JP2003165922A - Pigment dispersant, and pigment composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a colorless or slightly colored pigment dispersant excellent in usability, particularly in nonagglomerative characteristics, noncrystallizing characteristics and flowability. <P>SOLUTION: The pigment dispersant is represented by general formula (1) [wherein X is NH, O, CONH, SO<SB>2</SB>NH, CH<SB>2</SB>NH, CH<SB>2</SB>NHCOCH<SB>2</SB>NH or Y<SB>1</SB>-Y<SB>2</SB>-Y<SB>3</SB>(wherein Y<SB>1</SB>is CONH, SO<SB>2</SB>NH, CH<SB>2</SB>NH, NHCO or NHSO<SB>2</SB>; Y<SB>2</SB>is an alkylene, an alkenylene or an arylene; and Y<SB>3</SB>is NH or O); A is a terminal amino group; and B is O-R<SB>1</SB>, NH-R<SB>1</SB>(wherein R<SB>1</SB>is H, an alkyl, an alkenyl or an aryl), A, or a group of formula (6)]. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a pigment dispersant having excellent suitability for use, particularly non-aggregation, non-crystallinity, and fluidity, and more specifically, a pigment dispersant effective for inks and paints. , And a pigment composition containing the same.

[0002]

2. Description of the Related Art Generally, in various coatings or ink compositions, practically useful pigments exhibiting a clear color tone and high tinting strength are composed of fine particles. When dispersed in non-aqueous vehicles such as offset inks, gravure inks and paints, it is difficult to obtain stable dispersions of fine pigment particles, and therefore pigment dispersants are used to improve the affinity between pigments and vehicles. It is known to improve the properties and stabilize the dispersion.

Many proposals have been made for such pigment dispersants centering on copper phthalocyanine and quinacridone pigments.

For example, Japanese Examined Patent Publication No. 41-2466 and USP
There is known a method of mixing a compound obtained by introducing a substituent such as a sulfonic acid, a sulfonamide group, an aminomethyl group or a phthalimidomethyl group into a side chain with an organic pigment as a base skeleton as represented by 2855403. However, although these compounds have a large effect on the non-aggregation property of the pigment, the crystal stability, etc., since the compound to be added is derived from a compound having the same chemical structure as the pigment, it has an inherently strong coloring and a different hue. When it is used as a pigment, it is significantly restricted. Therefore, it is necessary to prepare a corresponding compound for each individual pigment, which is a significant disadvantage in producing a pigment composition. Further, since these compounds have properties similar to dyes, they may have poorer resistance than pigments, and when a pigment composition containing these compounds is used in ink or paint, the hue of the compound fades due to aging and the like. However, the coating film hue may change. In addition, after the coating film is formed, these compounds may float and the hue may shift due to high-temperature treatment such as boiling or baking or pressure bonding.

[0005]

As a result of earnest research in view of the above problems, the present inventor has found that a specific compound which does not have a pigment skeleton and is colorless or slightly colored improves the above various problems. The inventors have found that the pigment can be dispersed well, and have completed the present invention.

[0006]

That is, the present invention relates to a pigment dispersant represented by the following general formula (1). General formula (1)

[0007]

[Chemical 7]

(In the formula, X is --NH--, --O--, --CON
_{H -, - SO 2 NH -} , - CH 2 NH -, - CH 2 NHC
OCH ₂ NH- or -Y ₁ -Y ₂ -Y ₃ - represents, Y ₁ is _{-CONH -, - SO 2 NH -} , - CH 2 NH -, - NH
CO- or -NHSO ₂ - represents, Y ₂ is may have a substituent, an alkylene group, an alkenylene group or an arylene group, Y ₃ represents -NH- or -O-, A
Represents any group represented by the following general formulas (2) to (5), B represents —O—R ₁ , —NH—R ₁ , A or the following general formula (6), and R ₁ represents hydrogen. Represents an alkyl group, an alkenyl group or an aryl group, which may have an atom or a substituent. ) General formula (2)

[0009]

[Chemical 8]

General formula (3)

[0011]

[Chemical 9]

General formula (4)

[0013]

[Chemical 10]

General formula (5)

[0015]

[Chemical 11]

(In the formula, Z ₁ and Z ₂ are independently -NH.
Represents a — or —O—, Z ₃ represents a direct bond or represents —W—CONH— or —W—SO ₂ NH—, W
Represents an alkylene group, an alkenylene group or an arylene group which may have a substituent, and R ₂ and R ₃ each independently represent an alkyl group which may have a substituent or an alkenyl which may have a substituent. A group, or R ₂ and R ₃ together represent a 5-membered ring or 6-membered ring which may further contain a nitrogen atom, an oxygen atom or a sulfur atom, and i, j, k, l, m and n are Each independently represents an integer of 1 to 6. ) General formula (6)

[0017]

[Chemical 12]

(In the formula, X has the same meaning as in formula (1).) The present invention further relates to a pigment composition comprising a pigment and a pigment dispersant represented by formula (1).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The pigment dispersant of the present invention has a benzimidazolone structure in the triazine ring and an amino group represented by A in the general formula (1).

Y _{2 of the} general formula (1) and the general formula (4)
And W contained in Z _{3 of} (5) represents an alkylene group, an alkenylene group or an arylene group, which may have a substituent, but preferably has 20 or less carbon atoms, and more preferably is substituted. Examples thereof include a phenylene group which may have a group, a naphthylene group which may have a substituent and an alkylene group which has a substituent and has 10 or less carbon atoms.

R _{1 in the} general formula (1) represents an alkyl group, an alkenyl group or an aryl group which may have a substituent, preferably has 20 or less carbon atoms, and more preferably has a substituent. Examples thereof include a phenyl group which may have a substituent, a naphthyl group which may have a substituent and an alkyl group which has a substituent and has 10 or less carbon atoms.

The alkyl group which may have a substituent or the alkenyl group which may have a substituent contained in R ₂ and R ₃ of the general formulas (2) to (5) has 20 or less carbon atoms. Is preferred. As the unsubstituted alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples thereof include an isobutyl group, a pentyl group and a hexyl group. As the unsubstituted alkenyl group, vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1
-Butenyl group, 2-butenyl group, 2-pentenyl group, 2
-Methylallyl group and the like. The substituted alkyl group or alkenyl group is a group in which a hydrogen atom of the alkyl group or alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom or a bromine atom, a hydroxyl group or a mercapto group. Further, R ₂ and R ₃ may be united to form a 5-membered ring or 6-membered ring which may further contain a nitrogen atom, an oxygen atom or a sulfur atom, and as a preferable example, a piperidino group, Piperazino group, pipecorino group, N-
Examples thereof include a methylpiperazino group, a pyrrolidino group, a morpholino group, and a thiazolidino group.

Of these, A is preferably a group represented by the general formula (2), and R ₂ and R ₃ are preferably alkyl groups having 1 to 6 carbon atoms. Further, as X, —NH— is advantageous in synthesis and is preferable.

The amine component or alcohol component used to form the general formulas (2) to (5) is, for example,
Dimethylaminoethylamine, diethylaminoethylamine, N, N-dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, N, N-dibutylaminopropylamine, dimethylaminobutylamine, diethylaminobutylamine,
N, N-dipropylaminobutylamine, N, N-dibutylaminobutylamine, diethylaminohexylamine, N-aminomethylpiperidine, N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylpyrrolidine, N-aminopropylpyrrolidine , N
-Aminomethyl-2-pipecoline, N-aminoethyl-
4-pipecoline, N-aminopropyl-2-pipecoline, N-aminoethylmorpholine, N-aminopropylmorpholine, N, N-methyl-laurylaminopropylamine, N, N-dioleylaminoethylamine, N,
N-distearylaminobutylamine, 1-amino-4
-Dimethylaminocyclohexane, 1-amino-4-diethylaminocyclohexane, 1-amino-4-N, N
-Dibutylaminocyclohexane, 1-aminomethyl-
4-dimethylaminocyclohexane, 1-aminomethyl-4-diethylaminocyclohexane, 1-aminomethyl-4-N, N-dibutylaminocyclohexane, 1-
Aminoethyl-4-dimethylaminocyclohexane, 1
-Aminoethyl-4-diethylaminocyclohexane,
1-aminoethyl-4-N, N-dibutylaminocyclohexane, 1-amino-4-dimethylaminomethylcyclohexane, 1-amino-4-diethylaminomethylcyclohexane, 1-amino-4-N, N-dibutylaminomethylcyclohexane , 1-amino-4-dimethylaminoethylaminocyclohexane, 1-amino-4-dimethylaminopropylaminocyclohexane, 1-amino-4-diethylaminoethylaminocyclohexane,
1-amino-3,5-dimethylaminocyclohexane,
1-amino-3,5-diethylaminocyclohexane,
1-amino-3,5-N, N-dibutylaminocyclohexane, 1-amino-3,5-dimethylaminomethylcyclohexane, 1-amino-3,5-diethylaminomethylcyclohexane, 1-amino-3,5-N , N-dibutylaminomethylcyclohexane, 1-amino-4-
N-methylpiperazine cyclohexane, 1-amino-4
-N-ethylpiperazine cyclohexane, 1-amino-
Amines such as 4-N-butylpiperazinecyclohexane, dimethylaminomethanol, dimethylaminoethanol, diethylaminoethanol, N, N-dibutylaminomethanol, N, N-dibutylaminoethanol,
N, N-dibutylaminopropanol, diethylaminobutanol, N, N-dioleylaminobutanol, N
-Hydroxyethylpiperidine, N-hydroxypropylpiperidine, N-hydroxyethylpipecoline, N-
Examples thereof include amino alcohols such as hydroxypropylpipecoline, N-hydroxymethylpyrrolidine, N-hydroxybutylpyrrolidine, N-hydroxyethylmorpholine, and N-hydroxybutylmorpholine.

The structure of the pigment dispersant of the present invention has been described above. Examples of the pigment dispersant of the present invention include the following.

[0027]

[Chemical 13]

[0028]

[Chemical 14]

The method for producing the pigment dispersant of the present invention is as follows by way of example. First, 5-aminobenzimidazolone and cyanuric chloride are reacted in equimolar amounts in water, an aqueous acetic acid solution, an alcohol, a hydroalcohol mixed solvent, a general organic solvent such as xylol, and a compound represented by the following formula ( 7) is manufactured.

[0030]

[Chemical 15]

Then, in order to introduce A and B, the compounds represented by the following general formulas (8) to (11) are reacted in water or a general organic solvent to obtain the general formula (1). The pigment dispersant of the present invention represented by can be produced.

General formula (8)

[0033]

[Chemical 16]

General formula (9)

[0035]

[Chemical 17]

General formula (10)

[0037]

[Chemical 18]

General formula (11)

[0039]

[Chemical 19]

(In the formula, R ₂ , R ₃ , i, j, k, and l are the same as those in the general formulas (2) to (4).) In some cases, the compound ( Even if one chlorine atom of 8) is hydrolyzed during the reaction to form a hydroxyl group or an alkoxy group, it can be used as the pigment dispersant of the present invention.

The pigment dispersant obtained in the present invention exhibits excellent effects on all pigments which are generally commercially available. For example, organic pigments such as phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene / perinone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, benzimidazolone pigments, and azo pigments. And inorganic pigments such as carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, red iron oxide, iron black, zinc white, navy blue, and ultramarine blue.

Since the pigment dispersant of the present invention has a colorless or slightly colored hue, it is advantageous in that it has little change in hue even when added to various pigments and is excellent in versatility.

The pigment composition of the present invention comprises a pigment and a pigment dispersant represented by the general formula (1) added thereto.

The addition amount of the pigment dispersant represented by the general formula (1) is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.

When the addition amount of the pigment dispersant represented by the general formula (1) is less than 0.1 part by weight, the pigment dispersing effect is small and it is not preferable. Further, even if the amount is more than 30 parts by weight, the effect of the used amount cannot be obtained.

Examples of the method of using the pigment dispersant according to the present invention include the following methods. 1. A pigment composition obtained by previously mixing a pigment and a pigment dispersant is added to a vehicle and dispersed. 2. The pigment and the pigment dispersant are separately added to the vehicle and dispersed. 3. The pigment and the pigment dispersant are previously separately dispersed in the vehicle, and the resulting dispersion is mixed. In this case, the pigment dispersant may be dispersed only with the solvent. 4. After dispersing the pigment in the vehicle, the pigment dispersant is added to the resulting pigment dispersion. Etc., and any of these can achieve the desired effect.

As a method for preparing the pigment composition, a sufficient dispersion effect can be obtained by simply mixing the pigment powder and the pigment dispersant of the present invention. However, a kneader, a roll, an attritor, a super mill, various pulverizers, etc. By mechanical mixing, or by adding a solution containing the pigment dispersant of the present invention to the suspension system of the pigment in water or an organic solvent, depositing the pigment dispersant on the pigment surface, or having a strong dissolving power of sulfuric acid or the like. Even better results can be obtained by performing a careful mixing method such as co-dissolving an organic pigment and a pigment dispersant in a solvent and coprecipitating with a poor solvent such as water.

Further, for dispersing or mixing the pigment or the pigment dispersant in a non-aqueous or aqueous vehicle or a solvent,
Disperser, high speed mixer,
The pigment can be well dispersed by using a homomixer, a kneader, a roll mill, a sand mill, an attritor, or the like.

Therefore, according to the present invention, gravure ink such as lime rosin varnish, polyamide resin varnish or vinyl chloride resin varnish, nitrocellulose lacquer,
In non-aqueous vehicles such as aminoalkyd resin air-drying or baking paints, acrylic lacquers, aminoacrylic resin baking paints, urethane resin paints, etc. At the same time, it shows good fluidity such as decrease, and at the same time has no problems such as color separation and crystal change, so that the gloss of the printed matter or the coating film is good and therefore a beautiful product can be obtained.

The pigment dispersant and the pigment composition of the present invention are not limited to the non-aqueous vehicle, and also have excellent dispersing effect and coloring power even in the coloring of other printing inks and paints containing water and plastics. A colored product is obtained.
Furthermore, it is also effective for applications that require a high degree of pigment dispersion, such as magnetic paints, color filters and ink jets.

[0051]

EXAMPLES The present invention will be described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”.

Production Example 1 20 parts of 5-aminobenzimidazolone and 25 parts of cyanuric chloride were added to 300 parts of methanol, and the mixture was kept at 20 ° C. or lower for 2 hours.
The reaction is carried out for a time, then 50 parts of N, N-dibutylaminoethylamine are charged, and the mixture is heated under reflux for 2 hours. Then, methanol was distilled off, and 16 parts of sodium hydroxide and 100 parts of water were added.
0 part was added, filtered, washed with water and dried to obtain 70 parts of a pigment dispersant (a) having the following structure.

Pigment dispersant (a)

[0054]

[Chemical 20]

Production Example 2 A pigment having the following structure was prepared by the same reaction as in Production Example 1 except that 34 parts of N-aminoethylpiperidine was used instead of 50 parts of N, N-dibutylaminoethylamine in Production Example 1. 58 parts of dispersant (b) was obtained.

Pigment dispersant (b)

[0057]

[Chemical 21]

Production Example 3 In place of 50 parts of N, N-dibutylaminoethylamine of Production Example 1, dimethylaminoethoxypropylamine 2 was used.
0 parts were used and reacted as in Preparation Example 1, then
Hydrochloric acid was added with 100 parts of hydrochloric acid and 500 parts of water, and then methanol was distilled off to obtain 56 parts of sodium hydroxide and 500 parts of water.
Then, 47 parts of a pigment dispersant (c) having the following structure having the following structure was obtained.

Pigment dispersant (c)

[0060]

[Chemical formula 22]

Production Example 4 40 parts of 5-aminobenzimidazolone and 25 parts of cyanuric chloride are charged in 500 parts of methanol and reacted at 30 ° C. for 2 hours, then 14 parts of dimethylaminopropanol are charged and heated under reflux for 2 hours. Then, methanol is distilled off, 16 parts of sodium hydroxide and 1000 parts of water are added,
It was filtered, washed with water, and dried to obtain 58 parts of a pigment dispersant (d) having the following structure.

Pigment dispersant (d)

[0063]

[Chemical formula 23]

The pigment dispersants (e) to (h) shown in Table 1 were synthesized by the same method.

[0065]

[Table 1]

Examples 1 to 20 and Comparative Examples 1 to 18 Pigment dispersants (a) to (h) were added to various pigments so that the aminoalkyd resin varnish for baking paint had a pigment content of 6%.
A pigment composition containing any of the above was dispersed to prepare a coating material. In addition, as comparative examples, various pigments alone and organic pigment dispersants (i) to (l) having a pigment skeleton shown in Table 2 were similarly dispersed to prepare coating materials.

[0067]

[Table 2]

When the viscosity of each paint was measured, as shown in Table 3, those using the pigment dispersant of the present invention showed low viscosity, small thixotropy (TI value) and excellent fluidity. .

Also, the above coating composition was applied to Ford Cup #
The viscosity was adjusted to 4 seconds for 20 seconds (25 ° C.), and an intermediate coated plate (steel plate coated with a primer coating in advance) was coated with air spray so that the thickness of the dried coating film was about 30 μm. After leaving it for a minute, it was baked at 140 ° C. for 30 minutes.

As shown in Table 3, those using the pigment dispersant of the present invention showed better coating film gloss than the comparative examples. The hue was the same as that of the pigment alone without staining the hue of the base pigment.

Furthermore, a base paint of titanium oxide (titanium oxide dispersed in an aminoalkyd resin varnish) was applied to the above-mentioned baked coating plate, and after baking at 180 ° C. for 30 minutes, the hue of the white base paint applied portion was confirmed. As a result (bleed test), as shown in Table 3, in the case of using the organic dye dispersant, the hue of the lower layer was shifted and the upper layer was colored, but in the case of using the pigment dispersant according to the present invention, the hue change was observed. There was no.

On the other hand, the non-aggregation property and the non-crystallinity were evaluated by the color-separation stability which is a problem in practical use.

The above paint composition is diluted with the above base paint so that the ratio of pigment to titanium oxide is 1/10 to prepare a light color paint. Then, after diluting with xylene and adjusting the viscosity with a Ford cup # 4 for 20 seconds (25 ° C.), it was injected into a test tube and observed for changes in the glass wall surface. The pigment dispersant according to the present invention was used. The color separation with time was smaller than that of the comparative example.

[0074]

[Table 3]

Further, the pigment composition containing the above-mentioned pigment dispersants (a) to (h) did not cause aggregation even when used in nitrocellulose lacquer acrylic resin paints and gravure inks, and showed good fluidity.

[0076]

EFFECT OF THE INVENTION By using the pigment dispersant of the present invention, not only excellent non-aggregating property, non-crystallinity and fluidity but also excellent
It is possible to obtain inks and paints having excellent gloss and hue of the coating film.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 201/00 C09D 201/00 F term (reference) 4D077 AA03 AA08 AB03 AB05 AC05 CA17 DC01Y DC39Y 4J038 BA081 CG141 CH201 DD121 DD231 DG001 GA09 JB36 KA08 KA09 MA07 MA09 NA01 PA18 PA19 4J039 AB08 AD05 AE08 BC12 BC33 BC51 BC52 BC65 BC74 BE22 CA04 EA33 GA03

Claims (5)

[Claims] 1. A pigment dispersant represented by the following general formula (1). General formula (1) (In the formula, X is -NH-, -O-, -CONH-, -SO.
_{2 NH -, - CH 2 NH} -, - CH 2 NHCOCH 2 NH-
Or -Y ₁ -Y ₂ -Y ₃ - represents, Y ₁ is -CONH-,
_{-SO 2 NH -, - CH 2} NH -, - NHCO- or -
Represents NHSO ₂ —, Y ₂ represents an alkylene group, an alkenylene group or an arylene group, which may have a substituent,
Y ₃ represents —NH— or —O—, A represents any group represented by the following general formulas (2) to (5), and B represents —O.
-R _1, represents -NH-R _1, A or the following general formula (6), R ₁ may have a hydrogen atom or a substituent, represents an alkyl group, an alkenyl group or an aryl group. ) General formula (2) General formula (3) General formula (4) General formula (5) (In the formula, Z ₁ and Z ₂ are each independently —NH— or —O.
Represents-, and Z ₃ is directly bonded or -W-CON
H- or -W-SO ₂ NH- represents, W is may have a substituent, an alkylene group, an alkenylene group or an arylene group, each have a R _2, R ₃ are independently a substituent An alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a 5-membered ring or a 6-membered ring which may further contain a nitrogen atom, an oxygen atom or a sulfur atom in combination with R ₂ and R _3. I, j, k, l, m, and n each independently represent an integer of 1 to 6. ) General formula (6) (In the formula, X has the same meaning as in the general formula (1).) 2. The pigment dispersant according to claim 1, wherein Y ₁ is a group represented by formula (2). 3. The pigment dispersant according to claim ₂ , wherein R ₂ and R ₃ are alkyl groups having 1 to 6 carbon atoms. 4. The pigment dispersant according to claim 1, wherein X is —NH—. 5. A pigment composition comprising a pigment and the pigment dispersant according to any one of claims 1 to 4.