JP2005035949A - Phthalocyanine derivative, dispersing agent, pigment composition and pigment dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new pigment derivative-type dispersing agent, imparting easy dispersability to a pigment when used for the dispersion of the pigment, providing high stability to a produced pigment dispersion, usable in many solvents, and produceable in a good yield and high purity. <P>SOLUTION: The phthalocyanine derivative represented by general formula (1): Pc-(CO-R<SP>1</SP>-O-X)<SB>n</SB>---(1) [wherein, Pc is an n-valent phthalocyanine residue; R<SP>1</SP>is a group of -(O-R<SP>2</SP>-O-OC-R<SP>3</SP>-CO)<SB>p</SB>- or -(O-R<SP>4</SP>-CO)<SB>q</SB>-; X is hydrogen atom, -R<SP>2</SP>-OH or -R<SP>5</SP>-H; n is 1-8; p is 1-100; q is 2-200; with the proviso that when n is ≥2, p and q may be within the range of the above numbers as average in one molecule; and R<SP>2</SP>to R<SP>5</SP>are each a 1-20C divalent organic group] is used as the dispersing agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel dispersant used for dispersing a novel phthalocyanine derivative and pigment, a pigment composition and a pigment dispersion formed using the same.

  Production of a pigment dispersion in which a pigment is dispersed in a liquid is widely performed. However, in order to finely disperse a pigment and disperse the pigment in the liquid, generally a strong mechanical force and a long time are required. In addition, the pigment dispersed in the liquid in this manner often causes aggregation, which may impair the fluidity and color characteristics of the pigment dispersion. In order to facilitate dispersion by such mechanical force or to improve the stability of the pigment dispersion, it is widely used to use a dispersant.

Various types of dispersants are known, but they disperse by inhibiting the aggregation of the pigment by the site acting as an anchor by adsorbing to the pigment surface and the steric repulsion effect or electrostatic repulsion effect. Dispersants having both sites are generally widely used to exhibit high dispersion stability. Examples of such a dispersant include, for example, the dispersant shown in Non-Patent Document 1 below, that is, a cationic surfactant, an anionic surfactant, a nonionic surfactant, and a cationic polymer system. A dispersant, an anionic polymer dispersant, a nonionic polymer dispersant, and the like can be given.
However, difficult-to-disperse organic pigments having a condensed polycyclic structure such as phthalocyanine pigments are still difficult to disperse even when these dispersants are used, and the stability of the pigment dispersion is poor, and the effect of the dispersant is not sufficient. There is no problem. Organic pigments with a condensed polycyclic structure are highly industrially useful due to their rich hue variations and excellent chroma and tinting strength.Therefore, effective dispersants to replace these dispersants are desired. It was.

Japanese Patent Publication No. 51-15857 Japanese Patent Publication No. 7-78180 Japanese Patent Laid-Open No. 6-80898 Japanese Patent Laid-Open No. 10-36741 JP-A-6-247970 Japanese Patent Laid-Open No. 10-101673 Stabilization of pigment dispersion and surface treatment technology / evaluation (Technical Information Association, 2001) 29-46

Therefore, there is a proposal regarding a pigment derivative type dispersant having a pigment skeleton in the molecule. For example, Patent Document 1 discloses a pigment derivative type dispersant having a polyhydroxy acid chain, and Patent Document 2 discloses a pigment derivative type dispersant having a polyoxyalkylene chain. These pigment derivative type dispersants are expected to exhibit excellent dispersion stability because the pigment skeleton in the molecule can be effectively adsorbed on the pigment surface as an anchor site.
However, in these known pigment derivative type dispersants, the range of solvents that can be used in the production of pigment dispersions is extremely limited. For example, highly stable pigment dispersions can be obtained with ester solvents or ether ester solvents. It was almost impossible to make. Also, these known pigment derivative type dispersants are often difficult to synthesize due to their structure and cannot be produced in high yield and high purity, and require a lot of labor for purification, or There is a problem that sufficient dispersion stability cannot be obtained because it must be used in a state in which a large amount of impurities are contained. Therefore, it can be used for many solvents such as ester, ether ester, ether, alcohol, aromatic, etc., and can be produced with high yield and high purity. A pigment derivative type dispersant that can be used has been desired.

  Phthalocyanine derivatives obtained by modifying phthalocyanine with certain functional groups are disclosed in Patent Documents 3 and 4 and the like, and phthalocyanine derivatives having a sulfonamide group, an amide group, an amino group, a sulfo group, a carboxyl group, etc. are known. Yes. In addition, methods for synthesizing phthalocyanine derivatives obtained by modifying phthalocyanine with some carboxyl groups are disclosed in Patent Documents 5 and 6 and the like.

  Therefore, the present invention is a novel dispersant that imparts easy dispersibility to the pigment and imparts high stability to the produced pigment dispersion when used for dispersing the pigment, and can be used for many solvents. Thus, an object of the present invention is to provide a pigment derivative type dispersant that can be produced with high yield and high purity. Another object of the present invention is to provide a pigment composition and a pigment dispersion using the dispersant.

  As a result of studies to solve the above problems, the present inventors have found that a pigment derivative having a specific structure can be suitably used as a dispersant, and have completed the present invention.

The present invention is a phthalocyanine derivative represented by the following general formula (1) or a salt thereof.
Pc- (CO—R ¹ —O—X) _n (1)
(Wherein Pc is an n-valent phthalocyanine residue, R ¹ is a group consisting of — (O—R ² —O—OC—R ³ —CO) _p — or — (O—R ⁴ —CO) _q —. , X represents a hydrogen atom, —R ² —OH or —R ⁵ —H, n represents 1 to 8, p represents 1 to 100, q represents 2 to 200, and n is 2 or more. When p and q are within the above numerical range as an average in one molecule, R ^{2 to} R ⁵ represent a divalent organic group having 1 to 20 carbon atoms)

  The present invention also provides a pigment dispersant comprising the phthalocyanine derivative. Furthermore, the present invention is a composition in which the above-mentioned dispersant is blended with a pigment, and the pigment: dispersant weight ratio is 99: 1 to 50:50. In addition, the present invention is a pigment dispersion characterized in that the pigment composition is dispersed in a liquid.

Hereinafter, the present invention will be described in detail.
The phthalocyanine derivative of the present invention has a structure represented by the general formula (1). Here, Pc represents a phthalocyanine residue, which represents an n-valent group obtained by removing n hydrogen atoms bonded to the benzene ring of phthalocyanine. The phthalocyanine serving as the base of the residue may be either a conventionally known metal phthalocyanine or metal-free phthalocyanine, but from the viewpoint of excellent fastness, transition metal phthalocyanines such as copper phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine, and iron phthalocyanine are preferable. Furthermore, copper phthalocyanine is more preferable. The term phthalocyanine residue includes a phthalocyanine residue having a substituent.

  The method for producing the phthalocyanine derivative of the present invention is not particularly limited, but it is produced by introducing a polyester chain into a phthalocyanine carboxylic acid having n carboxyl groups (meaning including phthalocyanine polycarboxylic acid). Is advantageous. Methods for synthesizing phthalocyanine carboxylic acids are known. For example, (a) benzenepolycarboxylic acids such as pyromellitic acids, trimellitic acids, hemimellitic acids or derivatives thereof (including derivatives such as acid anhydrides and acid imides thereof) Is reacted with urea and metal salts to synthesize phthalocyanine carboxamide, and then hydrolyzes it. (B) A method in which phosgene is allowed to act on phthalocyanine to synthesize phthalocyanine carbonyl chloride, which is then hydrolyzed. c) A method of reacting phthalocyanine with trichloroacetic acid at a high temperature can be mentioned, but the method (a) is most preferable because it is a relatively safe and simple method. Specific examples of the method (a) are disclosed in, for example, Patent Documents 5 and 6 and the like, and according to this method, a transition metal phthalocyanine carboxylic acid or the like can be suitably synthesized. However, the method of synthesizing phthalocyanine carboxylic acid is not limited to the above method.

  In the phthalocyanine derivative of the present invention, n in the general formula (1) may be 1 to 8, but 1 to 4 is preferable from the viewpoint of the stability of the pigment dispersion, and 2 to 4 is more preferable. . The value of n can be freely selected by appropriately adjusting the synthesis raw materials and reaction conditions during the synthesis of phthalocyanine carboxylic acid. For example, in the above method (a), phthalocyanine octacarboxylic acid (n = 8) can be synthesized by using pyromellitic dianhydride as a raw material, and phthalocyanine tetracarboxylic acid by using trimellitic anhydride as a raw material. (N = 4) can be synthesized. Further, if trimellitic anhydride and phthalic anhydride are used in equimolar amounts, phthalocyanine dicarboxylic acid (n = 2) can be synthesized.

The method for introducing the polyester chain into the phthalocyanine carboxylic acid is not particularly limited. For example, the monomer is reacted in the presence of phthalocyanine carboxylic acid to simultaneously form the polyester chain and introduce the polyester chain into the phthalocyanine carboxylic acid. The method etc. can be mentioned. Here, the monomer refers to a low molecular compound capable of forming an esterification reaction to form a polyester chain. Typically, a diol represented by HO—R ² —OH, HOOC—R ³ — Examples thereof include dicarboxylic acids represented by COOH, hydroxy acids represented by HO—R ⁴ —COOH, and derivatives thereof. These compounds can form an ester by condensing the hydroxyl group and the carboxyl group. However, in order to increase the yield and purity of the phthalocyanine derivative to be produced, it is necessary to increase the reactivity of the phthalocyanine carboxylic acid and the monomer. For that purpose, a highly reactive group is used as a group causing the esterification reaction. It is preferable to use it. Specifically, a halocarbonyl group or an acid anhydride group is used instead of a carboxyl group, an epoxy group is used instead of a hydroxyl group, or a lactone cleavage group is used instead of a hydroxyl group and a carboxyl group. It is preferable to use it.

  Alternatively, it is possible to react only the above monomer, synthesize a polyester having a group capable of forming an ester bond by reacting with a carboxyl group in advance, and react this with phthalocyanine carboxylic acid. Again, in order to increase the reactivity of the phthalocyanine carboxylic acid, it is preferable to convert the carboxyl group to a more reactive group such as a halocarbonyl group.

  Specific examples of the method for introducing a polyester chain into phthalocyanine carboxylic acid using the above highly reactive group include (A) phthalocyanine carboxylic acid, a monomer having one epoxy group, and a cyclic acid anhydride group. A method of reacting a monomer having one, (B) a method of reacting a phthalocyanine carboxylic acid, a monomer having two epoxy groups and a monomer having two carboxyl groups, and (C) phthalocyanine carbonyl halide by acid-haliding phthalocyanine carboxylic acid (D) phthalocyanine carboxylic acid is acid-halidized to form a phthalocyanine carbonyl halide, which is terminated with a hydroxyl group synthesized in advance, and a monomer having two hydroxyl groups and a monomer having two halocarbonyl groups. Have one in It can be mentioned a method of reacting the ester and the like, synthetic methods are not limited thereto.

In the phthalocyanine derivative of the present invention, R ² , R ³ and R ⁴ in the general formula (1) are typically residues derived from diol, dicarboxylic acid, hydroxy acid or derivatives thereof, but more reactive. When using compounds with high groups (epoxies instead of diols, cyclic acid anhydrides instead of dicarboxylic acids, lactones instead of hydroxy acids, etc.), these residues are easily determined from the chemical formula of the compound used. Can be determined.
R ^2, R ³ and R ⁴ in one molecule may be the being the same or different, further, R ^2, R ³ and R ⁴ are different and are each the same for each repetition of the polyester chain It may be. R ⁵ in the end group X of the polyester chain may be the same as R ² , R ³ or R ⁴ but may be changed to R ² , R ³ or R ⁴ to favor the production of the phthalocyanine derivative. May be good.

R ² , R ^3, and R ⁴ in the general formula (1) are divalent organic groups having 1 to 20 carbon atoms, but have 1 to 12 carbon atoms in terms of the variety of usable solvents. It is more preferable that it has 2 to 8 carbon atoms. Advantageously, R ² , R ³ and R ⁴ are saturated or unsaturated divalent hydrocarbon groups, the structure of which may be either linear or branched, part or all of which forms a ring structure You may do it. Furthermore, when R ² , R ³ and R ⁴ contain oxygen, the hydrogen atom in the structure is substituted with a hydroxyl group, or an ether bond is formed through an oxygen atom in the carbon-carbon bond. Is good.

Such R ² , R ³ and R ⁴ can be freely selected by appropriately adjusting the type of monomer used. For example, if a monomer having an unsaturated bond is used, R ² , R ³ and R ⁴ having an unsaturated bond can be obtained, and if a monomer having an ether bond is used, R ² , R ³ and R having an ether bond can be obtained. ⁴ is obtained. Further, the structure of the group represented by the number of carbon atoms, the shape of the carbon skeleton, and the like can be freely selected by using a corresponding monomer.

Preferred examples of such R ² , R ³ and R ⁴ include a saturated or unsaturated alkylene group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and arylene. Groups, arylalkylene groups, alkylene groups having one or more ether bonds, arylalkylene groups having one or more ether bonds, alkylene groups having one or more ether bonds and one or more hydroxyl groups, etc. Can do. The structure of these divalent organic groups may be linear or branched, and a part or all of them may form a ring structure.

Specific examples of such R ² , R ³ and R ⁴ include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group. Propane-1,2-diyl group, butane-1,2-diyl group, pentane-1,2-diyl group, hexane-1,2-diyl group, cyclohexane-1,2-diyl group, cyclohexane-1, 4-diyl group, 4-methylcyclohexane-1,2-diyl group, 4-vinylcyclohexane-1,2-diyl group, 1-cyclohexene-1,2-diyl group, 4-cyclohexene-1,2-diyl group Ethene-1,2-diyl group, prop-1-ene-1,2-diyl group, prop-2-ene-1,2-diyl group, o-phenylene group, p-pheny group Len group, phenylethylene group, 3-methoxypropane-1,2-diyl group, 3-isopropyloxypropane-1,2-diyl group, 3-allyloxypropane-1,2-diyl group, 3-butoxypropane- 1,2-diyl group, 3-tert-butoxypropane-1,2-diyl group, 3- (2-ethylhexyl) oxypropane-1,2-diyl group, 3-phenoxypropane-1,2-diyl group, 3-oxapentane-1,5-diyl group, 3,6-dioxaoctane-1,8-diyl group, 3,6,9-trioxaundecane-1,11-diyl group, 2,9-dihydroxy- 4,7-dioxadecane-1,10-diyl group, 2,12-dihydroxy-4,7,10-trioxatridecane-1,13-diyl group, 2,15-dihydroxy-4,7 10,13-tetraoxahexadecane-1,16-diyl group, 2,9-dihydroxy-5-methyl-4,7-dioxadecane-1,10-diyl group, 2,10-dihydroxy-6,6-dimethyl- 4,8-dioxaundecane-1,11-diyl group, 2,13-dihydroxy-4,11-dioxatetradecane-1,14-diyl group, 2,6,10-trihydroxy-4,8-di Although an oxaundecane-1,11-diyl group etc. can be mentioned, it is not limited to these. These divalent organic groups may be used alone or in combination of two or more.

R ⁵ is a group derived from a monohydric alcohol represented by HR ⁵ —OH, and the number of carbons is preferably in the same range as R ² , R ³ or R ⁴ . The monohydric alcohol has a function of adjusting the molecular weight of the polyester chain by reacting with the terminal of the polyester chain to stop the polymerization. Preferable examples of such monovalent alcohols include alkyl alcohols, aryl alcohols, aralkyl alcohols, etc. having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 2 to 8 carbon atoms. it can. Specific examples of such monovalent alcohols include, but are not limited to, methanol, ethanol, propanol, butanol, hexanol, octanol, phenol, benzyl alcohol, and the like. These monohydric alcohols may be used alone or in combination of two or more.

In the phthalocyanine derivative of the present invention, each of R ² , R ³ or R ⁴ in the general formula (1) may be only one type or two or more types. When at least one of them is two or more, it constitutes polyester such as block, alternating or random, and any of these may be used. In the general formula (1), X represents an end group, and X is determined by the monomer at the end of the polyester chain. The end of the polyester chain is typically either a carboxyl group (X is a hydrogen atom) or a hydroxyl group (X is —R ² —OH), but is sealed with an alkyl group (X is —R ⁵ —H). It may be stopped. Moreover, when X is a hydrogen atom, these terminals may form a salt.

In the phthalocyanine derivative of the present invention, p in the description of the general formula (1) may be 1 to 100, preferably 3 to 70, more preferably 5 to 50 from the viewpoint of the stability of the pigment dispersion. Moreover, although q should just be 2-200, 6-140 are preferable from the stability point of a pigment dispersion, Furthermore, 10-100 are more preferable. The value of p or q can be freely selected by appropriately adjusting the molar ratio of phthalocyanine carboxylic acid and monomer at the time of producing the phthalocyanine derivative.
In the phthalocyanine derivative represented by the general formula (1), n polyester chains are bonded to a phthalocyanine residue, but it is not necessary that all the n polyester chains in one molecule are composed of the same polyester chain. , P or q may be different, or the types of R ² , R ³ or R ⁴ may be different. In addition, when n in the general formula (1) is 2 or more, p and q in one molecule do not need to be entirely within the range (including the case where part of p or q is 0), and average The value should be in that range.

The dispersant of the present invention comprises a phthalocyanine derivative represented by the general formula (1). The dispersant is advantageously in the form of a solid, all of which are active ingredients, but may be diluted with a solvent or the like for the purpose of facilitating handling, and may contain a small amount of other ingredients. Here, the active ingredient refers to a component having the ability to promote dispersion. When a solvent or the like is added to the dispersant, the solid content obtained by removing the solvent from the dispersant is preferably 10% by weight or more, and more preferably 30% by weight or more. Further, the solid content preferably contains 50% by weight or more, more preferably 70% by weight or more of the phthalocyanine derivative as an active ingredient.
As the solvent for diluting the dispersant, a solvent excellent in solubility of the dispersant is preferable. For example, ester solvents, ether ester solvents, ether solvents, alcohol solvents, aromatic solvents, ketone solvents, nitrogen-containing solvents. Examples of the solvent include aliphatic solvents and aliphatic solvents, and ester solvents and ether ester solvents are particularly preferable.

  The pigment composition of the present invention comprises a pigment and a dispersant comprising a phthalocyanine derivative represented by the general formula (1). Here, the weight ratio of both may be 99: 1 to 50:50, but is preferably 90:10 to 50:50, more preferably 80:20 to 60 from the viewpoint of the stability of the pigment dispersion. : 40 is more preferable. When the ratio of the dispersant is less than 1 when the sum of the two is 100, the dispersion of the pigment dispersion is insufficient due to the lack of the dispersant. On the other hand, when the ratio of the dispersant is larger than 50, not only the effect of the dispersant reaches a peak, but also the stability of the pigment dispersion produced due to the excessive dispersant may be impaired.

The pigment composition of the present invention may contain only a dispersant in the pigment, but may contain resins, solvents and the like, and may further contain a small amount of other components. Here, the solid content of the pigment composition excluding the solvent and the like preferably contains 30% by weight or more, and more preferably 50% by weight or more of the pigment and the dispersant. Moreover, when a solvent etc. are included, it is preferable that solid content is 5 weight% or more, Furthermore, it is 10 weight% or more.
Examples of the resin blended in the pigment composition include acrylic resin, alkyd resin, epoxy resin, melamine resin, urethane resin, vinyl resin, phenol resin, nitrocellulose resin, and the like. Not. The solvent is preferably a solvent that is excellent in the solubility of the dispersant and the resins. For example, an ester solvent, an ether ester solvent, an ether solvent, an alcohol solvent, an aromatic solvent, a ketone solvent, a nitrogen-containing solvent. Examples of the solvent include aliphatic solvents and aliphatic solvents, and ester solvents and ether ester solvents are particularly preferable.

  The pigment composition of the present invention is not particularly limited as long as it contains the pigment and the dispersant in a weight ratio of 99: 1 to 50:50. Examples of the form of the pigment composition include powder, wet cake, lump, and slurry. The pigment composition may be dispersed in a dispersion medium, for example, a colored resin in which the pigment composition is dispersed in a resin, a pigment dispersion in which the pigment composition is dispersed in a liquid, or the like. Good.

The pigment used in the pigment composition of the present invention may be any of conventionally known organic pigments, inorganic pigments, carbon black, and the like, but organic pigments having a condensed polycyclic structure have a remarkable effect of the dispersant of the present invention. Most preferred for being. Examples of organic pigments having a condensed polycyclic structure include phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, selenium pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and the like. However, usable pigments are not limited to these.
Since the phthalocyanine derivative of the present invention exhibits a blue hue, a particularly preferred pigment is a blue pigment such as phthalocyanine blue from the viewpoint that the hue change of the pigment is small and the color characteristics are excellent. Furthermore, since the dispersant of the present invention can improve the dispersibility with a small addition amount, the color characteristics of the resulting pigment composition or pigment dispersion are further improved.

  The pigment used in the pigment composition of the present invention can be blended with a modifier called a dispersion aid for the purpose of improving the wettability of the pigment surface and improving the dispersibility due to the electrostatic repulsion effect. . As the dispersion aid, a pigment derivative having a skeleton that is the same as or similar to that of the pigment to be dispersed and having a relatively low molecular weight (generally, a molecular weight of less than 2000) is preferable. Examples include amide derivatives, alkylamino derivatives, alkyl derivatives, and the like. When these pigment derivative type dispersion aids are used, they may be appropriately selected according to the pigment or solvent to be dispersed, and the use thereof is not particularly limited.

  Even if the pigment composition of the present invention is produced by simply blending a pigment and a dispersant, the intended effect can be obtained sufficiently. However, the pigment and the dispersant are mechanically mixed by a kneader, attritor, roll mill, etc., the dispersant is added to the slurry of the pigment in water or an organic solvent and stirred sufficiently, or strong such as dimethyl sulfoxide or pyridine Even better results can be obtained if the pigment and dispersant are blended more closely by a method such as coprecipitation in a poor solvent such as water after co-dissolving the pigment and dispersant in a solvent having a dissolving power. Can do.

  The pigment composition of the present invention can be made into a pigment dispersion by dispersing in a liquid as a dispersion medium. Such pigment dispersions can be blended with resins, solvents, other additives, and the like, which are appropriately selected and used depending on the use of the pigment dispersion. The solvent used as the dispersion medium or the solvent used in the pigment dispersion is preferably a solvent excellent in solubility of the dispersant and the resin, for example, an ester solvent, an ether ester solvent, an ether solvent, an alcohol solvent. A solvent, an aromatic solvent, a ketone solvent, a nitrogen-containing solvent, an aliphatic solvent and the like can be mentioned, and an ester solvent and an ether ester solvent are particularly preferable. Even when these solvents are used to dissolve resins, dispersants, and the like, they will be present as a main component or a minor component of the dispersion medium when they become a pigment dispersion.

  Examples of the resin used for the pigment dispersion include acrylic resin, alkyd resin, epoxy resin, melamine resin, urethane resin, vinyl resin, phenol resin, nitrocellulose resin, and the like. Not. In addition, examples of other additives include a surface conditioner and an antifoaming agent.

  The method for producing a pigment dispersion using the pigment composition of the present invention is not particularly limited, and a known method can be used. For example, a dispersion treatment using a kneader, an attritor, a roll mill, a bead mill, a paint shaker, a disperser, or the like can be given.

  The pigment composition or pigment dispersion in the present invention can be suitably used for paints, printing inks, plastic coloring, water paints, water inks, emulsion paints, emulsion inks, etc. A colored product having excellent stability and good coloring power can be obtained.

The reason why the phthalocyanine derivative of the present invention is excellent in suitability as a dispersant is due to the characteristics of its structure. Since the phthalocyanine derivative of the present invention has both a phthalocyanine residue as an anchor site adsorbed on the pigment surface and a polyester chain as a site that inhibits aggregation of the pigment and imparts dispersibility, it exhibits excellent dispersion stability. be able to. Moreover, since the structure also has the property that it can be produced with high yield and high purity, it is easy to produce, and can be suitably used as a dispersant without requiring purification.
Furthermore, the phthalocyanine derivative of the present invention has an ester bond as a linking group that bonds a phthalocyanine residue and a divalent organic group to each other. Since ester bonds have a high degree of freedom of rotation between bond atoms compared to amide bonds, sulfonamide bonds, etc., the phthalocyanine derivatives of the present invention have a highly flexible structure, and as a result, due to their suitability as dispersants. It will be excellent. And since the phthalocyanine derivative of the present invention has an ester bond, it is excellent in solubility in an ester solvent or an ether ester solvent. In the production of a pigment dispersion using these solvents, particularly good stability is obtained. A pigment dispersion can be provided.

  Since the phthalocyanine derivative in the present invention has a structure excellent in suitability as a dispersant, when used for dispersing a pigment, the phthalocyanine derivative is extremely dispersible in that it imparts easy dispersibility to the pigment and imparts high stability to the produced pigment dispersion. Useful. Further, the pigment composition and pigment dispersion in the present invention can be suitably used for paints, printing inks, plastic coloring, water paints, water inks, emulsion paints, emulsion inks and the like, which are extremely useful industrially. is there. Furthermore, since the phthalocyanine derivatives of the present invention are excellent in solubility in many solvents, they can be used as blue oil-soluble dyes themselves. Such oil-soluble dyes are used for coloring plastics and resins, oil-based inks, and the like. Useful.

Hereinafter, the present invention will be described specifically by way of examples. In the following, “part” means part by weight.
Analysis of the compound of this example was performed using an FT-NMR analyzer (trade name: JNM-EX270, manufactured by JEOL Zetham) and a high-speed GPC analyzer (trade name: HLC-8020, manufactured by Tosoh Corporation). ¹ H-NMR analysis was performed at 270 MHz in chloroform-d ₁ . Moreover, GPC analysis was implemented by measuring the light absorbency in 600 nm which is a wavelength which a phthalocyanine frame | skeleton has absorption using a ultraviolet visible detector.

A glass three-necked flask equipped with necessary equipment such as a stirrer and a reflux tube was charged with 100 parts of copper phthalocyanine tetracarboxylic acid, 1172 parts of 1,2-epoxyhexane and 1 part of benzyltriethylammonium chloride, and a nitrogen stream with sufficient stirring. The reaction was carried out at 120 ° C. for 2 hours. Next, while maintaining the temperature at 120 ° C., 1043 parts of a 50% maleic anhydride 50% dioxane solution was successively added dropwise over 2 hours. After dropping, the reaction was continued at 120 ° C. for 4 hours, and then the solvent was distilled off under reduced pressure to obtain 1223 parts of a blue resinous compound A.
In this compound A, R ^{2 in the} general formula (1) is a hexane-1,2-diyl group (—CH ₂ CH (C ₄ H ₉ ) —), and R ³ is an ethene-1,2-diyl group ( The phthalocyanine derivative which is -CH = CH-) was included as the main component. The results of ¹ H-NMR analysis of Compound A are shown in FIG. Moreover, the GPC analysis result of the compound A was the standard polystyrene conversion weight average molecular weight 6100, and polydispersity (dispersion index) 1.33. These analysis results supported the structure of the phthalocyanine derivative.
The compounds in the following examples were analyzed in the same manner, and it was confirmed that the phthalocyanine derivative of the present invention was contained as a main component.

Instead of 100 parts of copper phthalocyanine tetracarboxylic acid, 177 parts of copper phthalocyanine dicarboxylic acid was used and the same reaction as in Example 1 was performed to obtain 1276 parts of blue resinous compound B.
The result of ¹ H-NMR analysis of Compound B was almost the same as that of Compound A. Moreover, the GPC analysis result of the compound B was the standard polystyrene conversion weight average molecular weight 6600, and polydispersity 1.35.

Instead of 100 parts of copper phthalocyanine tetracarboxylic acid, 123 parts of copper phthalocyanine octacarboxylic acid was used and the same reaction as in Example 1 was performed to obtain 1253 parts of blue resinous compound C125.
The result of ¹ H-NMR analysis of Compound C was almost the same as that of Compound A. Moreover, the GPC analysis result of the compound C was a standard polystyrene conversion weight average molecular weight 3000 and polydispersity 1.38.

A glass three-necked flask equipped with necessary equipment such as a stirrer and a reflux tube was charged with 100 parts of copper phthalocyanine tetracarboxylic acid, 927 parts of ethylene glycol diglycidyl ether and 1 part of benzyltriethylammonium chloride under a nitrogen stream with sufficient stirring. The reaction was carried out at 120 ° C. for 2 hours. Next, 3535 parts of a 25% dioxane solution of phthalic acid was successively added dropwise over 2 hours while maintaining the temperature at 120 ° C. After the dropping, the reaction was continued at 120 ° C. for 4 hours, and then the solvent was distilled off under reduced pressure to obtain 1910 parts of a blue resinous compound D.
This compound D has a phthalocyanine derivative in which R ^{2 in the} general formula (1) is a 2,9-dihydroxy-4,7-dioxadecane-1,10-diyl group and R ³ is an o-phenylene group as its main component. Was included. The result of ¹ H-NMR analysis of Compound D showed multiple lines at 7.4 to 8.0, 3.1 to 4.2, and 2.4 to 2.9 ppm, respectively. Moreover, the GPC analysis result of the compound D was the standard polystyrene conversion weight average molecular weight 7100, and polydispersity 1.30.

The same reaction as in Example 4 was carried out using 1161 parts of diethylene glycol diglycidyl ether instead of 927 parts of ethylene glycol diglycidyl ether and 2513 parts of 25% dioxane solution of succinic acid instead of 3535 parts of 25% dioxane solution of phthalic acid. In this way, 1889 parts of a blue resinous compound E was obtained.
This compound E is a phthalocyanine derivative in which R ^{2 in the} general formula (1) is a 2,12-dihydroxy-4,7,10-trioxatridecane-1,13-diyl group and R ³ is an ethylene group. It was included as its main component. The result of ¹ H-NMR analysis of Compound E showed multiple lines at 3.1 to 4.3 and 2.0 to 2.9 ppm, respectively. Moreover, the GPC analysis result of the compound E was a standard polystyrene conversion weight average molecular weight 8100, and polydispersity 1.45.

A glass three-necked flask equipped with necessary equipment such as a stirrer and a reflux tube was charged with 100 parts of copper phthalocyanine tetracarboxylic acid and 665 parts of thionyl chloride and refluxed at a boiling point for 12 hours under a nitrogen stream with sufficient stirring. Thionyl chloride was distilled off under reduced pressure. To the blue solid remaining in the flask, 824 parts of succinyl dichloride and 2660 parts of chlorobenzene were added, and the temperature was raised to 80 ° C. under a nitrogen stream with sufficient stirring, and 363 parts of ethylene glycol was successively added dropwise over 2 hours. After the dropping, the reaction was continued at 80 ° C. for 4 hours, and then the solvent was distilled off under reduced pressure to obtain 880 parts of blue resinous compound F.
This compound F contained a phthalocyanine derivative in which R ² and R ^{3 in} the general formula (1) are both ethylene groups as its main component. The result of ¹ H-NMR analysis of Compound F showed a multiple line at 2.6 to 4.3 ppm. Moreover, the GPC analysis result of the compound F was a standard polystyrene conversion weight average molecular weight 5000 and polydispersity 1.41.

A glass three-necked flask equipped with necessary equipment such as a stirrer and a reflux tube was charged with 100 parts of copper phthalocyanine tetracarboxylic acid and 665 parts of thionyl chloride and refluxed at a boiling point for 12 hours under a nitrogen stream with sufficient stirring. Thionyl chloride was distilled off under reduced pressure. Add 1330 parts of chlorobenzene to the blue solid remaining in the flask, raise the temperature to 80 ° C. under a nitrogen stream with sufficient stirring, and separately synthesize polyester 50% chlorobenzene having a primary hydroxyl group at the terminal. 1294 parts of a solution (a product obtained by reacting 607 parts of ε-caprolactone, 39 parts of 1-butanol, 646 parts of chlorobenzene and 2 parts of tetrabutyl titanate at 120 ° C. for 4 hours) was successively added dropwise over 2 hours. After the dropping, the reaction was continued at 80 ° C. for 4 hours, and then the solvent was distilled off under reduced pressure to obtain 737 parts of a blue resinous compound G.
This compound G contained a phthalocyanine derivative in which R ^{4 in the} general formula (1) is a pentamethylene group and R ⁵ is a butylene group as its main component. The results of ¹ H-NMR analysis of Compound G showed multiple lines at 3.9 to 4.2, 2.2 to 2.4, and 1.2 to 1.7 ppm, respectively. Moreover, the GPC analysis result of the compound G was the standard polystyrene conversion weight average molecular weight 4900, and polydispersity 1.50.

  40 parts of any of the blue resinous compounds A to G obtained in Examples 1 to 7, 100 parts of ε-type copper phthalocyanine blue pigment (Pigment Blue 15: 6) and 860 parts of propylene glycol monomethyl ether acetate were blended, Dispersion treatment for 6 hours was performed using a paint shaker, and 1000 parts of pigment dispersions A to G were produced. Here, 0.4 mmφ zirconia beads were used at a filling rate of 40% for the media of the paint shaker. It should be noted that a pigment dispersion A is manufactured from Compound A (Example 8), and a pigment dispersion G is manufactured from Compound G (Example 14). Example numbers are assigned in that order.

Comparative Example 1
The same treatment as in Example 8 was performed without using 40 parts of the blue resinous compound A to produce 960 parts of a pigment dispersion X.

Comparative Example 2
In place of 40 parts of the blue resinous compound A, 40 parts of a polyester having a primary hydroxyl group at the end shown in Example 7 (one obtained by distilling off the solvent) was used, and the same treatment as in Example 8 was performed to disperse the pigment. Y1000 parts of body was produced.

(Characteristic evaluation of pigment dispersion)
The viscosity of the produced pigment dispersion was measured using a vibration viscometer (trade name: Viscomate VM-100, manufactured by Yamaichi Electronics Co., Ltd.). Moreover, the average particle diameter of the pigment in the pigment dispersion was measured using a particle size distribution meter (trade name: Concentrated particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.).
The pigment dispersion was evaluated according to the following criteria. Viscosity is less than 50 cP: ◯, 50 cP or more and less than 100 cP: Δ, 100 cP or more (including measurement impossible): ×. Further, the average particle diameter is less than 1000 nm: ◯, 1000 nm or more and less than 5000 nm: Δ, 5000 nm or more (including incapable measurement): ×.

  Table 1 shows the evaluation results of the pigment dispersions obtained in Examples and Comparative Examples. The pigment dispersions in the examples had a low viscosity, a small average particle size, and excellent dispersion stability as compared with the pigment dispersions in the comparative examples. On the other hand, the dispersion stability of the pigment dispersion in the comparative example was poor.

Graph showing ¹ H-NMR analysis result of blue resinous compound A

Claims (4)

A phthalocyanine derivative represented by the following general formula (1) or a salt thereof.
Pc- (CO—R ¹ —O—X) _n (1)
(Wherein Pc is an n-valent phthalocyanine residue, R ¹ is a group consisting of — (O—R ² —O—OC—R ³ —CO) _p — or — (O—R ⁴ —CO) _q —. , X represents a hydrogen atom, —R ² —OH or —R ⁵ —H, n represents 1 to 8, p represents 1 to 100, q represents 2 to 200, and n is 2 or more. When p and q are within the above numerical range as an average in one molecule, R ^{2 to} R ⁵ represent a divalent organic group having 1 to 20 carbon atoms)   A pigment dispersant comprising the phthalocyanine derivative according to claim 1.   A pigment composition comprising the pigment according to claim 2 and a pigment: dispersant weight ratio of 99: 1 to 50:50.   A pigment dispersion, wherein the pigment composition according to claim 3 is dispersed in a liquid.

Images