the above general formulas (4) and (5) are displayed by abstracting only main parts, and the structure in which the constituent units of X and Z are linked is representatively displayed. A structure in which X, Z, and-(N = C = N)-are randomly bonded is also included. And it can be said that General formula (4) is a basic structure of the carbodiimide type compound of this invention, On the other hand, about General formula (5), it can be said that it is a preferable structure which aimed at multifunctionality.

Furthermore, the site of Y in the above formula (5) is a structural unit other than (i) to (e), in which a compound capable of reacting with an isocyanate group is bonded by opening a linking group by the same reaction. There may be. As such a compound having a functional group capable of reacting with an isocyanate group, a compound having a low reactivity with a carbodiimide group and selectively reacting with an isocyanate group first is preferable. For example, a low molecular weight compound such as methanol or ethanol is used. Alcohol compounds; secondary amine compounds such as diethylamine and dibutylamine can be mentioned.

In addition, the linking group formed when the polyacryl side chain is introduced by reacting the carbodiimide group with an acid group at one end of the polyacryl compound is usually a carbodiimide group, a carboxyl group, a sulfone group. It is formed by the reaction with an acid group such as an acid group, and is formed when the side chains (a) to (e) above are introduced by reacting a reactive functional group with a carbodiimide group. The linking group is usually formed by the reaction of a carbodiimide group with a carboxyl group, sulfonic acid group, phosphoric acid group, hydroxyl group, amino group, or the like, and has the following structure.

For example, the linking group formed from the reaction between the carbodiimide group and the carboxyl group is represented by the following general formulas (6) and (7). The linking group formed from the reaction between the carbodiimide group and the hydroxyl group includes the following general groups. The linking group represented by the formulas (8) and (9) and formed from the reaction between the carbodiimide group and the amino group is represented by the following general formula (10), and is formed from the reaction between the carbodiimide group and the sulfonic acid group. The group is represented by the following general formula (11), and the linking group formed from the reaction between the carbodiimide group and the phosphate group is represented by the following general formula (12).

In addition, the linking group formed by reacting a functional group capable of reacting with an isocyanate group is usually formed by a reaction between an isocyanate group and a hydroxyl group, a primary or secondary amino group, etc. It becomes the structure like this.
For example, the linking group formed from the reaction between an isocyanate group and a hydroxyl group is represented by the following general formula (13), and the linking group formed from the reaction between an isocyanate group and an amino group is represented by the following general formula (14). It is represented by

In the above formula, R represents a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms.
As described above, the carbodiimide-based compound of the present invention has the general formulas (6), (7), (11), (12) as a starting material, for example, at the site that was the carbodiimide group of the carbodiimide compound of the general formula (1) ), At least one polyacryl side chain is introduced through one of the linking groups to form a compound having a structural unit of X in the general formula (4). Further, in the same manner, other functional side chains are introduced, a compound having a Z structural unit of the general formula (5), and at both ends or one end of the molecule, the compounds of the general formulas (13) and (14) A compound in which a functional chain or the like is introduced via any one of the linking groups, or a compound in which a carbodiimide group remains in the molecule is preferable.

In the present invention, the polyacryl compound to be reacted with the carbodiimide compound is obtained by polymerizing an acid group-free (meth) acrylic monomer in the presence of an acid group-containing chain transfer agent. Therefore, a polyacryl compound having one acid group only at one end of the molecule and no acid group or plural acid groups is not included. As a result, an unreacted polyacrylic compound does not remain, and there is no gelled product generated in the reaction with the carbodiimide compound, and a carbodiimide-based compound according to the molecular design can be obtained.

In addition, since the obtained carbodiimide compound has a polyacryl side chain in the side chain, the side chain forms a domain in the dispersion medium and acts as a steric hindrance, thereby dispersing the pigment. It becomes possible to disperse stably in the medium.
Furthermore, the carbodiimide compound of the present invention can be multi-functionalized by introducing other functional side chains. For example, the pigment dispersion function, which is a basic performance, depends on the type of pigment used. Thus, by introducing a functional group or a side chain having a dispersion stabilizing action by covalent bond or adsorption with the pigment surface, it becomes possible to exert a further sufficient effect. That is, when using a pigment having a functional group that reacts with a carbodiimide group on the surface as described later, the carbodiimide compound has one or more carbodiimide groups in the molecule and uses a covalent bond between the functional groups. By doing so, it becomes possible to exhibit the effect of further pigment dispersion. Moreover, when using the pigment which has an acidic site | part on the surface, if it has a basic nitrogen containing chain | strand in a molecule | numerator as a carbodiimide type compound, adsorption | suction by an acid-base affinity can be utilized. The “basic nitrogen-containing chain” has at least one basic nitrogen-containing group, and the “basic nitrogen-containing group” contains nitrogen that forms a quaternary ammonium ion in water. In addition to the above groups, nitrogen groups which act as Lewis bases are included, and typical examples thereof include amino groups and nitrogen-containing heterocyclic groups. Furthermore, when using adsorption due to affinity due to the similarity in the molecular structure of the pigment, the carbodiimide compound consists of a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain in the molecule. It has at least one chain selected from the group.

On the other hand, from the viewpoint of stably dispersing the pigment in the dispersion medium, the carbodiimide compound further has at least one chain selected from the group consisting of a polyester chain and a polyether chain in the molecule. May be. In the carbodiimide-based compound, the polyester chain and the polyether chain may have a main chain or a side chain, and among them, those having a side chain are more preferable.
In addition, when the carbodiimide compound of the present invention is used for the purpose of curing with active energy rays, it has a radical-initiating chain and / or an ultraviolet-sensitized chain from the viewpoint of improving curability by the active energy beam. More preferably.

3) Method for producing carbodiimide compound In the method for producing a carbodiimide compound of the present invention, all reactions, i.e., reactions for introducing a side chain, include carbodiimide group, carboxyl group, sulfonic acid group, phosphorus Conventional methods can be used for the reaction with an acid group, a hydroxyl group, an amino group, or the like, or for the reaction between an isocyanate group and a hydroxyl group, an amino group, or the like. Further, the order of introducing the polyacrylic chain and various functional chains is not particularly limited. For example, when two or more compounds having a functional group that reacts with a carbodiimide group are used, they are added separately or simultaneously. Even when two or more compounds having a functional group that reacts with an isocyanate group are used, they can be reacted separately or simultaneously. In addition, when using a compound having a functional group that reacts with a carbodiimide group and a compound having a functional group that reacts with an isocyanate group, if the same compound is finally obtained, even if it is reacted with a carbodiimide group first, Either of them may be reacted with an isocyanate group.

The polyacryl side chain introduced into the molecule of the carbodiimide compound, the type and ratio of each functional chain, the amount of the remaining carbodiimide group, etc., for example, the pigment and dispersion when used as a pigment dispersant It is preferable to set each material appropriately so as to be a compound having a good performance balance by appropriately setting according to the type of medium or the like and the performance required in other application fields.

The number average molecular weight of the carbodiimide compound obtained from the production method of the present invention is preferably 1000 or more and 100,000 or less. When the number average molecular weight becomes too high, when the pigment is dispersed in the dispersion medium using the carbodiimide compound of the present invention, or when it is a pigment dispersion composition, it becomes difficult to obtain a product having an appropriate viscosity. This is not particularly preferred when a pigment dispersion composition with a high concentration is required. On the other hand, if the number average molecular weight is too low, the dispersion stability of the pigment in the dispersion medium is lowered, which is not preferable. More preferably, it is 1000 or more and 50000 or less.
A carbodiimide compound obtained by the above production method is also one aspect of the present invention.

<About the manufacturing method of a pigment dispersion composition>
Next, a method for producing a pigment dispersion composition, in which a pigment is dispersed using the carbodiimide compound, will be described.
That is, the method for producing the pigment dispersion composition of the present invention is a method for transferring an acid group-free radical polymerizable unsaturated monomer containing at least one acid group-free (meth) acrylic monomer to an acid group-containing chain transfer. Polymerized in the presence of an agent to obtain a polyacryl compound containing an acid group at one end of the molecule, the acid group at one end of the molecule of the resulting polyacryl compound, and a carbodiimide compound having a carbodiimide equivalent of 100 to 50000 A carbodiimide compound is obtained by reacting with a carbodiimide group to obtain a carbodiimide compound, and a pigment is dispersed using the carbodiimide compound.
As the carbodiimide compound used in the method for producing a pigment dispersion composition of the present invention, depending on the functional group on the pigment surface, the presence or absence of adsorption points, the type of dispersion medium, the use of the obtained pigment dispersion composition, etc. The carbodiimide compounds having the functional groups and functional chains (a) to (e) can be appropriately prepared and used.
In the method for producing a pigment dispersion composition of the present invention, the pigment includes a carbodiimide compound and at least a covalent bond, an adsorbed acid-base affinity, or an affinity resulting from similarity in molecular structure. For example, organic pigments and inorganic pigments generally used for printing inks, paints, ink jet ink compositions, color filter resist compositions, and the like can be used.

First, as a pigment having a carbodiimide group and a carbodiimide group and a covalent bond, those having a functional group that reacts with a carbodiimide group on the pigment surface are preferable, among which a carboxyl group, a sulfonic acid group, a phosphoric acid group, An organic pigment or an inorganic pigment having at least one functional group selected from the group consisting of a hydroxyl group and an amino group is preferable.
Examples of the organic pigment include dye lake pigments, azo series, benzimidazolone series, phthalocyanine series, quinacridone series, anthraquinone series, dioxazine series, indigo series, thioindico series, perylene series, perinone series, diketopyrrolopyrrole series, Isoindolinone, nitro, nitroso, anthraquinone, flavanthrone, quinophthalone, pyranthrone, indanthrone, and the like as carbon black (preferably having a carboxyl group at pH 7 or less) ), Titanium oxide, bengara, graphite, iron black, chromium oxide green, aluminum hydroxide and the like.

In addition, when the pigment surface does not have a functional group that reacts with a carbodiimide group, the functional group can be introduced by surface treatment. For example, "Pigment dispersion stabilization and surface treatment technology / evaluation" first printing, technology Information Association (Publishing), December 25, 2001, p. The functional group capable of reacting with the carbodiimide group can be introduced by the plasma treatment described in 76 to 85, oxygen / ultraviolet treatment, or the low temperature plasma method described in JP-A-58-217559. Further, a pigment can be coated with an insulating compound (silica, silane compound, titanium compound, etc.), and a functional group that reacts with a carbodiimide group can be introduced.

Next, as a pigment having an adsorption part based on acid-base affinity for a carbodiimide compound having a basic nitrogen-containing chain, an organic pigment or an inorganic pigment having an adsorption part with a basic nitrogen-containing group on the pigment surface It is preferable that
The adsorbing portion with the basic nitrogen-containing group is typically an acid group, preferably a functional group capable of adsorbing with a basic nitrogen-containing group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. is there.
Examples of organic pigments having adsorbing moieties with these basic nitrogen-containing groups include dye lake pigments, azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, indigo, thioindico, and perylene. , Perinone, diketopyrrolopyrrole, isoindolinone, nitro, nitroso, anthraquinone, flavanthrone, quinophthalone, pyranthrone, indanthrone, and other inorganic pigments such as carbon black (Preferably, those having a carboxyl group at pH 7 or lower) and the like.

It should be noted that even a pigment having no adsorbing part with a basic nitrogen-containing group may be introduced with a carboxyl group or a sulfonic acid group by treating with a normal functional group introduction method such as a derivative treatment or sulfonation treatment on the pigment surface. Can do.
Next, similarity in molecular structure to a carbodiimide compound having at least one chain selected from the group consisting of a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain in the molecule The pigment having an adsorbing part due to the affinity due to the structure has the same or similar structure as at least one chain selected from the group consisting of a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain. An organic pigment or an inorganic pigment; a pigment derivative chain that does not have the same or similar structure as at least one chain selected from the group consisting of a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain An organic pigment or an inorganic pigment having a sufficient adsorptive power with at least one chain selected from the group consisting of a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain.

Adsorption due to affinity due to such similarity in molecular structure, for example, pigments that do not have a functional group capable of reacting with a carbodiimide group and / or an isocyanate group (when no covalent bond is available); can react with a carbodiimide group Even if the pigment has a functional group, the functional group capable of reacting with the carbodiimide group of the pigment is, for example, an amino group or a hydroxyl group, and the temperature at which the functional group reacts with the carbodiimide group is 100 ° C. or more (covalent bond) This is more effective when the use of is conditionally difficult.

As a suitable combination of at least one kind of chain selected from the group consisting of such a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain and a pigment, for example, (1) Pigment derivative As for the phthalocyanine pigment derivative chain as the chain, there is a combination with Pigment Black 7 in addition to the phthalocyanine pigment as the pigment, and (2) for the β-naphthol orange dye derivative chain as the dye derivative chain, In addition to naphthol pigments, there are combinations with condensed azo pigments. (3) For the anthraquinone derivative chain as the dye intermediate chain, in addition to the dianthraquinonyl pigment as a pigment, a diketopyrrolopyrrole pigment, Condensed azo pigments, isoindole pigments, perinone pigments, azo pigments having a heterocyclic ring, quinacridone pigments, And a combination of the bromo anthanthrone pigment and / or benzimidazolone pigment.

As a method of obtaining a pigment dispersion composition using the carbodiimide compound, for example, (I) a dispersion medium capable of stably dispersing the pigment after treating the pigment with only the carbodiimide compound, and if necessary A method of obtaining a pigment composition by adding various binder resins, photopolymerizable compounds, solvents, surfactants, and other additives and stirring the mixture; (II) a dispersion medium in which a carbodiimide compound is dissolved and the pigment can be stably dispersed In the method of obtaining a pigment dispersion composition by processing while dispersing the pigment in step (3), particularly in applications using a photopolymerizable material, (III) in a photopolymerizable compound in which a carbodiimide compound is dissolved and the pigment can be stably dispersed And a method of obtaining a pigment dispersion composition by treating while dispersing the pigment.
In (II) and (III), various types of binder resins, photopolymerizable compounds, solvents, surfactants, and other additives may be included as needed during pigment dispersion and after pigment dispersion.

The term “treatment” as used in the present invention means that the entire surface or part of the surface of the pigment dispersed particles is treated with a carbodiimide compound. Specifically, a mixture of the pigment, the carbodiimide compound, and, if necessary, a dispersion medium, other additives, a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, A method of kneading, dispersing and treating using a high-pressure dispersing device or the like is mentioned.

As the method for obtaining the pigment dispersion composition of the above (I), a method can be used in which the pigment is treated at a temperature equal to or higher than the melting point of the carbodiimide compound and then dispersed in a suitable dispersion medium for any application. . In addition, when processing the pigment which has a functional group which can react with a carbodiimide group, the temperature which can accelerate | stimulate reaction between this functional group is about 100 degrees C or less, Preferably, it heats to 40-80 degreeC. Is preferred.

On the other hand, in the method of obtaining the pigment dispersion composition of the above (II) and (III), the treatment is possible even at a relatively low temperature, but the functional group capable of reacting with the carbodiimide group is a carbodiimide compound having a carbodiimide group in the molecule. In the case of treating a pigment having a group, it is more preferable to further heat to a temperature that promotes the reaction.

Examples of the dispersion medium that can be used in the method for obtaining the pigment dispersion composition include organic dispersion media such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl. (Poly) alkylene glycol monoalkyl ethers such as ether and propylene glycol monoethyl ether; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate; Diethylene glycol diethyl ether, diethylene glycol methyl ether Ethers such as ether and tetrahydrofuran; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethyl hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, ethyl acetate, n-butyl acetate , Esters such as isobutyl acetate, n-butyl propionate, methyl acetoacetate, n-amyl formate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; n-methylpyrrolidone, N, N-dimethylformua De, N, N-amides of dimethyl acetamide and the like; alcohol solvents such as isopropyl alcohol and normal propyl alcohol. In addition, these dispersion media can be used individually or in mixture of 2 or more types.
Moreover, as an aqueous medium, only water may be sufficient and combined use with a water-miscible organic type dispersion medium may be sufficient.

It is preferable that the usage-amount of the pigment in the said pigment dispersion composition is 5-97 mass% in a mass fraction with respect to the total solid in a pigment dispersion composition.
The mass ratio of the carbodiimide compound in the pigment dispersion composition is preferably 3 parts by mass or more and 100 parts by mass or less, more preferably 5 parts by mass with respect to 100 parts by mass of the pigment (total amount of used pigments). As described above, the amount is 50 parts by mass or less, but it is preferable to adjust by the amount of functional groups that react with and adsorb to the carbodiimide compound existing on the pigment surface, dispersion performance, fluidity, required performance, and the like.
The pigment dispersion composition obtained by the above production method is also one aspect of the present invention.

Next, the active energy ray-curable composition, which is an application as the final composition of the present invention, will be described.
<Active energy ray-curable composition>
The above-mentioned pigment dispersion composition is prepared by further adding various binder resins, photopolymerizable compounds, photopolymerization initiators, sensitizers, solvents, surfactants, and the like as necessary, for example, active energy ray curable printing ink. It is used as an active energy ray-curable composition such as an active energy ray-curable coating material, an active energy ray-curable inkjet ink composition, a pigment dispersion resist composition for a black matrix, and a color filter.

In the present invention, as an example of a preferable application of the active energy ray-curable composition, a pigment dispersion resist composition for a black matrix and a color filter will be described in more detail.
The pigment-dispersed resist composition is an active energy ray-curable resist composition that can be developed with an alkali, mainly from pigments, carbodiimide compounds, film-forming resins, photopolymerizable compounds, photopolymerization initiators, and solvents. It is comprised and contains various additives, such as a sensitizer and a polymerization inhibitor, as necessary. The pigment dispersion resist composition of the present invention contains various additives such as a film-forming resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, a sensitizer, and a polymerization inhibitor, depending on the purpose. In addition.

First, the pigment used in the pigment dispersion resist composition for black matrix and color filter of the present invention will be described.
A typical pigment constituting the black matrix pigment dispersion resist composition includes carbon black. As the carbon black, it is preferable to use a carbon black having an average primary particle size of 0.15 μm or less. When such a carbon black is dispersed, a complementary color pigment is mixed as necessary to change the hue. Neutral black is preferred.
As the organic pigment constituting the pigment-dispersed resist composition for color filters, it is preferable to use a higher-grade organic pigment in order to form a film having a clear hue.
Specific examples of the higher organic pigment include C.I. I. CI Pigment Red 9, 19, 38, 43, 88, 122, 123, 144, 149, 155, 166, 168, 177, 178, 179, 180, 188, 190, 202, 207, 208, 209, 216, 217, 220, 224, 226, 242, 254, 264, etc .; I. CI Pigment Blue (15), 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 29, 60, 64, etc .; I. CI Pigment Green 7, 10, 36, 37, all brominated C.I. I. CI Pigment Green 36 (CI Pigment Green 36 has a chlorine atom and a bromine atom bonded to the benzene ring, and all of these chlorine atoms were substituted with a bromine atom. As a yellow pigment; C.I. I. CI Pigment Yellow (CI Pigment Yellow) 17, 20, 24, 81, 83, 93, 95, 97, 108, 109, 110, 117, 123, 125, 128, 129, 137, 138, 139, 147, 150, 153, 154, 166, 168, 180, 185, etc .; C.I. I. CI Pigment Violet 19, 23, 29, 30, 31, 37, 50, 88, etc .; as an orange pigment, C.I. I. CI pigment orange (CI Pigment Orange) 31, 38, 40, 43, 48, 61, 64, 71 and the like.
The amount of these pigments used is preferably 5 to 80% in terms of mass fraction with respect to the total solid content in the pigment-dispersed resist composition.
Further, the mass ratio of the carbodiimide compound is preferably 3 parts by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more, based on 100 parts by weight of the pigment (total amount of used pigments). The amount is preferably 50 parts by mass or less.

Examples of the film forming resin constituting the pigment dispersion resist composition include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, monoalkyl citraconic acid. Carboxyl group-containing unsaturated monomers such as esters, styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide , A copolymer obtained by reacting at least one selected from the group consisting of a polystyrene macromonomer and a polymethyl methacrylate macromonomer, Can alkali-soluble resin is exemplified having a sill groups, it may be used in combination alone or in combination.

Examples of the photopolymerizable compound constituting the pigment-dispersed resist composition include monomers and oligomers having a photopolymerizable unsaturated bond.
Specifically, examples of the monomer having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, Acrylate; aralkyl methacrylate or acrylate such as benzyl methacrylate or benzyl acrylate; alkoxyalkyl methacrylate or acrylate such as butoxyethyl methacrylate or butoxyethyl acrylate; aminoalkyl such as N, N-dimethylaminoethyl methacrylate or N, N-dimethylaminoethyl acrylate Methacrylate or acrylate; diethylene glycol monoethyl ether, triethylene glycol Methacrylic acid ester or acrylic acid ester of polyalkylene glycol monoalkyl ether such as butyl ether and dipropylene glycol monomethyl ether; Methacrylic acid ester or acrylic acid ester of polyalkylene glycol monoaryl ether such as hexaethylene glycol monophenyl ether; Isobonyl methacrylate Or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate can be exemplified.

Examples of monomers having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, and glycerol dimethacrylate. , Neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate Dipentaerythritol pentamethacrylic Bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, Examples include tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.
As the oligomer having a photopolymerizable unsaturated bond, one obtained by appropriately polymerizing the monomer can be used.
These photopolymerizable compounds can be used alone or in combination of two or more.

Although it does not specifically limit as a photoinitiator which comprises the said pigment dispersion resist composition, For example, benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, Benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1 -Chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, , 4-dimethyl anthraquinone, 2-phenyl-anthraquinone, triazine photopolymerization initiators, and the like. These can be used alone or in combination of two or more.

As the solvent constituting the pigment-dispersed resist composition, the same dispersion media as described above can be used. Preferably, the boiling point at normal pressure (1.013 × 10 ² kPa) is 100 to 220. An ester organic solvent, an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, a nitrogen-containing organic solvent, etc. If a solvent having a boiling point exceeding 220 ° C. is contained in a large amount, the solvent does not sufficiently evaporate when pre-baking the formed coating film, and remains in the dried coating film. May decrease. Further, when a large amount of a solvent having a boiling point of less than 100 ° C. is contained, it is difficult to uniformly apply the coating uniformly, and a coating film having excellent surface smoothness may not be obtained.

Specific examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol. Ether-based organic solvents such as monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Ether ester organic solvents such as cetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone and δ-butyrolactone; methyl 2-hydroxypropionate, 2 -Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ester organic solvents such as ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-amyl formate; N-methylpyrrolidone, N, N-dimethylformamide, N, N -Nitrogen-containing organic solvents, such as a dimethylacetamide, etc. can be illustrated, and can be used individually or in mixture of 2 or more types.

Among these solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate in terms of solubility, dispersibility, coatability and the like of the alkali-soluble resin. , Cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, and the like are more preferable. Is propylene glycol monomethyl ether acetate.

Further, when two or more of these solvents are used, the preferred solvents are all of the solvents used in the pigment-dispersed resist composition from the viewpoints of solubility of the alkali-soluble resin, pigment dispersibility, coatability, and the like. The content is preferably 50% by mass or more, and more preferably 70% by mass or more.
As the above-mentioned pigment-dispersed resist composition, various additives such as other photopolymerizable compounds other than those described above, thermal polymerization inhibitors, ultraviolet absorbers and antioxidants may be used as necessary. it can.

Examples of the method for producing the pigment dispersion resist composition of the present invention using the above materials include, for example, a pigment dispersion composition, a photopolymerizable compound, a photopolymerization initiator, a film-forming resin, and an organic solvent. In addition, a method of adding other additives and stirring and mixing using a stirring device or the like can be used. However, this manufacturing method is an example of a preferred embodiment of the present invention, and the present invention is not limited thereto.
A pigment dispersion resist composition containing the above-described pigment dispersion composition is also one aspect of the present invention.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” means “mass%” and “parts” means “parts by weight”.
[Synthesis of a polyacryl compound having an acid group at one end to be reacted with a carbodiimide group of a carbodiimide compound]
Preparation Example 1 (Polyacryl compound having a number average molecular weight of 3000)
In a four-necked flask equipped with a nitrogen gas introduction tube, a stirring rod, a dropping funnel, and a thermometer, 150 parts of propylene glycol monomethyl ether acetate was charged and heated to 85 ° C. While stirring while maintaining the internal temperature at about 85 ° C., a mixture of 150 parts of benzyl methacrylate, 5.5 parts of 3-mercaptopropionic acid, and 1.5 parts of azobisisobutyronitrile was added dropwise over 2 hours. Thereafter, the mixture was stirred for 2 hours while maintaining the internal temperature at about 85 ° C., 80.25 parts of propylene glycol monomethyl ether acetate was added, and a polyacryl compound 1 having a carboxyl group at one end and having a number average molecular weight of 3000 (solid content) 40% solution) was obtained.

Preparation Example 2 (Polyacryl compound having a number average molecular weight of 4000)
In a four-necked flask equipped with a nitrogen gas introduction tube, a stirring rod, a dropping funnel, and a thermometer, 150 parts of propylene glycol monomethyl ether acetate was charged and heated to 85 ° C. While stirring at an internal temperature of about 85 ° C., a mixture of 150 parts of benzyl methacrylate, 4.1 parts of 3-mercaptopropionic acid, and 1.5 parts of azobisisobutyronitrile was added dropwise over 2 hours. Thereafter, the mixture was stirred for 2 hours while maintaining the internal temperature at about 85 ° C., 78.15 parts of propylene glycol monomethyl ether acetate was added, and a polyacryl compound 2 having a carboxyl group at one end and having a number average molecular weight of 4000 (solid content) 40% solution) was obtained.

Preparation Example 3 (Polyacryl compound having a number average molecular weight of 5000)
In a four-necked flask equipped with a nitrogen gas introduction tube, a stirring rod, a dropping funnel, and a thermometer, 150 parts of propylene glycol monomethyl ether acetate was charged and heated to 85 ° C. A mixture of 150 parts of benzyl methacrylate, 3.2 parts of 3-mercaptopropionic acid and 1.5 parts of azobisisobutyronitrile was added dropwise over 2 hours while stirring at an internal temperature of about 85 ° C. Thereafter, the mixture was stirred for 2 hours while maintaining the internal temperature at about 85 ° C., 76.8 parts of propylene glycol monomethyl ether acetate was added, and a polyacryl compound 3 having a carboxyl group at one end and having a number average molecular weight of 5000 (solid content) 40% solution) was obtained.

[Synthesis of a carbodiimide compound having a polyacryl chain in the side chain]
Example 1 (Introduction of a polyacryl compound having a reaction rate of 50% carbodiimide group of a carbodiimide compound and a number average molecular weight of 3000 as a side chain)
A four-necked flask equipped with a nitrogen gas introduction tube, a stir bar, and a thermometer is charged with 19.0 parts of a carbodiimide compound having an isocyanate group of 316 and 5.2 parts of methyldiethanolamine and maintained at about 100 ° C. for 2 hours. Then, the isocyanate group and the hydroxyl group are reacted, and then 35.4 parts of propylene glycol monomethyl ether acetate and 228.1 parts of polyacryl compound 1 (solid content 40% solution) are charged and kept at about 80 ° C. for 2 hours. A carbodiimide group and a carboxyl group were reacted to obtain a carbodiimide compound 1 (solid content 40% solution) having a number average molecular weight of about 5200 and a carbodiimide equivalent of 3799.

Example 2 (Introduction of a polyacryl compound having a reaction rate of 50% carbodiimide group of a carbodiimide compound and a number average molecular weight of 4000 as a side chain)
A four-necked flask equipped with a nitrogen gas introduction tube, a stir bar, and a thermometer is charged with 19.0 parts of a carbodiimide compound having an isocyanate group of 316 and 5.2 parts of methyldiethanolamine and maintained at about 100 ° C. for 2 hours. Then, 35.4 parts of propylene glycol monomethyl ether acetate and 303.2 parts of polyacryl compound 2 (solid content 40% solution) are charged and kept at about 80 ° C. for 2 hours. A carbodiimide group and a carboxyl group were reacted to obtain a carbodiimide compound 2 (solid content 40% solution) having a number average molecular weight of about 6600 and a carbodiimide equivalent of 4787.

Example 3 (Introduction of a polyacrylic compound having a reaction rate of 50% carbodiimide group of a carbodiimide compound and a number average molecular weight of 5000 as a side chain)
A four-necked flask equipped with a nitrogen gas introduction tube, a stir bar, and a thermometer is charged with 19.0 parts of a carbodiimide compound having an isocyanate group of 316 and 5.2 parts of methyldiethanolamine and maintained at about 100 ° C. for 2 hours. Then, the isocyanate group and the hydroxyl group were reacted, and then 35.4 parts of propylene glycol monomethyl ether acetate and 386.2 parts of polyacryl compound 3 (solid content 40% solution) were charged and held at about 80 ° C. for 2 hours. A carbodiimide group and a carboxyl group were reacted to obtain a carbodiimide compound 3 (solid content 40% solution) having a number average molecular weight of about 8100 and a carbodiimide equivalent of 5879.

Example 4 (Polyacryl compound having a reaction rate of carbodiimide group of carbodiimide compound of 60% and number average molecular weight of 4000 is introduced as a side chain)
A four-necked flask equipped with a nitrogen gas introduction tube, a stir bar, and a thermometer is charged with 19.0 parts of a carbodiimide compound having an isocyanate group of 316 and 5.2 parts of methyldiethanolamine and maintained at about 100 ° C. for 2 hours. Then, the isocyanate group and the hydroxyl group were reacted, and then 35.4 parts of propylene glycol monomethyl ether acetate and 363.8 parts of polyacryl compound 2 (solid content 40% solution) were charged and held at about 80 ° C. for 2 hours. A carbodiimide group and a carboxyl group were reacted to obtain a carbodiimide compound 4 (solid content 40% solution) having a number average molecular weight of about 7700 and a carbodiimide equivalent of 6980.

[Pigment dispersant used in comparative example]
Comparative pigment dispersant A
PB821 (trade name, manufactured by Ajinomoto Co., Inc.) was used as the comparative pigment dispersant A.
Comparative pigment dispersant B
Disperbyk-161 (trade name, manufactured by Big Chemie) was used as Comparative Pigment Dispersant B.

Examples 5-8, Comparative Examples 1-2
[Preparation of pigment dispersion composition of carbon black]
Carbon black was kneaded with a bead mill at a temperature of 60 ° C. all day and night at the temperature of 60 ° C. to prepare pigment dispersion compositions of treated carbon black of Examples 5 to 8 and Comparative Examples 1 and 2.
In Table 1, carbon black represents carbon black having an average primary particle diameter of 56 nm and pH = 3.1. The unit of the numerical value representing the composition is “part by mass”.

[Preparation of pigment dispersion resist composition for black matrix]
After the pigment dispersion composition of the treated carbon black of Examples 5 to 8 and Comparative Examples 1 and 2 and other materials were uniformly mixed using a high-speed stirrer so as to have the composition shown in Table 2, a filter having a pore size of 3 μm The pigment dispersion resist composition liquid for black matrix of Examples 5-8 and Comparative Examples 1-2 was obtained. The unit of the numerical value representing the composition is “part by mass”.

[Evaluation test]
1. Dispersion Stability The treated carbon black pigment dispersion composition of Examples 5 to 8 and Comparative Examples 1 and 2 and the pigment dispersion resist composition for black matrixes of Examples 5 to 8 and Comparative Examples 1 and 2 were put in glass bottles, respectively. The state after sealing and storing at room temperature for 7 days was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 and 2.
Evaluation criteria A: Neither thickening nor sediment is observed.
B: Thickening and sediment that return to the original level when shaken lightly are observed.
C: Thickening or sediment that does not return to the original value even when shaken strongly is observed.

2. Optical density (OD value) of resist pattern
The pigment dispersion resist composition for black matrix, for which the evaluation of A or B was obtained with the above dispersion stability, was applied on a glass substrate with a spin coater so as to have a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes. Then, it exposed with the high pressure mercury lamp, and also post-baked for 30 minutes at 230 degreeC, and obtained the resist pattern formed only in the solid part. The optical density (OD value) of the resist pattern of the obtained solid part was measured with a Macbeth densitometer (trade name: TD-931, manufactured by Gretag Macbeth). The measurement results are shown in Table 2.
3. Resistance Value of Resist Pattern The surface resistance value of the resist pattern obtained by the above method was measured with a resistance meter (trade name: R8340 / 8340A, manufactured by Advantest). The evaluation results are shown in Table 2.

4). Resist pattern developability A pigment-dispersed resist composition for a black matrix whose A or B evaluation was obtained with the above dispersion stability was applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm. Pre-baked for 3 minutes. The obtained coating film was developed using a 0.15% Na ₂ CO ₃ aqueous solution, and the developability was evaluated according to the following evaluation criteria from the time until the resist composition in the uncured portion could be completely removed. The evaluation results are shown in Table 2.
A: It can be completely removed within 30 seconds.
B: It can be completely removed within 60 seconds over 30 seconds.
C: Even if it exceeds 60 seconds, it cannot be completely removed.

Examples 9-16, Comparative Examples 3-4
[Preparation of pigment dispersion composition of organic pigment]
C. plasma treated with the composition of Table 3 I. Pigment red 122, plasma treated C.I. I. Pigment Blue 15: 3 was kneaded with a bead mill at a temperature of 60 ° C. all day and night to prepare pigment dispersion compositions of treated organic pigments of Examples 9 to 16 and Comparative Examples 3 to 4. The unit of the numerical value representing the composition is “part by mass”.

[Preparation of pigment dispersion resist composition for color filter]
The pigment dispersion compositions of the treated organic pigments of Examples 9 to 16 and Comparative Examples 3 to 4 and other materials were uniformly mixed using a high-speed stirrer so as to have the composition shown in Table 4, and then a filter having a pore size of 3 μm. The pigment dispersion resist composition liquid for color filters of Examples 9-16 and Comparative Examples 3-4 was obtained. The unit of the numerical value representing the composition is “part by mass”.

[Evaluation test]
1. Dispersion Stability The pigment dispersion compositions of the treated organic pigments of Examples 9 to 16 and Comparative Examples 3 to 4 and the pigment dispersion resist compositions for color filters of Examples 9 to 16 and Comparative Examples 3 to 4 were put in glass bottles, respectively. The state after sealing and storing at room temperature for 7 days was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 3 and 4.
Evaluation criteria A: Neither thickening nor sediment is observed.
B: Thickening and sediment that return to the original level when shaken lightly are observed.
C: Thickening or sediment that does not return to the original value even when shaken strongly is observed.

2. Resist pattern developability A pigment-dispersed resist composition for a color filter, for which the above-mentioned dispersion stability was evaluated as A or B, was applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm. Pre-baked for 3 minutes. The obtained coating film was developed using a 0.15% Na ₂ CO ₃ aqueous solution, and the developability was evaluated according to the following evaluation criteria from the time until the resist composition in the uncured portion could be completely removed. The evaluation results are shown in Table 4.
A: It can be completely removed within 30 seconds.
B: It can be completely removed within 60 seconds over 30 seconds.
C: Even if it exceeds 60 seconds, it cannot be completely removed.

In Tables 1 to 4, “PGMEA” represents propylene glycol monomethyl ether acetate, and in Tables 2 and 4, “BMA / MAA copolymer” represents benzyl methacrylate / methacrylic acid copolymer, “DPEHA” represents dipentaerythritol hexaacrylate, and “Irgacure 907” represents 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by Ciba Specialty Chemicals. Represents the product name.

Claims (7)

An acid group-free radically polymerizable unsaturated monomer containing at least one acid group-free (meth) acrylic monomer is polymerized in the presence of an acid group-containing chain transfer agent to form an acid at one end of the molecule. Obtaining a polyacrylic compound containing groups,
The manufacturing method of the carbodiimide type compound which introduce | transduces a polyacryl chain | strand by making the acid group in the one terminal of the molecule | numerator of the obtained polyacrylic compound react with the carbodiimide group of the carbodiimide compound of carbodiimide equivalent 100-50000. An acid group-free radically polymerizable unsaturated monomer containing at least one acid group-free (meth) acrylic monomer is polymerized in the presence of an acid group-containing chain transfer agent to form an acid at one end of the molecule. Obtaining a polyacrylic compound containing groups,
By introducing a polyacryl chain by reacting an acid group at one end of the molecule of the obtained polyacryl compound and a carbodiimide group of a carbodiimide compound having a carbodiimide equivalent of 100 to 50,000, a carbodiimide compound is obtained,
A method for producing a pigment dispersion composition, wherein a pigment is dispersed using the carbodiimide compound. 3. The production method according to claim 1, wherein the acid group-containing chain transfer agent is a thiol-based acid group-containing chain transfer agent. Furthermore, at least one chain selected from the group consisting of a basic nitrogen-containing chain, a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, and a dye intermediate chain is introduced into the molecule of the carbodiimide compound. The manufacturing method of any one of 1-3. The carbodiimide type compound obtained by the manufacturing method of any one of Claim 1, 3-4. The pigment dispersion composition obtained by the manufacturing method of any one of Claims 2-4. A pigment-dispersed resist composition comprising the pigment-dispersed composition according to claim 6.