JP2006176657A - Carbodiimide-based compound and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbodiimide-based compound having good dispersibility of pigments and improved adhesiveness to plastic moldings and films; a pigment-dispersion composition which utilizes the compound and can suitably be used in a wide range of applications such as a coating, a printing ink, an ink-jet ink and a photosensitive resist composition; and a printing ink composition and a pigment-dispersion resist composition comprising the pigment-dispersion composition. <P>SOLUTION: The carbodiimide-based compound is obtained by introducing a side chain containing an amide group by reacting a compound having a functional group which reacts with a carbodiimide group and at least one amide group with a carbodiimide group of a carbodiimide compound having a carbodiimide equivalent of 100-50,000. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a carbodiimide compound and its use. More specifically, the present invention relates to a carbodiimide that realizes good dispersibility of pigments and good adhesion to plastic molded products and films (especially those containing amide groups). A pigment dispersion composition containing the compound as a system compound and an intermediate composition, which can be suitably used in a wide range of printing inks, paints, inkjet inks, photosensitive resist compositions, etc., and further as a final composition, The present invention relates to a printing ink or a photosensitive resist composition using a pigment dispersion composition.

Since carbodiimide compounds are few compounds having good reactivity with acid groups such as carboxyl groups, they have been mainly used as crosslinking agents for resins containing acid groups. However, in addition to such crosslinking reactivity, carbodiimide compounds have the feature that various functional chains can be easily introduced. Recently, multifunctional polymer compounds have been designed taking advantage of these features. The use in various fields is being studied.

For example, from the viewpoint of application to pigment dispersion technology, the applicant of the present application can introduce a functional chain into a carbodiimide compound to achieve high functionality, disperse a difficult-to-disperse pigment more finely, and further stabilize the state. The following proposals have already been made to develop a sustainable method.
(1) 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 (for example, see Patent Document 1)
(2) As a method of utilizing the adsorptive power with the pigment surface, a method using a carbodiimide compound as a starting material and utilizing an acid-base affinity (for example, see Patent Document 2)
(3) A method using 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.

Furthermore, the present applicant has found that by introducing a functional chain different from the above functional chain into the carbodiimide compound, a different effect can be added in addition to the basic performance of pigment dispersibility.

First, the applicant applied paints and films for plastic moldings based on the idea of improving adhesiveness by introducing functional chains to improve wettability and affinity to the plastic surface. Ink for ink was examined.
For example, in a gravure printing ink composition for surface printing, as a binder, generally a dispersion of pigment, adhesion to a plastic film, a polyamide resin for obtaining a good gloss of printed matter, and sufficient heat resistance in printed matter In combination with a cellulose derivative such as a nitrocellulose resin for obtaining the above (see, for example, Patent Documents 4 and 5).

However, such a printing ink composition for surface printing mainly composed of a binder resin does not provide sufficient performance when higher pigment dispersibility is required such as long-term storage and severe printing conditions. There wasn't. In order to increase the range of ink design by making it possible to select materials that are disadvantageous to the adhesion to plastic films as necessary in order to improve the total performance, the adhesion in the basic composition There was a need to make it even better.
International Publication WO 03/075527 Pamphlet International Publication WO04 / 000950 Pamphlet International Publication WO04 / 003085 Pamphlet JP 07-331154 A Japanese Patent Laid-Open No. 10-330669

Accordingly, an object of the present invention is to provide a carbodiimide compound that has good dispersibility of pigments and further improves adhesion to plastic moldings and films, and paints, printing inks, and inkjets using the compounds. It is to provide a pigment dispersion composition that can be suitably used in a wide range of inks, photosensitive resist compositions and the like, a printing ink composition containing the pigment dispersion composition, and a pigment dispersion resist composition.

As a result of intensive studies to solve the above problems, the present inventors have a functional group that reacts with a carbodiimide group in a carbodiimide group of a carbodiimide compound having a carbodiimide equivalent of 100 to 50000, and at least one amide It was found that all of the above problems could be solved by reacting a compound having a group and using a carbodiimide compound having a side chain containing an amide group in the molecule, thereby completing the present invention. It was.
That is, the present invention comprises (1) reacting a carbodiimide group having a carbodiimide equivalent of 100 to 50000 with a carbodiimide group having a functional group that reacts with a carbodiimide group and having at least one amide group, The present invention relates to a carbodiimide compound obtained by introducing a chain containing an amide group.
The present invention also includes (2) a basic nitrogen-containing chain, a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, a dye intermediate chain, a polyester chain, a polyether chain, and a polyacryl chain. The carbodiimide type compound according to item (1), which contains at least one chain selected from the group.
The present invention also relates to (3) a pigment dispersion composition obtained by dispersing a pigment using the carbodiimide compound described in the above item (1) or (2).
The present invention also relates to (4) a printing ink composition containing the pigment dispersion composition described in (3) above.
The present invention also relates to (5) a pigment-dispersed resist composition containing the pigment-dispersed composition described in (3) above.

Hereinafter, the present invention will be described in more detail.
<About carbodiimide compounds>
The carbodiimide compound of the present invention is obtained by introducing a chain having an amide group into a carbodiimide group of a carbodiimide compound having a carbodiimide equivalent of 100 to 50000 using a reactive functional group. It is applied in various applications that require pigment dispersion stability as performance. Since the carbodiimide compound of the present invention has an amide group, the carbodiimide compound can be suitably used in applications such as paints and printing inks that require adhesion to molded articles and films of polyamide resins.
In the following, a chain that is branched from a portion derived from a carbodiimide compound, formed by reacting a carbodiimide group of a carbodiimide compound with a compound having a group that reacts with a carbodiimide group is referred to as a “side chain”. . 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”.
The carbodiimide-based compound of the present invention may be one in which all carbodiimide groups have reacted with other functional groups, or may have an unreacted carbodiimide group.

1) Material for synthesizing a carbodiimide compound First, a carbodiimide compound as a starting material and a compound for introducing a side chain containing an amide group are explained as essential constituent materials of the carbodiimide compound of the present invention. To do.
1-1) Carbodiimide compound In order to obtain the carbodiimide compound of the present invention, the carbodiimide compound used as a starting material has at least one carbodiimide group, that is, a group represented by -N = C = N- in the molecule. Here, the compounds will be described more specifically by exemplifying preferred forms (a) to (d) below. The carbodiimide compound 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, for example, U.S. Pat. No. 2,941,956, JP-B-47-33279, JP-A-5-178954, JP-A-6-56950, and the like. The method is mentioned.

Regarding the carbodiimide compound having an isocyanate group obtained by using such a production method, for example, a compound obtained by decarboxylation of K mol (K is an integer of 2 or more) diisocyanate compound is represented by the following general formula (1 ).
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 carbodiimide compounds using tetramethylxylylene diisocyanate as raw materials, such as 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 Q mol (Q ≧ 1) of a diisocyanate compound.
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).
BN = C = N- (A-N = C = N) _Q- 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 materials as the synthetic material (a). Examples of the monoisocyanate compound include aliphatic, alicyclic, aromatic or araliphatic monoisocyanate compounds such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, and phenyl isocyanate. it can.

(D) A compound obtained by decarboxylation of 1 mol of a monoisocyanate compound and R mol (where R ≧ 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) _R- 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 that can be used can be the same as the synthetic material of the above (a), and the monoisocyanate compound can be the same as the synthetic material of the above (c).
The carbodiimide compounds (a) to (d) may be used alone as a starting material of the carbodiimide compound, or two or more kinds may be used in combination.

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 carbodiimide compound is too high, the weight ratio of the side chain having an amide group to the whole molecule of the resulting carbodiimide compound is reduced, and the dispersion stability of the pigment and the polyamide resin as a composition are reduced. Adhesiveness and the like are reduced. On the other hand, a compound having a low carbodiimide equivalent is advantageous in that it is possible to increase the weight ratio of the side chain having an amide group and the side chain having each functionality described later to the entire molecule of the carbodiimide compound. However, it is difficult to synthesize the carbodiimide compound itself and to control the reaction for introducing a side chain. A more preferable carbodiimide equivalent is 200 or more and 10,000 or less.

1-2) Compound for Introducing Side Chain Containing Amide Group Next, a compound used for introducing a side chain containing an amide group into the carbodiimide compound will be described.
The carbodiimide compound of the present invention uses a method of introducing a side chain by a reaction between a carbodiimide group and a functional group that reacts with the carbodiimide group, and has an amide group in the side chain. Therefore, as a compound introduced as a side chain, a compound having a functional group that reacts with a carbodiimide group and having an amide group can be used. Here, the amide group is a group represented by —NH—CO—.
Furthermore, examples of the functional group that reacts with the carbodiimide group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, and an amino group, and an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. It is preferable.

As a compound having such a functional group and an amide group, for example,
(1) As a specific example of a compound obtained by reacting an acid anhydride with a polyamide polyol, one kind of carboxylic acid such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid or the like Mixtures of two or more, linear or branched aliphatic polyamines having 2 to 12 carbon atoms, such as ethylenediamine and 1,12-dodecanediamine, and alicyclic polyamines such as isophoronediamine , Phthalic anhydride, maleic anhydride, polyamide polyol obtained by condensation polymerization reaction of one or more aromatic polyamines such as 4,4′-diaminodiphenyl ether and mixtures of aminoalcohols and aminophenols Compounds obtained by reacting acid anhydrides such as acid, succinic anhydride, benzoic anhydride, and styrene-maleic anhydride resin etc,
(2) Polyamino acids, specifically, copolyamino acids composed of α-amino acids such as lysine, glutamic acid, arginine, serine, tyrosine and cysteine, homopolyamino acids such as polylysine, γ-polylysine and γ-polyglutamic acid, gelatin Such as protein, etc.
(3) Ring-opening polymerization of lactams using (poly) hydroxycarboxylic acid Specifically, lactic acid, 12-hydroxystearic acid, ricinoleic acid, ricinoleic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxy Valeric acid, ε-hydroxycaproic acid, hydroxyethyloxycarboxylic acid, 2-hydroxynaphthalene-3-carboxylic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2-oxidedecanoic acid, glycolic acid, malic acid, gluconic acid, And ring-opening polymerization of lactams such as ε-caprolactam and ω-laurolactam, using the condensate of hydroxycarboxylic acid as an initiator,
(4) One of the hydroxyl groups of a hydroxy compound having a tertiary amino group, an amide group and an ester bond obtained by reacting a lactone with an amine compound having a tertiary amino group and a primary or secondary amino group, Further, those obtained by reacting an acid anhydride group, specifically, for example, dimethylaminoethylamine, diethylaminoethylamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N- Aminopropyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylmolybdenum Aliphatic polyamines such as holine, methyliminobispropylamine, N-aminopiperidine; 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 2-methylaminoethylpyridine, 4-alkylaminoethylpyridine, etc. Substituted pyridines; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (3-aminopropyl) -imidazole; 2-amino-4-methylpyrimidine, 2- Aromatic monocyclic amines such as mercaptopyrimidine, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 2-aminothiazole; 6-aminopurine (adenine), 4- Aminoquinaldine, guanine, 2-aminobenzimidazole Amine compounds having a tertiary amino group and a primary or secondary amino group such as condensed polycyclic aromatic amines such as benzimidazole, allopurinol, benzotriazole, and theophine, and propiolactone, valerolactone, caprolactone, or substituted derivatives thereof After reacting with lactones, etc., one of the hydroxyl groups of the resulting compound is reacted with an acid anhydride such as phthalic anhydride, maleic anhydride, succinic anhydride, benzoic anhydride, styrene-maleic anhydride resin, etc. And the like.

(1) Synthesis of polyamide polyol and method of reacting acid anhydride, (3) Ring-opening polymerization of lactams using (poly) hydroxycarboxylic acid, (4) Tertiary amino group As a method for reacting an acid anhydride group with one of the hydroxyl groups of a hydroxy compound having an amide group and an ester bond, a conventional method can be used.

1-3) Materials for introducing other functional chains Further, depending on the required performance, one or two molecular chains and functional groups having various functionalities such as the following (a) to (e) A compound having a plurality of functions can be obtained by introducing more than one species 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) Carbodiimide group (a) Basic nitrogen-containing chain (c) Pigment derivative chain, pigment intermediate chain, dye derivative chain and / or dye intermediate chain (d) Polyester chain, polyether chain and polyacryl chain At least one chain selected from the group (e) a chain having an ultraviolet sensitizing ability and / or a chain having a radical initiating ability

Here, in order to introduce the carbodiimide group of (a), in the production of the carbodiimide compound, when introducing a side chain containing an amide group, at least one carbodiimide group in the molecule of the carbodiimide compound, The introduction of the functional chain described in (a) is used as it is left unreacted, and the introduction of the functional chain described in International Publication WO 04/000950 and 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), use the material described in International Publication WO 03/075527, for example. Can do.

For the introduction of the functional chain described in (e), for example, when the above carbodiimide group can react with a functional group or 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 compound having 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 thereof include -hydroxy-cyclohexyl phenyl ketone, dimethylaminobenzoic acid, diethylaminobenzoic acid, and N-alkyl dialkanolamines such as N-ethyldiethanolamine and N-methyldiethanolamine.

2) Molecular structure and effect of carbodiimide compound The carbodiimide compound is obtained by using the above-mentioned material, and is introduced into the carbodiimide compound as a starting material as a side chain containing the above amide group. Is introduced via reaction with a carbodiimide group.
As such a carbodiimide-based compound, for example, when a compound having the structure of the above formula (1) is used as a carbodiimide compound as a starting material, it can be schematically represented as the following general formula (4).
OCN-X _(L) -(N = C = N) _(N-L) -OCN (4)
[Wherein X independently represents a structural unit containing a side chain containing an amide group bonded via a linking group obtained by a reaction between a carbodiimide group and a functional group capable of reacting with the carbodiimide group. L represents the number of structural units of X in the molecule 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. In this general formula, A is omitted. ]

Moreover, about the introduction | transduction of the chain | strands (a)-(e) which have other functions used 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 material, 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. Represents a structural unit containing the functional chains of (a) to (e) above. Z is a structural unit which contains the functional chain of (a)-(e) which respectively independently couple | bonded through the coupling group by reaction with the carbodiimide group and the functional group which can react with it. 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 this general formula, A is omitted. ]

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 Y site 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 via a linking group by the same reaction. 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 side chain is introduced by reacting a functional group capable of reacting with a carbodiimide group is usually a carbodiimide group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, It is formed by reaction with an amino group or the like, and has the following structure.

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

The linking group formed by reacting a reactive functional group with an isocyanate group is usually formed by a reaction of an isocyanate group with a hydroxyl group, a primary or secondary amino group, or the like.
For example, a linking group formed from a reaction between an isocyanate group and a hydroxyl group is represented by the following general formula (13), and a linking group formed from a reaction between an isocyanate group and a primary or secondary amino group is represented by the following general formula: It is represented by (14).

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 any one of the general formula (6) to the general formula (12) as a starting material, for example, at a site that is a carbodiimide group of the carbodiimide compound of the general formula (1). By introducing at least one side chain containing an amide group through a linking group, a compound having a structural unit of X in the general formula (4) is formed. Further, by introducing another functional side chain in the same manner, the compounds having the structural unit of Z in the general formula (5), the general formulas (13), (14 It is preferable that the compound is 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.

Since the carbodiimide compound of the present invention has a side chain containing an amide group, the affinity for a polar solvent as a compound is improved, and in particular, an amide group is present in a molecule such as a polyamide resin molded product or a nylon film. The adhesiveness with respect to the plastic which it has can be made favorable.
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 utilizing adsorption due to affinity due to the similarity of the molecular structure of the pigment, the carbodiimide compound includes a pigment derivative chain, a pigment intermediate chain, a dye derivative chain and / or a dye intermediate chain in the molecule. To have.

On the other hand, from the viewpoint of more stably dispersing the pigment in the dispersion medium, the carbodiimide compound further includes at least one selected from the group consisting of a polyester chain, a polyether chain, and a polyacryl chain in the molecule. It is preferable that it has a chain, and among these, what it has as a side chain is more preferable. Since these side chains form domains in the dispersion medium and act as steric hindrance when the pigment is dispersed in the dispersion medium, the pigment can be more stably dispersed in the dispersion medium. It is considered a thing.
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 producing the carbodiimide compound of the present invention using the above-mentioned materials, all reactions, that is, reactions for introducing a side chain, include a carbodiimide group, a carboxyl group, and a sulfonic acid. Conventional methods can be used for the reaction of a group, a phosphate group, a hydroxyl group, an amino group, etc., and the reaction of an isocyanate group with a hydroxyl group, an amino group, or the like. Furthermore, the order of introducing 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 may be reacted 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 side chain containing an amide group to be introduced into the molecule, the type and ratio of each functional chain, and the amount of the remaining carbodiimide group are, for example, a pigment or dispersion medium when used as a pigment dispersant. It is preferable that the respective materials are blended so as to finally become a compound having a good performance balance by appropriately setting depending on the type of the above and the performance required in other fields of use.

The number average molecular weight of the carbodiimide compound of the present invention obtained from the above materials and production method is preferably 1000 or more and 100,000 or less. If the number average molecular weight is too high, it becomes difficult to obtain a pigment having an appropriate viscosity when the pigment is dispersed in a dispersion medium or a pigment dispersion composition. It is not preferable when necessary. 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.

<Pigment dispersion composition>
Next, a pigment dispersion composition in which a pigment is dispersed using the carbodiimide compound will be described.
As the carbodiimide compound used in the pigment dispersion composition of the present invention, not only a carbodiimide compound having a side chain containing an amide group, but also the presence or absence of a functional group or adsorption point on the pigment surface, the type of dispersion medium, and the obtained Depending on the intended use of the pigment dispersion composition, the above-described carbodiimide compounds having the functional groups and functional chains (a) to (e) can be appropriately selected and used.
In the pigment dispersion composition of the present invention, the pigment may be adsorbed with a carbodiimide compound, at least covalently bonded, adsorbed with acid-base affinity, or with affinity due to similarity in molecular structure. For example, organic pigments and inorganic pigments generally used for printing inks, paints, inkjet 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) Material), 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 typically includes 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, or 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, for a carbodiimide compound having a pigment derivative chain, a pigment intermediate chain, a dye derivative chain and / or a dye intermediate chain in the molecule, as a pigment having an adsorption part due to affinity due to the similarity of the molecular structure Is an organic or inorganic pigment having the same or similar structure as the pigment derivative, pigment intermediate, dye derivative and / or dye intermediate; the same or similar to the pigment derivative, pigment intermediate, dye derivative and / or dye intermediate Even if it is not the structure of these, it is preferable that they are an organic pigment and an inorganic pigment which have sufficient adsorption power with these.
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.

Examples of suitable pigment derivatives, pigment intermediates, dye derivatives and / or combinations of dye intermediates and pigments include (1) phthalocyanine pigment derivatives as pigment derivatives, phthalocyanine pigments as pigments In addition, there is a combination with pigment black 7, and (2) a β-naphthol orange dye derivative as a pigment derivative has a combination with a condensed azo pigment in addition to a naphthol pigment as a pigment, (3) As for the anthraquinone derivative as a dye intermediate, in addition to the dianthraquinonyl pigment as a pigment, a diketopyrrolopyrrole pigment, a condensed azo pigment, an isoindori pigment, a perinone pigment, an azo pigment having a heterocyclic ring, quinacridone Pigments, dibromoanthanthrone pigments and / or benzimidazolones And a combination of the fee.

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 particular, in applications where a photopolymerizable material is used, (III) light in which a carbodiimide compound is dissolved and light capable of stably dispersing the pigment is used. Examples thereof include a method of obtaining a pigment dispersion composition by processing while dispersing the pigment in the polymerizable compound.

In (II) and (III), various binder resins, photopolymerizable compounds, solvents, surfactants, other additives, and the like can be added as needed during pigment dispersion and after pigment dispersion. .
“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, Examples thereof include a method of kneading, dispersing and treating using a high-pressure dispersing device or the like.

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 above 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.

The amount of the pigment used in the pigment dispersion composition is preferably 5 to 97% in terms of mass fraction with respect to the total solid content in the 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.

Next, the active energy ray-curable composition and the printing ink composition, which are uses 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-dispersed resist composition of the present invention can be applied to the pigment-dispersed composition according to the purpose, in addition to a film-forming resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, various kinds of sensitizers, polymerization inhibitors, and the like. It is obtained by adding an additive.

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. All of these chlorine atoms were substituted with a bromine atom. A chemical structure); 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 and the like; 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 use ratio of the carbodiimide compound is preferably 3 parts by mass or more, and 100 parts by mass or less, preferably 5 parts by mass or more, with respect to 100 parts by mass of the pigment (the total amount of pigments used). , 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 , Which is a copolymer obtained by reacting at least one selected from the group consisting of polystyrene macromonomer and 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 pentamethacrylate 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 dimethylacetamide can be exemplified, and these can be used alone or in admixture of two or more.

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 in terms of solubility of the alkali-soluble resin, pigment dispersibility, coatability and the like. Preferred are acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, and the like Preferred 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 pigment-dispersed resist composition, other photopolymerizable compounds other than those described above, and various additives such as thermal polymerization inhibitors, ultraviolet absorbers, antioxidants, and the like are used as necessary. Can do.
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, a solvent, depending on the purpose. 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 pigment dispersion composition is also one aspect of the present invention.

<Composition for printing ink>
The printing ink composition of the present invention is obtained by further adding various binder resins, solvents, antiblocking agents, plasticizers, surfactants and the like to the pigment dispersion composition according to the purpose. Water-based gravure printing ink composition for printing or back printing, and ink composition for gravure printing such as solvent-type gravure printing ink composition for surface printing or back printing .

First, the pigment used for the printing ink composition of this invention is demonstrated.
As the pigment constituting the printing ink composition of the present invention, inorganic, organic pigments or extender pigments that can generally be used in printing ink compositions can be used.
Specific examples of the inorganic pigment include titanium oxide, bengara, antimony red, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine blue, carbon black, graphite, and the like, and organic pigments include soluble azo pigments and insoluble azo pigments. Azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, and the like.
Examples of extender pigments include calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc.
The content of these pigments in the printing ink composition is usually about 1 to 50% by weight.
Further, the use ratio of the carbodiimide compound is preferably 3 parts by mass or more, and 100 parts by mass or less, preferably 5 parts by mass or more, with respect to 100 parts by mass of the pigment (the total amount of pigments used). , 50 parts by mass or less.

As the binder resin constituting the printing ink composition of the present invention, those conventionally used in printing ink compositions can be used.
Specific examples include synthetic resins such as polyester resins, polyurethane resins, acrylic resins, polyamide resins, and vinyl acetate resins; natural resin resins such as rosin and derivatives thereof, nitrified cotton, and cellulose derivatives. These binder resins are appropriately selected according to the use for front printing, back printing and the like and the type of solvent used.

As the solvent constituting the printing ink composition of the present invention, those conventionally used in printing ink compositions can be used.
Specifically, aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; methanol, ethanol, propanol, Examples include alcohols such as normal propyl alcohol; various organic solvents such as glycols such as ethylene glycol and propylene glycol and derivatives thereof, water, and the like, and are usually used as a mixed solvent.
In the printing ink composition of the present invention, various additives such as a surfactant, an anti-blocking agent, a wax, and a plasticizer can be used as needed in addition to the above-described components.
A printing ink composition containing the pigment dispersion composition is also one aspect of the present invention.

As a method for producing the printing ink composition of the present invention using the above materials, for example, a binder resin, a solvent, and other additives are added to the pigment dispersion composition according to the purpose, and a stirrer or the like is used. However, this production method is an example of a preferred embodiment of the present invention, and the present invention is not limited to this.

The printing ink composition obtained by the above production method can be printed on various adherends mainly using a gravure printing method.
Here, as an adherend printed on the printing ink composition, polyester film such as normal stretched polypropylene (OPP) film, unstretched polypropylene (CPP) film, modified polypropylene, polyethylene terephthalate (PET) film, nylon ( NY) and various plastic films such as polystyrene, stretched polypropylene (VM-OPP) film on which a metal such as aluminum is deposited, unstretched polypropylene (VM-CPP) film, stretched polyethylene terephthalate (VM-PET), etc. Is mentioned.

The carbodiimide compound of the present invention can achieve good dispersion of the pigment by introducing a side chain containing the amide group as described above into the molecule, and the resulting pigment dispersion composition contains a pigment. Even if the amount is high, it has good dispersion stability and fluidity. Further, when the pigment dispersion composition is used in the pigment dispersion resist composition of the present invention, the pigment dispersion resist composition has good pigment dispersion stability, and the film formed thereby uses carbon black as the pigment. In some cases, the thin film has a large concealing power and is excellent in insulation, and when an organic pigment is used as the pigment, it has a high transmittance and a high contrast. In addition, when the pigment dispersion composition is used in paints or printing inks, the adhesion to a polyamide-based plastic molded product or film is particularly good.

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”.
Examples 1-3 and Comparative Examples 1-3
1. Pigment-dispersed resist composition for black matrix and color filter <Preparation of carbodiimide compound>
(Carbodiimide compound 1)
A four-necked flask equipped with a reflux condenser, a nitrogen gas inlet tube, a stirrer, and a thermometer, 50.0 parts by mass of a carbodiimide compound having an carbodiimide equivalent of 315 having an isocyanate group, and a poly (3-methylpentyl adipate) having a molecular weight of 1000 115.7 parts by weight of a diol was charged and held at about 100 ° C. for 5 hours to react an isocyanate group with a hydroxyl group, and then 79.4 parts by weight of a polycaprolactone ring-opened product having a molecular weight of 1000 having a carboxyl group at the terminal. And kept at about 100 ° C. for 2 hours to completely react the carbodiimide group and the carboxyl group. Furthermore, one end of amide alcohol having a molecular weight of 216 obtained by reacting 114 parts by mass of ε-caprolactone and 102 parts by mass of N, N-dimethyl-1,3-propanediamine was reacted with 49.1 parts of maleic anhydride. After charging 21.0 parts by mass of an amide alcohol having a carboxyl group at the end with a molecular weight of 265.1 and reacting a carbodiimide group and a carboxyl group at 100 ° C., 266.1 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was added. Then, a carbodiimide compound 1 (solid content 50% by mass) having a tertiary amino group, an amide group, a side chain having an ester bond and a polyester side chain in the molecule was obtained.

<Regarding the pigment dispersant used in the comparative example>
Comparative pigment dispersant PB821 (trade name, manufactured by Ajinomoto Co., Inc.) was used as comparative pigment dispersant A.

<Preparation of pigment dispersion composition>
The pigments were kneaded with a bead mill with the composition shown in Table 1 all day and night to prepare the pigment dispersion compositions of Examples 1 to 3 and Comparative Examples 1 to 3.
In Table 1 above, 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 Example 1 and Pigment Dispersion Resist Composition for Black Matrix of Comparative Example 1 and Preparation of Color Dispersion Resist Composition for Color Filters of Examples 2 and 3 and Comparative Examples 2 and 3>
The pigment dispersion composition of carbon black of Example 1 and Comparative Example 1 and other materials were uniformly mixed using a high-speed stirrer so as to have the composition shown in Table 1, and then filtered through a filter having a pore size of 3 μm. The pigment dispersion resist composition liquid for black matrix of Example 1 and Comparative Example 1 was obtained. Further, in Examples 2 and 3 and Comparative Examples 2 and 3, C.I. I. Pigment Red 122 (PR122) pigment dispersion composition or C.I. having an amino group and an adsorption site. I. Pigment Blue 15: 3 (PB15: 3) pigment dispersion composition and other materials were uniformly mixed using a high-speed stirrer so as to have the composition shown in Table 1, and then filtered with a filter having a pore diameter of 3 μm. Thus, pigment dispersion resist composition liquids for color filters 2 and 3 and Comparative Examples 2 and 3 were obtained.

In Table 1 above, “BMA / MAA copolymer” represents a benzyl methacrylate / methacrylic acid copolymer, “DPEHA” represents dipentaerythritol hexaacrylate, “Irgacure 907” represents 2-methyl- It represents 1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name, manufactured by Ciba Specialty Chemicals), and “PGMEA” is the same as described above. The unit of the numerical value representing the composition is “part by mass”.

<Performance evaluation of pigment dispersion composition of carbon black and pigment dispersion resist composition for black matrix>
(Evaluation test)
1. Dispersion stability The carbon black pigment dispersion composition of Example 1 and Comparative Example 1 and the pigment dispersion resist composition were each taken in a glass bottle, sealed, and stored at room temperature for 7 days, and then evaluated according to the following evaluation criteria. . The evaluation results are shown in Table 1.
A: Thickening and sediment are not recognized.
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. Light-shielding property of resist pattern A pigment-dispersed resist composition for a black matrix whose A or B evaluation 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 at 100 ° C. After pre-baking for 3 minutes, it was exposed with a high-pressure mercury lamp, and further post-baked at 230 ° C. for 30 minutes to obtain a resist pattern formed only with a solid portion. 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 1.

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 1.

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 1.
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.

<Performance Evaluation of Pigment Dispersion Composition for Color Filter and Pigment Dispersion Resist Composition for Color Filter>
(Evaluation test)
1. Dispersion Stability Each of the pigment dispersion compositions of Examples 2 and 3 and Comparative Examples 2 and 3 and the pigment dispersion resist composition was placed in a glass bottle, sealed and stored at room temperature for 7 days, and evaluated according to the following evaluation criteria. did. The evaluation results are shown in Table 1.
A: Thickening and sediment are not recognized.
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. A pigment-dispersed resist composition for developing a color filter having a resist pattern 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. 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 1.
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.

Example 4 and Comparative Example 4
2. Printing ink composition for surface printing gravure <Preparation of carbodiimide compound>
(Preparation of polyamide compound)
A four-necked flask equipped with a nitrogen gas inlet tube, a stirrer, and a thermometer was charged with 90.0 parts of dimer acid, 18.0 parts of hexamethylenediamine, and 14.6 parts of oleic acid, and was placed in a nitrogen gas atmosphere at 200 ° C. And a polyamide compound having a number average molecular weight of about 2270 and an acid value of about 25 was obtained.

(Preparation of carbodiimide compound 2)
In a four-necked flask equipped with a reflux condenser, a nitrogen gas inlet tube, a stirring bar, and a thermometer, 50.0 parts of a polycarbodiimide compound having a carbodiimide equivalent of 316 having an isocyanate group and a poly (3-methylpentyl adipate) having a molecular weight of 1000 118.2 parts of diol was charged and held at about 100 ° C. for 5 hours to react an isocyanate group with a hydroxyl group. Then, 203.3 parts of a mixed solvent of toluene / isopropyl alcohol (IPA) = 1: 1 was charged. Next, a polyamide varnish composed of 179.3 parts of the polyamide compound obtained above and 269 parts of a toluene / IPA = 1: 1 mixed solvent was charged, and held at about 80 ° C. for 2 hours to react the carbodiimide group with the carboxyl group. The carbodiimide compound 2 having a number average molecular weight of about 5900 and a carbodiimide equivalent of 4393 (solid Minute 42.4%) was obtained.

<Preparation of polyamide resin varnish>
In a mixed solvent of 46.7 parts by mass of toluene and 23.3 parts by mass of isopropyl alcohol, 30.0 parts by mass of a commercially available polyamide resin (Rheamide S2600, manufactured by Kao Corporation) is dissolved to obtain a polyamide resin varnish having a solid content of 30%. Obtained.

<Preparation of nitrocellulose varnish>
Nitrogenated cotton RS1 / 2 (manufactured by Daicel Chemical Industries, Ltd.) 20.0 parts by mass as nitrocellulose was dissolved in 80.0 parts by mass of a toluene / ethyl acetate / isopropyl alcohol = 2/1/1 mixture to obtain a solid content of 20%. Of nitrocellulose varnish was obtained.

<Pigment dispersion composition of Example 4>
The pigment, the carbodiimide compound 2 and the dispersion medium were charged so as to have the composition shown in Table 2, and the mixture was heated to 60 ° C. and kneaded with a bead mill to obtain the pigment dispersion composition of Example 4.

<Pigment dispersion composition of Comparative Example 4>
A pigment, a polyamide resin varnish and a dispersion medium were charged so as to have the composition shown in Table 2, and kneaded with a bead mill (kneaded for the same time as in Example 4 without heating to 60 ° C.). Obtained.

<Printing ink composition for gravure for surface printing of Example 4 and Comparative Example 4>
Polyamide resin varnish, nitrocellulose varnish and solvent were added to and mixed with the pigment dispersion composition of Example 4 and the pigment dispersion composition of Comparative Example 4 so as to have the composition shown in Table 2, and surface printing of Example 4 and Comparative Example 4 was performed. A gravure printing ink composition was obtained.
In Table 2, the unit of the numerical value representing the composition is “part by mass”.

(Performance evaluation)
<Evaluation test>
1. Dispersion Stability The pigment dispersion compositions of Example 4 and Comparative Example 4 and the printing ink composition for gravure for surface printing were each taken in a glass bottle, sealed and stored at room temperature for 7 days, and evaluated according to the following evaluation criteria. The results are shown in Table 2.
A: Thickening and sediment are not recognized.
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. Adhesive Example 4 and the printing ink composition for gravure for surface printing of Comparative Example 4 were printed with an OPP film (Pyrene P-2161, film thickness 30 μm, manufactured by Toyobo Co., Ltd.), PET film (E-5102, film) It was printed on a 12 μm thick Toyobo Co., Ltd.), NY film (OSN, membrane pressure 15 μm, Toyobo Co., Ltd.) and dried with warm air to obtain a printed matter. The cellophane tape was affixed to the printed surface of these printed materials, and the adhesiveness was evaluated from the degree to which the printed film peeled off from the film when rapidly removed. The results are shown in Table 2.
Evaluation criteria A: Film coating does not peel from film at all B: Part of film coating peels from film C: Film coating peels from film

The carbodiimide compound of the present invention can achieve good dispersion of the pigment by introducing a side chain containing the amide group as described above into the molecule, and the resulting pigment dispersion composition contains a pigment. Even if the amount is high, it has good dispersion stability and fluidity. Further, when the pigment dispersion composition is used in the pigment dispersion resist composition of the present invention, the pigment dispersion resist composition has good pigment dispersion stability, and the film formed thereby uses carbon black as the pigment. In some cases, the thin film has a large hiding power and excellent insulation, and when an organic pigment is used as the pigment, it has a high transmittance and a high contrast. It is. In addition, when the pigment dispersion composition is used in paints or printing inks, the adhesion to a polyamide-based plastic molded product or film is particularly good.

Claims (5)

A carbodiimide compound having a carbodiimide equivalent of 100 to 50,000 is reacted with a compound having a functional group that reacts with a carbodiimide group and a compound having at least one amide group to introduce a chain containing an amide group. A carbodiimide compound. Furthermore, at least one selected from the group consisting of a basic nitrogen-containing chain, a pigment derivative chain, a pigment intermediate chain, a dye derivative chain, a dye intermediate chain, a polyester chain, a polyether chain, and a polyacryl chain in the molecule The carbodiimide compound according to claim 1 containing a chain. A pigment dispersion composition obtained by dispersing a pigment using the carbodiimide compound according to claim 1. A printing ink composition comprising the pigment dispersion composition according to claim 3. A pigment dispersion resist composition comprising the pigment dispersion composition according to claim 3.