JP5228368B2 - Vinyl-based dispersant, method for producing the same, and pigment dispersion using the same - Google Patents

Description

  The present invention relates to a vinyl-based dispersant capable of producing a pigment dispersion excellent in dispersibility, fluidity, and storage stability, a production method thereof, and a pigment dispersion using the same.

  Generally, when manufacturing ink etc., it is known that it is difficult to disperse | distribute a pigment stably at high concentration, and it is known that it causes various problems with respect to a manufacturing process or the product itself.

  For example, dispersions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from a disperser, and if the dispersibility is poor, gelation occurs during storage. It may wake up and become difficult to use. Furthermore, regarding the surface of the color-exposed product, a state defect such as a decrease in gloss and a leveling defect occurs. In addition, when different types of pigments are used in combination, color unevenness due to aggregation or phenomena such as sedimentation may cause color unevenness or a significant reduction in coloring power.

  Therefore, in general, a dispersant is used in order to keep the dispersion state good. The dispersant has a structure of a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance between the two sites. Among them, a dispersant with a graft structure having a main chain part and a side chain part is effective in maintaining a good dispersion state because the side chain acts as a solvent-affinity part as the part where the main chain adsorbs to the pigment. It is.

  Various dispersants are used in accordance with the surface state of the pigment to be dispersed, but acidic pigments are generally used for pigments having a surface that is biased toward basicity. In this case, the acidic functional group becomes the adsorption site of the pigment. Known graft dispersants having acidic functional groups are those obtained by grafting polyester, polyether, polyurethane, or the like to acrylic resins having phosphoric acid groups or carboxylic acids (for example, Patent Document 1 or Patent Document 2). .

  However, when phosphoric acid is used, it may cause problems in terms of storage stability, heat resistance, chemical resistance, etc., and such a dispersant having a phosphoric acid group may be used in inks and paints to be applied. It was scarcely deployable. On the other hand, when carboxylic acid is used, it has a certain degree of dispersion ability, but it is necessary to increase the amount of use in order to produce a stable dispersion with low viscosity.

In addition, Patent Document 3, Patent Document 4, Patent Document 5 and the like have proposed a method in which a pigment is used as a base skeleton and a synergist having an acidic group or a basic group as a substituent in a side chain is mixed with a pigment dispersion. However, this alone does not necessarily provide a satisfactory effect, and it has been proposed to use a dispersant having a counter ion for synergists having an acidic group or basic group as a substituent as described above. (Patent Documents 6 and 7). Here, the synergist has a structure similar to the chemical structure of the pigment that forms the pigment, and is strongly adsorbed to the pigment by π-π interaction, and the surface of the pigment is covered by the ionic functional group contained in the synergist. The effect of the dispersant or pigment carrier having a counter ion is increased by making it acidic or basic.
JP 9-157538 A JP 2000-104005 A JP-A-63-305137 JP-A-1-247468 JP-A-3-26767 JP-A 63-248864 JP-A-9-176511

  An object of the present invention is to provide a vinyl-based dispersant capable of producing a pigment dispersion excellent in dispersibility, fluidity, and storage stability, a method for producing the same, and a pigment dispersion using the same.

The above-described problems can be solved by the vinyl dispersant according to the present invention. That is, in the following general formula (6) or (7) having a unit (G) represented by the following general formula (1) having 2 or 3 aromatic carboxylic acids and a side chain having a number average molecular weight of 500 to 8000. It is related with the vinyl type dispersing agent characterized by including the unit (B) shown, the ratio of the side chain with respect to the total unit total being 30-70 weight part, and a number average molecular weight being 1000-50000.

General formula (1):
[In general formula (1),
R ¹ is a hydrogen atom or a methyl group,
X ¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) —, or —CH ₂ O—,
E ^1a is a repeating unit represented by —R ^1a —O—,
E ^1b is a repeating unit represented by —C (═O) —R ^1b —O—,
R ^1a is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ^1b is a linear or branched alkylene group having 4 to 8 carbon atoms,
m1a is an integer of 0 to 10,
m1b is an integer of 0 to 5,
Y ¹ is a monovalent group represented by the following general formula (2) or general formula (3). ]

General formula (2):
[In general formula (2),
Two of A ^{1 to} A ³ are —C (═O) OH,
The other is a hydrogen atom, —C (═O) OH, or —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms),
k is 1 or 2. ]

General formula (3):
[In general formula (3),
Two of A ^{5 to} A ⁷ are —C (═O) OH,
The other is a hydrogen atom, —C (═O) OH, or —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms ) ,
R ² is a direct bond, —CH ₂ —, —O—, —C (═O) —, —C (═O) OCH ₂ CH ₂ OC (═O) —, —C (═O) OCH (OC (═O) CH ₃ ) CH ₂ OC (═O) —, —SO ₂ —, —C (CF ₃ ) ₂ —, a group represented by the following formula (4), or represented by the following formula (5). Group. ]

Formula (5)

In another preferred embodiment of the vinyl dispersant according to the present invention, the unit (B) is represented by the following general formula (6).
General formula (6):

(In general formula (6),
R ³ is a hydrogen atom or a methyl group,
X ² is a direct bond or a divalent organic residue,
E ^2a is a repeating unit represented by —R ^2a —O— or —O—R ^2a —,
E ^2b is a repeating unit represented by —C (═O) —R ^2b —O— or —O—R ^2b —C (═O) —,
R ^2a is a linear or branched alkylene group having 1 to 4 carbon atoms,
R ^2b is a linear or branched alkylene group having 2 to 10 carbon atoms,
m2a is 0-20,
m2b is 0-20,
X ³ is a direct bond or —O—.
Y ² is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. )
In another preferred embodiment of the vinyl dispersant according to the present invention, the unit (B) is represented by the following general formula (7).
General formula (7)

[In general formula (7),
R ⁴ is a hydrogen atom, a methyl group, or —C (═O) —O—R ¹¹ ,
R ¹¹ is a linear or branched alkyl group having 1 to 18 carbon atoms,
X ⁴ is a direct bond or a divalent organic residue,
R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an aromatic group or —C (═O) —X ⁵ —R ⁷ ;
X ⁵ is —O— or —NH—.
R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkyl group may have an aromatic group substituent;
m3 is 10-100,
Y ³ is a polymerization stopping group of the vinyl polymer. ]
In another preferred embodiment of the vinyl dispersant according to the present invention, it is represented by the following general formula (8).
General formula (8)

[In general formula (8),
(L) is a main chain constituent unit represented by the following general formula (9),
General formula (9)

[In general formula (9),
R ⁸ is a hydrogen atom or a methyl group,
R ⁹ is an aromatic group or —C (═O) —X ⁶ —R ¹⁰ ;
X ⁶ is —O— or —NH—,
R ¹⁰ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkyl group may have an aromatic group substituent. ],
[The arrangement of the carboxyl group-containing unit (G), the side chain-containing unit (B), and the main chain constituent unit (L) is not limited to the order, and is represented by the general formula (8). In the vinyl polymer main chain, each unit (G), (B), and (L) is included in any order, and each unit (G), (B), and (L ) Can be included in random or block type,
When the unit (G) having the carboxyl group, the unit (B) having the side chain, and the main chain constituent unit (L) contained in the general formula (8) are present in plural Can be the same or different from each other,
p1, p2, and p3 represent the average number of each structural unit per molecule of the vinyl-based dispersant,
p1 is 0.3 or more and 30 or less, p2 is 0.5 or more and 50 or less, and p3 is 6 or more and 250 or less. ]
In the said General formula (9), it is preferable that p1 exceeds 3.0 and is 20 or less.
The present invention also relates to a unit represented by the general formula (6) or (7) having a unit (G) represented by the general formula (1) having 2 or 3 aromatic carboxylic acids and a side chain having a number average molecular weight of 500 to 8000. and a unit (B) represented by), the proportion of side chains relative to the total units total Ri 30-70 wt% der a number average molecular weight, a method for producing a vinyl-based dispersing agent is from 1,000 to 50,000 And at least a step [1] of forming an aromatic carboxyl group serving as an anchor portion by reacting an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride with a compound having an acid anhydride reactive group. The present invention relates to a method for producing a vinyl dispersant.

A preferred embodiment of the production method includes a step [2] of forming a unit having a side chain having a number average molecular weight of 500 to 8000 .

  In another preferred embodiment of the production method, the method includes a step [3] of forming a main chain by vinyl polymerization.

The present invention also relates to a general formula (6) having a pigment, a unit (G) represented by the general formula (1) having two or three aromatic carboxylic acids, and a side chain having a number average molecular weight of 500 to 8,000. or and a unit (B) represented by (7), the proportion of side chains relative to the total units total Ri 30-70 wt% der, vinyl having a number average molecular weight, characterized in that 1000 to 50000 The present invention relates to a pigment dispersion containing a dispersant.

  Furthermore, the present invention provides at least one basic synergist selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. It contains the said pigment dispersion containing.

  By using the vinyl dispersant of the present invention, particularly the vinyl dispersant produced by the method of the present invention, a pigment dispersion excellent in dispersibility, fluidity and storage stability can be obtained at a low use amount. be able to.

In general, a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent as a dispersion medium, and it has been explained that the performance of a dispersant is determined by the balance of these two parts. . That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important.
General formula (1):

[In general formula (1),
R ¹ is a hydrogen atom or a methyl group,
X ¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) —, or —CH ₂ O—,
E ^1a is a repeating unit represented by —R ^1a —O—,
E ^1b is a repeating unit represented by —C (═O) —R ^1b —O—,
R ^1a is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ^1b is a linear or branched alkylene group having 4 to 8 carbon atoms,
m1a is an integer of 0 to 10,
m1b is an integer of 0 to 5,
Y ¹ is a monovalent group represented by the following general formula (2) or general formula (3). ]
General formula (2):

[In general formula (2),
Two of A ^{1 to} A ³ are —C (═O) OH,
The other is a hydrogen atom, —C (═O) OH, or —C (═O) OR ^c, where R ^c is an alkyl group having 1 to 18 carbon atoms, or a vinyl-based copolymer. Combined residue Q),
k is 1 or 2. ]
General formula (3):

[In general formula (3),
Two of A ^{5 to} A ⁷ are —C (═O) OH,
The other is a hydrogen atom, —C (═O) OH, or —C (═O) OR ^c (where R ^c is an alkyl group having 1 to 18 carbon atoms, or vinyl Copolymer residue Q),
R ² is a direct bond, —CH ₂ —, —O—, —C (═O) —, —C (═O) OCH ₂ CH ₂ OC (═O) —, —C (═O) OCH (OC (═O) CH ₃ ) CH ₂ OC (═O) —, —SO ₂ —, —C (CF ₃ ) ₂ —, a group represented by the following formula (4), or represented by the following formula (5). Group. ]
Formula (4)

Formula (5)

In the unit (G) having a carboxyl group represented by the general formula (1), Y ¹ represented by the general formula (2) or the general formula (3) is a ring-constituting carbon atom of the aromatic ring. A plurality of carboxyl groups that have two or three directly bonded carboxyl groups and are directly bonded to the ring-constituting carbon atoms of this aromatic ring are suitable as the adsorption site for the pigment. However, when Y ¹ has only one carboxyl group (outside the scope of the present invention), high dispersibility, fluidity, and storage stability are not exhibited, which is not preferable.

In the general formula (1), from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability, in the general formula (1), X ¹ is —C (═O) O—, and E ^1a is —R ^1a —. The following general formula (1 ′), which is O— and E ^1b is —C (═O) —R ^1b —O—, is preferable.
General formula (1 ′):

R ^1a is preferably an alkylene group having 2 to 4 carbon atoms (for example, an ethylene group, a linear or branched propylene group, or a linear or branched butylene group), and m 1a is 0 to 10 (More preferably 0 to 5), R ^1b is preferably a pentamethylene group, and m1b is preferably 0 to 5 (more preferably 0 to 3).

In particular, Y ¹ is preferably a group represented by the general formula (2), more preferably k is 1. When Y ¹ is represented by the general formula (3), R ² is represented by a direct bond, —C (═O) OCH ₂ CH ₂ OC (═O) —, or the above formula (4). It is preferably a group.

Furthermore, in the general formula (2), two of A ^{1 to} A ³ are —C (═O) OH, and the other is a hydrogen atom, or —C (═O) OH, or -C (= O) O-Q (where Q is a vinyl-based copolymer residue, specifically, in the portion other than Y ¹ -C (= O) O- in the general formula (1)) Preferably).

The side chains in the vinyl-based dispersing agent of the present invention, the unit having a side chain of (B), corresponds to the portion constituting the main chain -CH ₂ -CR ^a - (where, R ^a represents a hydrogen atom, a methyl group, Or, it is —C (═O) —O—R ^b , where R ^b is a linear or branched alkyl group having 1 to 18 carbon atoms. In the vinyl dispersant of the present invention, the side chain portion becomes an affinity site for the solvent which is a dispersion medium, and aggregation of the pigment can be suppressed by steric repulsion. That is, the vinyl dispersant of the present invention includes units (B) having side chains having a number average molecular weight of 500 to 15000, and has 30 to 70% by weight of the side chains with respect to the total of all units. Thus, the steric repulsion effect by the side chain portion is excellent, and high dispersibility, fluidity, and storage stability can be obtained. The number average molecular weight of the side chain is more preferably 600 to 12000, and most preferably 650 to 8000. If it is less than 500, the steric repulsion effect due to the solvent-affinity site is reduced, which may be undesirable. Moreover, when exceeding 15000, the viscosity of a dispersion becomes high and may be unpreferable.

  The ratio of the side chain to the total of all units is preferably 40 to 60% by weight, most preferably 45 to 55% by weight. If it is less than 30% by weight, the steric repulsion effect by the solvent-affinity part is reduced, which may be unfavorable because the dispersion stability deteriorates. On the other hand, if it exceeds 70% by weight, the viscosity of the dispersion may increase, which may be undesirable.

  The structure of the side chain is preferably a polyether, polyester, or vinyl copolymer from the viewpoint of reducing the viscosity and storage stability of the pigment dispersion.

As a preferable structure of the unit (B) having a side chain, a polyether and / or polyester represented by the following general formula (6) can be exemplified.
General formula (6):

[In general formula (6),
R ³ is a hydrogen atom or a methyl group,
X ² is a direct bond or a divalent organic residue,
E ^2a is a repeating unit represented by —R ^2a —O— or —O—R ^2a —,
E ^2b is a repeating unit represented by —C (═O) —R ^2b —O— or —O—R ^2b —C (═O) —,
R ^2a is a linear or branched alkylene group having 1 to 4 carbon atoms,
R ^2b is a linear or branched alkylene group having 2 to 10 carbon atoms,
m2a is 0-20,
m2b is 0-20,
X ³ is a direct bond or —O—.
Y ² is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. ]
In the general formula (6), R ^2a is an alkylene group having 2 to 4 carbon atoms (for example, an ethylene group, a linear or branched propylene group, or a linear or branched butylene group). Preferably, m2a is preferably 0-15, more preferably 0-10, and R ^2b is an alkylene group having 2 to 10 carbon atoms, particularly preferably a pentamethylene group, m2b Is preferably 3-15, more preferably 3-10. X ² is a direct bond or a divalent organic residue, and is preferably a direct bond or —CH ₂ CH ₂ NHC (═O) —. When X ² is a direct bond, E ^2a is —R ^2a —O—, E ^2b is —C (═O) —R ^2b —O—, X ³ is a direct bond, and Y ² is The following general formula (6 ′) of a combination that is a hydrogen atom is preferable.
General formula (6 ')

Further, in the general formula (6 ′), R ^2a is preferably an ethylene group, a linear or branched propylene group, or a linear or branched butylene group, and m2a is 0 to 3. (More preferably 1), R ^2b is preferably a pentamethylene group, and m2b is preferably 3-10.

When X ² is —CH ₂ CH ₂ NHC (═O) —, E ^2a is —O—R ^2a —, and E ^2b is —O—R ^2b —C (═O) —. , X ³ is —O—, and Y ² is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and the following general formula (6 ″) is preferable.
General formula (6 '')

Furthermore, in the general formula (6 ″), R ^2a is preferably an ethylene group, a linear or branched propylene group, or a linear or branched butylene group, and m2a is 0 to 3. (More preferably 0), R ^2b is preferably a pentamethylene group, and m2b is preferably 3-10.

Another preferred structure of the unit (B) having a side chain is a vinyl copolymer represented by the following general formula (7).
General formula (7):

[In general formula (7),
R ⁴ is a hydrogen atom, a methyl group, or —C (═O) —O—R ¹¹ ,
R ¹¹ is a linear or branched alkyl group having 1 to 18 carbon atoms,
X ⁴ is a direct bond or a divalent organic residue,
R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an aromatic group or —C (═O) —X ⁵ —R ⁷ ;
X ⁵ is —O— or —NH—.
R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkyl group may have an aromatic group substituent;
m3 is 10-100,
Y ³ is a polymerization stopping group of the vinyl polymer. ]
In the general formula (7), the repeating units represented by (—CH ₂ —CR ⁵ R ⁶ —) may be the same (homopolymer) or different (copolymer). Good. m3 is 10-100. R ⁶ represents an aromatic group, or —C (═O) —X ⁵ —R ⁷ (X ⁵ represents —O— or —NH—, R ⁷ represents a hydrogen atom or a carbon atom number of 1 to 18). In particular, R ⁶ is a phenyl group, or R ⁵ is —O—, where —C (═O) —O—R ⁷ (where R ⁷ is a methyl group). , An ethyl group, a linear or branched butyl group). X ⁴ is a direct bond or a divalent organic residue, preferably a direct bond, or —C (═O) OCH ₂ CH ₂ S—, —C (═O) NHCH ₂ CH ₂ S—. is there.

Y ³ in the general formula (7), that is, the polymerization terminator of the vinyl polymer is any known polymer terminator introduced when the usual ethylenically unsaturated monomer is polymerized by a usual method. And are obvious to those skilled in the art. Specifically, for example, it can be a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Even if Y ³ has any of these chemical structures, the dispersant of the present invention can exert its effect without being affected by the polymerization termination group Y ³ .

Preferred vinyl dispersants according to the present invention include a carboxyl group-containing unit (G) represented by the general formula (1), a unit (B) having a side chain represented by the general formula (2), The block copolymer or random copolymer which consists of each structural unit with a main chain structural unit (L) and represented by following General formula (8) can be mentioned.
General formula (8)

(L) is a main chain constituent unit represented by the following general formula (9).

General formula (9)

[In general formula (9),
R ⁸ is a hydrogen atom or a methyl group,
R ⁹ is an aromatic group or —C (═O) —X ⁶ —R ¹⁰ ;
X ⁶ is —O— or —NH—,
R ¹⁰ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkyl group may have an aromatic group substituent. ],
The arrangement of the unit (G) having a carboxyl group, the unit (B) having a side chain, and the main chain constituent unit (L) is not limited to the order thereof, and the vinyl represented by the general formula (8) In the polymer main chain, each unit (G), (B), and (L) is included in any order, and each unit (G), (B), and ( L) can be included in a random type or a block type, the unit having a carboxyl group (G), the unit having a side chain (B) contained in the general formula (8), and When a plurality of main chain structural units (L) are present, they can be the same or different from each other, and p1, p2, and p3 are the structural units per molecule of the vinyl-based dispersant. The average number is shown, and p1 is 0.3 or more and 30 or less (preferably 0.35 or more and 2 Or less, more preferably 0.4 to 20), p2 is 0.5 or more and 50 or less (preferably 0.8 to 30), p3 is 6 or more 250 or less (preferably 10 to 100).

Moreover, in the said General formula (8), the unit (G) which has a carboxyl group, the unit (B) which has a side chain, and the main chain structural unit (L) exist in a block copolymerization form or a random copolymerization form, respectively. can do. Further, the unit (G), the unit (B), and the unit (L) may be present in plural in the general formula (8). In this case, the respective units are the same as each other. Or it can be different. For example, the main chain structural unit (L) can include structural units having two or more structures. The arrangement of the units (G), units (B), and units (L) does not mean that (G) _p1 , (B) _p2 , and (L) _p3 are included in this order, It means that each unit (G), unit (B), and unit (L) can be included in any order.

  As a preferable form of the unit (G) having a carboxyl group and the unit (B) having a side chain contained in the vinyl dispersant according to the present invention represented by the general formula (8), the unit (G) This is the same as the unit (B).

  The main chain structural unit (L) is other than the unit (G) and the unit (B) and is represented by the following general formula (9).

  General formula (9)

[In general formula (9),
R ⁸ is a hydrogen atom or a methyl group,
R ⁹ is an aromatic group or —C (═O) —X ⁶ —R ¹⁰ ;
X ⁶ is —O— or —NH—,
R ¹⁰ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkyl group may have an aromatic group substituent. ]
In the general formula (9), R ⁸ is a methyl group, and R ⁹ is —C (═O) —O—CH ₂ —Ar (where Ar is an aromatic group, particularly a phenyl group). The main chain structural unit (L1) is preferably included, and the main chain structural unit (L1) is preferably contained in an amount of 1 or more and 100 or less on average per vinyl polymer molecule.

Further, as the main chain structural unit (L), a R ⁸ is a hydrogen atom or a methyl group, R ⁹ is -C (= O) -O-R 10 ( where, R ¹⁰ is 1 to 18 carbon atoms It is preferable that the main chain structural unit (L2) which is a linear or branched alkyl group) is included. It is more preferable that the main chain structural unit (L2) coexists with the main chain structural unit (L1) in the vinyl dispersant.

Furthermore, as the main chain structural unit (L), a main chain structural unit (L3) in which R ⁸ is a hydrogen atom and R ⁹ is an aromatic group (particularly a phenyl group) alone, or It is preferable to include the main chain structural unit (L1) and / or the main chain structural unit (L2) together. Further, as the main chain structural unit (L), a main chain structural unit (L4) in which R ⁸ is a hydrogen atom or a methyl group, and R ⁹ is a carboxyl group, the main chain structural unit (L1), main chain It can also be included together with the structural unit (L2) and / or the main chain structural unit (L3).

The terminal of the main chain of the vinyl dispersant represented by the general formula (8) is a known polymerization method of an ethylenically unsaturated monomer or a structure considered in the polymerization process, for example, derived from a polymerization initiator, chain transfer The number average molecular weight of the vinyl dispersant in the present invention, which may have a chemical structure derived from an agent, a solvent, or an ethylenically unsaturated monomer, is preferably 500 or more and 50000 or less, more preferably It is 1000 or more and 40000 or less, Most preferably, it is 1500 or more and 30000 or less. Even if it is less than 500 or exceeds 50,000, the viscosity of the dispersion may increase, which may be undesirable.

  Next, the manufacturing method of the dispersing agent by this invention is demonstrated. The dispersant of the present invention can be produced by the production method of the present invention.

  The method for producing a dispersant in the present invention comprises reacting an acid anhydride group of an aromatic tricarboxylic acid anhydride or aromatic tetracarboxylic acid anhydride with an acid anhydride reactive group of a compound having an acid anhydride reactive group. A step [1] of forming an aromatic carboxyl group, and further a step [2] of forming a unit having a side chain and / or a step [3] of forming a main chain by vinyl polymerization. .

  First, the step of reacting an acid anhydride group of an aromatic tricarboxylic acid anhydride or aromatic tetracarboxylic acid anhydride with an acid anhydride reactive group of a compound having an acid anhydride reactive group in the present invention [1] Will be described.

  As said process [1], the following process or the combination of these processes is mentioned, for example.

(I) Reacting an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride with an ethylenically unsaturated monomer (h) having an acid anhydride reactive group to produce an ethylenically unsaturated monomer having a carboxyl group A step [1a] of synthesizing the monomer (g),
(Ii) A vinyl copolymer which is a main chain having an acid anhydride reactive group is synthesized in advance, and an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride is converted into an acid anhydride reactive group of the vinyl copolymer. A step [1b] of synthesizing a vinyl copolymer containing a unit (G) having a carboxyl group by reacting with
(Iii) While reacting an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride with an ethylenically unsaturated monomer (h) having an acid anhydride reactive group, a vinyl copolymer as a main chain is produced. Step of synthesis [1c].

  Examples of the aromatic tricarboxylic acid anhydride used in the above step include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzenetricarboxylic acid). Acid anhydride)), naphthalene tricarboxylic acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1 , 2,8-naphthalene tricarboxylic acid anhydride), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid Anhydride, 2,3,2'-biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid Objects, and the like 3,4,4'-biphenyl sulfonic tricarboxylic anhydride.

  In the method of the present invention, in an aromatic tetracarboxylic dianhydride described later, one acid anhydride group in one molecule is converted to water, an alcohol having 1 to 18 carbon atoms, or a cyclohexane having 5 to 18 carbon atoms. Alcohol (eg, methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol or cyclopentanol, linear or branched hexanol or cyclohexanol , Linear or branched heptanol or cycloheptanol, linear or branched octanol or cyclooctanol, linear or branched nonanol or cyclononanol, linear or branched decanol or cyclodecane Nord, linear or branched Examples include decanol or cyclododecanol, linear or branched myristyl alcohol or cyclomyristyl alcohol, linear or branched cetyl alcohol or cyclocetyl alcohol, linear or branched stearyl alcohol, or cyclostearyl alcohol. The aromatic tetracarboxylic acid monoanhydride and the aromatic tetracarboxylic acid monoester monoanhydride that have been opened in (1) can also be used as the aromatic tricarboxylic acid anhydride in the method of the present invention. In the present specification, the aromatic tetracarboxylic acid monoester monoanhydride is described as an aromatic tricarboxylic acid anhydride. Specific examples of these aromatic tetracarboxylic anhydride monoester monoanhydrides will be apparent to those skilled in the art from the aromatic tetracarboxylic dianhydrides described below.

  Water, alcohol having 1 to 18 carbon atoms, and cycloalcohol having 5 to 18 carbon atoms used for the ring-opening reaction of the aromatic tetracarboxylic acid anhydride can be used alone or in combination of two or more. .

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3, 3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-fura Tetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4 , 4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride Bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmeta Dianhydrides, 9,9-bis (3,4-dicarboxyphenyl) fluoric acid dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluoric acid dianhydride and the like. Can be mentioned.

  What is preferably used in the present invention is trimellitic anhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid from the viewpoint of reducing the viscosity of the pigment dispersion or various inks. Dianhydride, ethylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride is preferred.

  Moreover, the aromatic tricarboxylic acid anhydride and aromatic tetracarboxylic acid anhydride mentioned above can also be used individually or in combination of 2 or more types.

  Examples of the ethylenically unsaturated monomer (h) having an acid anhydride reactive group in the step [1a] include an ethylenically unsaturated monomer (ha) having a hydroxyl group.

  The ethylenically unsaturated monomer (ha) having a hydroxyl group may be any monomer as long as it is a monomer having a hydroxyl group and having an ethylenically unsaturated double bond. (Meth) acrylate monomers such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate and cyclohexanedi Hydroxyalkyl (meth) acrylates such as methanol mono (meth) acrylate, alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth) acrylamide monomers having a hydroxyl group, such as N- (2-Hydroxyethyl) (meth) acrylamide N- (hydroxyalkyl) (meth) acrylamides such as N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, or vinyl ether monomers having a hydroxyl group, such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, hydroxyalkyl vinyl ethers such as 2- (or 3- or 4-) hydroxybutyl vinyl ether, or allyl ether monomers having a hydroxyl group, for example, Examples include hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, 2- (or 3- or 4-) hydroxybutyl allyl ether. What is preferably used in the present invention is 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate.

  The ethylenically unsaturated monomers (ha) having a hydroxyl group mentioned above can be used alone or in combination of two or more.

  In the step [1b], the acid anhydride reactive group in the vinyl copolymer which is a main chain portion synthesized in advance includes, for example, a hydroxyl group, and the ethylenically unsaturated monomer (ha) having the hydroxyl group described above. It can obtain by copolymerizing the ethylenically unsaturated monomer containing.

  In addition, the hydroxyl group of the compound obtained by adding alkylene oxide and / or lactone to the acid anhydride reactive group (preferably 0 to 3 mol) may also be used as the acid anhydride reactive group in step [1]. it can. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bond form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

  As a specific example of the step [1a], as shown in the step [1a-9] of Example 9, an ethylenic unsaturated group having a carboxyl group is obtained by reacting trimellitic anhydride with 2-hydroxyethyl methacrylate. A monomer (g9) can be obtained. As another specific example, as shown in Step [1a-10] of Example 10, pyromellitic anhydride is reacted with 2-hydroxyethyl methacrylate, and the resulting ethylenically unsaturated group having a carboxyl group is obtained. By adding water to the monomer (g10 ′) and hydrolyzing the remaining acid anhydride groups, an ethylenically unsaturated monomer (g10) having a carboxyl group can be obtained.

  As a specific example of the step [1b], as shown in the step [1b-2] of Example 2, a vinyl copolymer obtained by copolymerizing an ethylenically unsaturated monomer containing 4-hydroxybutyl acrylate A vinyl copolymer containing a unit (G2) having a carboxyl group can be obtained by reacting the hydroxyl group therein with trimellitic anhydride.

  The reaction temperature in the step [1] is preferably 80 ° C to 180 ° C, more preferably 90 ° C to 160 ° C. If the reaction temperature is less than 80 ° C, the reaction rate may be slow and may not be preferable, and if it exceeds 180 ° C, the reaction may be difficult to complete. In particular, in the step [1a], it is preferable to carry out at 80 ° C. to 150 ° C. by adding a polymerization inhibitor while allowing dry air to flow into the reactor so that the monomer does not thermally polymerize. Is 90 ° C to 130 ° C. If it exceeds 150 ° C., the monomer may be unfavorably thermally polymerized. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like. The reaction ratio in the step [1a] is 0.5 << H when the number of moles of the acid anhydride reactive group is <H> and the number of moles of the acid anhydride group of the carboxylic acid anhydride is <N>. > / <N> <10, more preferably 0.7 << H> / <N> <7.0, most preferably 1.0 << H> / <N> <5.0. is there. If <H> / <N> <0.5, a large amount of carboxylic acid anhydride remains, which is not preferable. When 10 << H> / <N>, a large amount of the ethylenically unsaturated monomer (h) having an acid anhydride reactive group remains, and another ethylenically unsaturated monomer that can be copolymerized in a later step It is not preferable because the amount of body decreases. Moreover, when making it react by <H> / <N> <1, you may hydrolyze the remaining acid anhydride with a required amount of water or a C1-C18 alcohol.

  In the step [1], a catalyst may be used. As the catalyst, tertiary amine compounds can be used, such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and the like.

  Next, the step [2] of forming a unit having a side chain in the present invention will be described. The structure of the side chain in the present invention is not particularly limited, but is preferably a polyether, polyester, or vinyl copolymer from the viewpoint of reducing the viscosity of the dispersant.

  Examples of the step [2] in the present invention include the following steps or a combination of these steps.

(I) a step [2a] of synthesizing an ethylenically unsaturated monomer (b) having a side chain;
(Ii) a step [2b] of forming a side chain using a reactive functional group in the vinyl co-aggregate which is a main chain portion and synthesizing a vinyl copolymer containing a unit (B) having a side chain;
The step [2a] is not particularly limited, and for example, an ethylene having a group that reacts with a functional group such as a polyether, polyester, or vinyl copolymer having a functional group such as a hydroxyl group at one end. Examples include a step of reacting with an ethylenically unsaturated monomer and a step of ring-opening polymerization of alkylene oxide and / or lactone from a hydroxyl group in the ethylenically unsaturated monomer.

As a specific example, as shown in the step [2a-9] of Example 9, ε-caprolactone was ring-opening polymerized using dodecanol as an initiator to synthesize a polyether having a hydroxyl group at one end, and methacryloyloxyethyl isocyanate. To obtain an ethylenically unsaturated monomer (b9) having a polyester side chain. As another specific example, ethylenically unsaturated monomer (b _2a ) having a polyester side chain by ring-opening polymerization of δ-valerolactone and ε-caprolactone using 2-hydroxyethyl methacrylate as an initiator. Can be obtained.

  As the step [2b], for example, a vinyl copolymer having a group (for example, an isocyanate group) that reacts with a functional group such as a polyether, polyester, or vinyl copolymer having a functional group such as a hydroxyl group at one end. And a step of ring-opening polymerization of alkylene oxide and / or lactone from a hydroxyl group or amino group in the vinyl co-aggregate which is the main chain portion. The vinyl copolymer used in the step [2b] is not particularly limited as long as it can form the unit (B) having a side chain. It may be used, and is preferably a vinyl copolymer produced by the step [3] described later.

As a specific example, an ethylenically unsaturated monomer containing methacryloyloxyethyl isocyanate is copolymerized, and the isocyanate group in the obtained vinyl co-aggregate is reacted with a one-end methoxylated polyethylene glycol to form a polyether side. A vinyl co-aggregate containing a chain-containing unit (B _2b ) can be obtained. As another specific example, as shown in the step [2b-1] of Example 1, a vinyl coaggregate (a step of copolymerizing an ethylenically unsaturated monomer containing 2-hydroxyethyl methacrylate [3 The vinyl copolymer containing the unit (B1) having a polyester side chain can be obtained by ring-opening polymerization of ε-caprolactone using the hydroxyl group in (1) as an initiator.

  Next, the process [3] for producing a main chain in the present invention will be described. The step [3] of forming a main chain by vinyl polymerization in the present invention is an ethylenically unsaturated monomer capable of forming a carboxyl group-containing ethylenically unsaturated monomer (g) and / or a carboxyl group-containing unit. Ethylenic unsaturation comprising a body (g ′) and an ethylenically unsaturated monomer (b) having a side chain and / or an ethylenically unsaturated monomer (b ′) capable of forming a unit having a side chain A process for synthesizing a vinyl copolymer by copolymerizing monomers will be described.

  The ethylenically unsaturated monomer (g ′) capable of forming a unit having a carboxyl group may form a unit (G) having a carboxyl group by the step [1b] after the step [3]. An ethylenically unsaturated monomer that can be formed, preferably an ethylenically unsaturated monomer having a hydroxyl group (ha), and an ethylenically unsaturated monomer having a side chain (b) ') Represents an ethylenically unsaturated monomer capable of forming the unit (B) having a side chain by the step [2b] after the step [3], preferably ethylene having a hydroxyl group. The unsaturated monomer (ha).

  Further, the ethylenically unsaturated monomer (g ′) capable of forming a unit having a carboxyl group and the ethylenically unsaturated monomer (b ′) capable of forming a unit having a side chain are the same even if they are different. If it is the same, 2-hydroxyethyl methacrylate or 4-hydroxybutyl acrylate is preferable.

  The ethylenically unsaturated monomer (g) having a carboxyl group is preferably the one obtained in the step [1a], and the ethylenically unsaturated monomer (b) having the side chain is Even if it is obtained in the step [2a], a commercially available polyester, polyether or vinyl copolymer having an ethylenically unsaturated bond may be used. Examples of the product include Nippon Oil & Fats Uniox series, Blemmer series, Daicel Chemicals Plaxel F series, Toagosei Co., Ltd. macromonomer series, and the like.

  In the step [3], the copolymer can be copolymerized with another ethylenically unsaturated monomer, and the other ethylenically unsaturated monomer may have 1 to 1 carbon atoms which may be substituted with an aromatic group. 18 alkyl (meth) acrylates, N-alkyl (meth) acrylamides having 1 to 18 carbon atoms, styrene, ethylenically unsaturated monomer (h) having a hydroxyl group, and ethylenically unsaturated monomer having a carboxyl group It is preferably selected from the body.

  Examples of the unsubstituted alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, linear or branched propyl (meth) acrylate, and linear or branched butyl (meth) acrylate. , Linear or branched pentyl (meth) acrylate, cyclopentyl (meth) acrylate, linear or branched hexyl (meth) acrylate, cyclohexyl (meth) acrylate, linear or branched heptyl (meth) Acrylate, cycloheptyl (meth) acrylate, linear or branched octyl (meth) acrylate, cyclooctyl (meth) acrylate, linear or branched nonyl (meth) acrylate, cyclononyl (meth) acrylate, linear Shape or branch Decyl (meth) acrylate, cyclodecyl (meth) acrylate, linear or branched dodecyl (meth) acrylate, cyclododecyl (meth) acrylate, linear or branched myristyl (meth) acrylate, cyclomyristyl (meta ) Acrylate, linear or branched cetyl (meth) acrylate, cyclocetyl (meth) acrylate, and linear or branched stearyl (meth) acrylate, or cyclostearyl (meth) acrylate. Examples of the alkyl (meth) acrylate substituted with an aromatic ring include benzyl (meth) acrylate. Examples of the aliphatic polycyclic (meth) acrylate include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.

  Examples of the unsubstituted N-alkyl (meth) acrylamide include, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, linear or branched N-propyl (meth) acrylamide, linear or Branched N-butyl (meth) acrylamide, linear or branched N-pentyl (meth) acrylamide, N-cyclopentyl (meth) acrylamide, linear or branched N-hexyl (meth) acrylamide, N -Cyclohexyl (meth) acrylamide, linear or branched N-heptyl (meth) acrylamide, N-cycloheptyl (meth) acrylamide, linear or branched N-octyl (meth) acrylamide, N-cyclooctyl (Meth) acrylamide, linear or branched N Nonyl (meth) acrylamide, N-cyclooctyl (meth) acrylamide, linear or branched N-decyl (meth) acrylamide, N-cyclodecyl (meth) acrylamide, linear or branched N-dodecyl (meta ) Acrylamide, N-cyclododecyl (meth) acrylamide, linear or branched N-myristyl (meth) acrylamide, N-cyclomyristyl (meth) acrylamide, linear or branched N-cetyl (meth) acrylamide N-cyclocetyl (meth) acrylamide, linear or branched N-stearyl (meth) acrylamide, or N-cyclostearyl (meth) acrylamide. Examples of the alkyl (meth) acrylamide substituted with an aromatic ring include N-benzyl (meth) acrylamide. Here, “(meth) acrylate” refers to methacrylate or acrylate, and “(meth) acrylamide” refers to methacrylamide or acrylamide.

  Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, acrylic acid dimer, caprolactone adduct of acrylic acid ( Examples of the addition mole number are 1 to 5), and caprolactone adduct of methacrylic acid (addition mole number is 1 to 5).

  Other ethylenically unsaturated monomers mentioned above can be used in combination of two or more.

  In the step [3], it is preferable to perform polymerization at 50 ° C. to 150 ° C. using a polymerization initiator while replacing the reaction vessel with nitrogen. As the polymerization initiator, alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, isobutyl peroxide, laurolyl peroxide, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3, 3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate organic peroxides such as t-butylperoxyisobutyrate, 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisdiisobutyrate, 2,2′-azobis (2,4 -Azo compounds such as dimethylvaleronitrile) and 2,2-azobis (2-methylbutyronitrile). Of these, azo compounds are preferably used. The polymerization initiator is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total of ethylenically unsaturated monomers.

  In the step [3], a chain transfer agent can also be used. Chain transfer agents include methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, ethylene glycol bisthioglycolate, butanediol bisthioglycolate, hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate , Pentaerythritol tetrakisthioglycolate, methyl mercaptopropionate, methoxybutyl mercaptopropionate, octyl mercaptopropionate, tridecyl mercaptopropionate, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthio Examples include propionate and α-methylstyrene dimer.

  In the step [3], it is preferable to use a solvent. Solvents include acetates such as ethyl acetate, propyl acetate, butyl acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone; xylene, toluene, ethylbenzene, etc. Aromatic hydrocarbons can be used. The above-mentioned solvents or other solvents can be used alone or in combination of two or more.

  Specifically, as the step [3], as shown in the step [3-1] of Example 1, butyl methacrylate, methyl methacrylate, benzyl methacrylate, and 2-hydroxyethyl methacrylate (form a unit having a carboxyl group). A hydroxyl group by copolymerizing an ethylenically unsaturated monomer (g′1) that can be formed and an ethylenically unsaturated monomer (b′1) that can form a unit having a side chain) A vinyl copolymer can be obtained. As another specific example, as shown in Step [3-9] of Example 9, n-butyl methacrylate, methyl methacrylate, benzyl methacrylate, an ethylenically unsaturated monomer having a carboxyl group (g9) ( The step [1a-9] in which trimellitic anhydride is reacted with 2-hydroxyethyl methacrylate and the ethylenically unsaturated monomer (b9) having a side chain (opening ε-caprolactone to dodecanol) The unit (G9) having a carboxyl group and the unit (B9) having a side chain are obtained by copolymerizing a step [2a-9] obtained by ring polymerization and further reacting with methacryloyloxyethyl isocyanate. A vinyl copolymer containing can be obtained.

As described above, the vinyl dispersant of the present invention can be produced by a production method including at least the step [1]. Furthermore, it can be manufactured by a manufacturing method including the step [2] and / or the step [3]. In the case of including a plurality of steps, the steps can be performed a plurality of times in an arbitrary order. For example, as shown in Example 1, step [3] -step [1] -step [2], even in the order of step [3] -step [1] -step [1] 2]-Step [3] order.
For example, the pigment can be favorably dispersed by the dispersant of the present invention. Examples of the pigment that can be dispersed by the dispersant of the present invention include various pigments used in inks and the like. Organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ansan There are throne pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments and the like. More specific examples are indicated by generic names of color indexes. Pigment Black 7, Pigment Blue 6, 15, 15 : 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 144, 146, 149, 166, 168 , 177, 178, 179 185, 206, 207, 209, 220, 221, 238, 242, 254, 255, 256, 257, 264, 266, 268, 269, 272, 279, Pigment Violet 19, 23, 29, 30, 37, 40, 50, Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 191, 193, 194, 199, 205, 206, 212, 213, 214, 215, 219, Pigment Orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74, 81 and the like.

  Further, the dispersant of the present invention includes titanium oxide, iron oxide, antimony pentoxide, zinc oxide, silica and other metal oxides, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, carbon black. It can also be used for inorganic pigments.

  Furthermore, the dispersant of the present invention is used for dispersion of fine particles other than pigments, for example, solid fine particles containing metal fine particles such as gold, silver, copper, platinum, iron, cobalt, nickel, titanium and / or alloys thereof. be able to.

The dispersant of the present invention is not limited to the above-illustrated pigments, but may be applied to any fine powders. However, since the dispersant of the present invention has a carboxyl group and has strong interaction with solid fine particles (particularly pigments) whose surface is neutral to basic, such solid fine particles (particularly pigments) are preferred. In particular, in the case of an organic pigment, a pigment whose surface is biased to basic is preferable. The pigment whose surface is biased to basic is the formula:
[P] = [As]-[Bs]
([As] is the “surface base amount of the pigment”, and [Bs] is the “surface acid amount of the pigment”)
The [P] value calculated by is a pigment having a value of 30 μmol / g or more. The surface base amount and the surface acid amount of the pigment can be determined by the method described in the literature (coloring material, 61 [12], 692-698, 1988), for example.

  The pigment dispersion of the present invention refers to a paste or a chip that can be obtained by dispersing a pigment with the dispersant of the present invention. A pigment dispersion can be obtained only with the dispersant and the pigment of the present invention. In addition, a pigment dispersion may be obtained by dispersing the pigment in a pigment carrier (resin, its precursor, or a mixture thereof), a solvent, or a varnish other than the dispersant using the dispersant of the present invention. it can.

  The blending amount of the dispersant is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 75 parts by weight, and most preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the pigment. If the dispersant is less than 0.1 parts by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and if it exceeds 100 parts by weight, the dispersibility may be deteriorated.

  The pigment dispersion of the present invention includes at least one selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. A synergist having a basic group (hereinafter sometimes referred to as a basic synergist) can be added. The basic synergist adsorbs to the surface of the pigment, and even a non-neutral to basic pigment can make the surface basic. On the other hand, the dispersant of the present invention has a specific structure having two or three aromatic carboxyl groups, and this structure and the basic group of the basic synergist (present on the pigment surface) are The pigment can stably exist in the dispersion medium due to electrostatic interaction, and the polymer part present in the dispersant has affinity with the solvent as the dispersion medium.

  Basic synergists that can be contained in the pigment dispersion of the present invention include “pigment derivatives having basic groups”, “anthraquinone derivatives having basic groups”, “acridone derivatives having basic groups”, and “bases” It can be selected from the group consisting of “triazine derivatives having a functional group”.

Examples of the basic group include at least one group selected from the group consisting of groups represented by the following general formula (21), the following general formula (22), the following general formula (23), and the following general formula (24). be able to.
Formula (21):

Formula (22):

Formula (23):

General formula (24):

In the general formula (21) to the general formula (24),
Each J independently represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond;
f represents an integer of 1 to 10,
R ³¹ and R ³² are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ³¹ and R ³² in the formula Together with a nitrogen atom, represents a heterocyclic residue which contains a nitrogen atom, an oxygen atom, or a sulfur atom and may be substituted;
R ³³ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. ,
K represents —NR ³⁸ —Z—NR ³⁹ — or a direct bond;
R ³⁸ and R ³⁹ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
Z represents an alkylene group that may be substituted, an alkenylene group that may be substituted, or a phenylene group that may be substituted;
W represents a substituent represented by the general formula (21) or a substituent represented by the general formula (23);
T represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (21), or a substituent represented by the general formula (23).

In a preferred form of the substituent represented by the general formula (21), J is —SO ₂ — or —CO—, f is 1 to 5 (more preferably 2 to 4), and R ³¹ and R ³² Are each independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, or an iso-butyl group, or R ³¹ and R ³² are combined with a nitrogen atom in the formula In this case, morpholine is formed.

In a preferred form as the substituent represented by the general formula (22), R ³¹ and R ³² are each independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group. This is the case.

In a preferable form as the substituent represented by the general formula (23), J is —CH ₂ NHCOCH ₂ —, and R ³³ is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group. Or, it is an iso-butyl group, and R ^{34 to} R ³⁷ are hydrogen atoms.

In a preferred form as the substituent represented by the general formula (24), J is a direct bond or —SO ₂ —, K is a direct bond or —NH—Z—NH—, Z is a phenylene group, T is a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group, W is a substituent represented by the general formula (21), and J in W is a direct bond, —SO ₂ — or —CO And f in W is 1 to 5 (more preferably 2 to 4), and R ³¹ and R ^{32 in} W are each independently a methyl group, an ethyl group, an n-propyl group, iso This is the case when it is a -propyl group, n-butyl group or iso-butyl group.

  Examples of the amine compound used for forming the substituent represented by the general formula (21) to the general formula (24) include a secondary or tertiary monoamine, a diamine, a cyclic amine, and a carboxyl group-containing cyclic amine. , Hydroxyl group-containing cyclic amines, and cyclic diamines. Specifically, dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine , Diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpro Ruamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hex Ruaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpipecoline Razine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like can be mentioned.

  Examples of the “pigment part constituting the pigment derivative having a basic group” include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, and flavantrons. Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes Derived from organic dyes such as selenium dyes and metal complex dyes. Further, “anthraquinone derivative having a basic group” or “acridone derivative having a basic group” includes, on the anthraquinone ring or acridone ring, in addition to the basic group, an alkyl group such as a methyl group or an ethyl group, an amino group It may have a substituent such as a group, a nitro group, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a halogen such as chlorine.

  Further, the triazine moiety constituting the “triazine derivative having a basic group” includes, in addition to the basic group, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, etc.), an amino group, an alkylamino group (for example, Dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro group, hydroxyl group, alkoxy group (eg methoxy group, ethoxy group, butoxy group etc.), halogen atom (eg chlorine atom, bromine atom etc.), phenyl group (For example, an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen atom and the like may be substituted) and a phenylamino group (for example, an alkyl group, an amino group, an alkylamino group, It may have a substituent such as a nitro group, a hydroxyl group, an alkoxy group, or a halogen atom. Preferred triazine moieties are derived from 1,3,5-triazine.

The “pigment derivative having a basic group”, “anthraquinone derivative having a basic group”, and “acridone derivative having a basic group” used in the present invention can be synthesized by various known synthesis methods by known methods. it can. For example, after introducing a substituent represented by the following formula (27) to the following formula (30) into an organic dye, anthraquinone or acridone, it reacts with these substituents to react with the above general formula (21) to the above general formula ( 24) an amine compound capable of forming the substituent represented by, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) Propylamino] -1,3,5-triazin-2-ylamino] aniline and the like can be obtained.
Formula (27): —SO ₂ Cl
Formula (28): -COCl
Formula (29): —CH ₂ NHCOCH ₂ Cl
Formula (30): —CH ₂ Cl
Further, when the organic dye is an azo dye, the substituent represented by the general formula (21) to the general formula (24) is previously converted to a diazo component (for example, a compound having a diazo group) or a coupling component (for example, Azo pigment derivatives can also be produced by introducing them into a compound having an acetamide group) and then performing a coupling reaction.

  The “triazine derivative having a basic group” used in the present invention can be synthesized by a known method through various synthetic routes. For example, starting from cyanuric chloride, an amine compound that forms a substituent represented by the general formula (21) to the general formula (24) on at least one chlorine atom of cyanuric chloride, for example, N, N-dimethyl It can be obtained by reacting aminopropylamine or N-methylpiperazine or the like and then reacting the remaining chlorine atom of cyanuric chloride with various amine compounds or alcohol compounds.

  In the pigment dispersion of the present invention, the amount of the basic synergist is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight with respect to 100 parts by weight of the pigment. When the basic synergist is less than 1 part by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and / or light resistance may be deteriorated.

  The pigment dispersion of the present invention can be obtained by mixing various solvents, resins, varnishes and the like, if necessary, and dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor or the like. Pigments, synergists with basic groups, dispersants, and other resins may be dispersed after mixing all the components, but only with pigments and synergists having basic groups at first, or basic groups It is also possible to disperse only with a synergist having a dispersant and a dispersant, or only a synergist having a pigment and a basic group and a dispersant, and then adding another component.

  Also, before dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc., pre-dispersion using a kneader mixer such as a kneader, three-roll mill, etc., solid dispersion with a two-roll mill, etc., or pigment A synergist having a basic group and / or a dispersant may be treated. In addition, any disperser or mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic disperser can be used for producing the dispersion of the present invention.

  Examples of various solvents that can be used in the pigment dispersion of the present invention include organic solvents and water. When used in an active energy ray-curable dispersion, an active energy ray-curable liquid monomer or liquid oligomer may be used as a medium instead of a solvent.

  Examples of resins that can be used in the pigment dispersion of the present invention include petroleum resin, casein, shellac, rosin-modified maleic resin, rosin-modified phenol resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, Rubber, oxidized rubber, hydrochloric acid rubber, phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane Resins, silicone resins, fluororesins, drying oils, synthetic drying oils, styrene-modified maleic acid, polyamide resins, chlorinated polypropylene, butyral resins, vinylidene chloride resins, and the like.

  In addition, the pigment dispersion of the present invention includes, as other additives, a photopolymerization initiator, a chain transfer agent, a photopolymerizable compound, a thermopolymerizable compound, a crosslinking agent, a plasticizer, a surface conditioner, an ultraviolet light inhibitor, a light Stabilizers, antioxidants, antistatic agents, antiblocking agents, antifoaming agents, viscosity modifiers, waxes, surfactants, leveling agents and the like can be added.

  The pigment dispersion of the present invention can be used in non-aqueous, aqueous or solvent-free paints, gravure inks, offset inks, ink jet inks, color filter inks, digital paper inks, plastic colorants, and the like.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.
Example 1
Step [3-1]: 320 parts of methoxypropyl acetate was charged into a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tank, 40.0 parts butyl methacrylate, 40.0 parts methyl methacrylate, 200 parts benzyl methacrylate, 120 parts 2-hydroxyethyl methacrylate, 48 parts methoxypropyl acetate, and dimethyl-2,2'-azobisdiisobutyrate 24 A mixed solution in which the parts were mixed uniformly in advance was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction. Thus, a vinyl resin intermediate (1) having a number average molecular weight of 3200 was obtained.

  Step [1b-1]: A reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 200 parts of vinyl resin intermediate (1) in solids and 36 parts of trimellitic anhydride. , And reacted at 100 ° C. for 4 hours.

Step [2b-1]: Further, 224 parts of ε-caprolactone and 0.1 part of monobutyltin (IV) oxide were added and reacted at 120 ° C. for 3 hours, the number average molecular weight of the side chain was 950, and the ratio was 53 A weight percent vinyl dispersant (1) was obtained.
Example 2
Step [3-2]: 420 parts of methoxypropyl acetate was charged into a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen, and then dropped. From the tank, 50.0 parts butyl methacrylate, 50.0 parts methyl methacrylate, 250 parts benzyl methacrylate, 150 parts 4-hydroxybutyl methacrylate, 60 parts methoxypropyl acetate, and 30 dimethyl-2,2'-azobisdiisobutyrate. A mixed solution in which the parts were mixed uniformly in advance was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction. Thus, a vinyl resin intermediate (2) having a number average molecular weight of 3000 was obtained.

  Step [1b-2]: A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 125 parts of vinyl resin intermediate (2) in solids and 8 parts of trimellitic anhydride. And reacted at 100 ° C. for 3 hours.

Step [2b-2]: Furthermore, 187 parts of ε-caprolactone and 0.1 part of monobutyltin (IV) oxide were added and reacted at 120 ° C. for 4 hours. The number average molecular weight of the side chain was 950, and the ratio was 65% by weight of a vinyl dispersant (2) was obtained.
Example 3
The number average molecular weight of the side chain is 950 in exactly the same manner as in Example 2 except that the amount of trimellitic anhydride charged in Example 2 is 24 parts and the amount of ε-caprolactone is 102 parts. Yes, and a vinyl dispersant (3) having a ratio of 44% by weight was obtained.
Example 4
Step [3-4]: A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 320 parts of methoxypropyl acetate, heated to 110 ° C., the inside of the reaction vessel was purged with nitrogen, and then dropped. From the tank, 200 parts of Bremer 50POEP-800B (polyether containing ethylenically unsaturated bond: manufactured by NOF Corporation), 120 parts of benzyl methacrylate, 80 parts of 2-hydroxyethyl methacrylate, 48 parts of methoxypropyl acetate, and dimethyl-2, A mixed solution in which 24 parts of 2′-azobisdiisobutyrate was uniformly mixed in advance was added dropwise over 2 hours, and then stirred at the same temperature for 3 hours to complete the reaction. Thus, a vinyl resin intermediate (4) having a number average molecular weight of 2500 and a side chain number average molecular weight of 750 was obtained.

Step [1b-4]: In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 200 parts of vinyl resin intermediate (4) in solids, 33 parts of trimellitic anhydride, , 8-diazabicyclo- [5.4.0] -7-undecene was charged in 0.2 parts and reacted at 130 ° C. for 3 hours to obtain a vinyl dispersant (4) having a side chain ratio of 44% by weight. .
Example 5
Step [3-5]: After charging 62.5 parts of methoxypropyl acetate in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, heating to 110 ° C., and replacing the inside of the reaction vessel with nitrogen From a dropping tank, 125 parts of a 50% solution in which macromonomer AA-6 (polymethyl methacrylate containing ethylenically unsaturated bond: Toagosei Co., Ltd.) was previously dissolved in methoxypropyl acetate, 75 parts of benzyl methacrylate, 2-hydroxy A mixed solution in which 50 parts of ethyl methacrylate, 10 parts of methoxypropyl acetate and 5 parts of dimethyl-2,2′-azobisdiisobutyrate are uniformly mixed in advance is added dropwise over 2 hours, and then stirred at the same temperature for 3 hours. To finish the reaction. Thus, a vinyl resin intermediate (5) having a number average molecular weight of 5300 and a side chain number average molecular weight of 5250 was obtained.

Step [1b-5]: In a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 200 parts of vinyl resin intermediate (5) in solids, 16 parts of trimellitic anhydride, , 8-diazabicyclo- [5.4.0] -7-undecene was charged in 0.2 parts and reacted at 130 ° C. for 3 hours to obtain a vinyl dispersant (5) having a side chain ratio of 46% by weight. .
Example 6
A number average molecular weight of 5000 is the same as that of Example 5 except that macromonomer AS-6 (polystyrene containing ethylenically unsaturated bond: manufactured by Toagosei Co., Ltd.) is used instead of macromonomer AA-6 in Example 5. Through a vinyl resin intermediate (6) having a side chain number average molecular weight of 6000, a vinyl dispersant (6) having a side chain ratio of 46% by weight was obtained.
Example 7
In the same manner as in Example 5, except that macromonomer AB-6 (ethylenically unsaturated bond-containing polybutyl acrylate: manufactured by Toagosei Co., Ltd.) was used instead of macromonomer AA-6 in Example 5, the number average was obtained. Via a vinyl resin intermediate (7) having a molecular weight of 5500 and a side chain number average molecular weight of 5850, a vinyl dispersant (7) having a side chain ratio of 45% by weight was obtained.
Example 8
The number average molecular weight of the side chain is 1250 in exactly the same manner as in Example 2 except that the amount of trimellitic anhydride charged in Example 2 is 24 parts and the amount of ε-caprolactone is 155 parts. Yes, and a vinyl dispersant (8) having a ratio of 50% by weight was obtained.
Example 9
Step [2a-9]: In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 186.3 parts of dodecanol, 342.3 parts of ε-caprolactone, 0.15 part of monobutyltin (IV) oxide as a catalyst After being replaced with nitrogen gas, heated and stirred at 120 ° C. for 4 hours, 155 parts of methacryloyloxyethyl isocyanate and 0.3 part of hydroquinone monomethyl ether were added, and the mixture was further heated and stirred for 2 hours to have a polyester side chain. An ethylenically unsaturated monomer (b9) was obtained.

  Step [1a-9]: In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 192 parts of trimellitic anhydride, 130.1 parts of 2-hydroxyethyl methacrylate, 1,8-diazabicyclo- [ 5.4.0] -7-Undecene (0.2 parts) and hydroquinone monomethyl ether (0.3 parts) were added and reacted at 100 ° C. for 5 hours while flowing dry air to add trimellitic acid to 2-hydroxyethyl methacrylate. An ethylenically unsaturated monomer having a carboxyl group (g9) was obtained.

  Step [3-9]: After charging 450.5 parts of methoxypropyl acetate into a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, raising the temperature to 110 ° C., and replacing the inside of the reaction vessel with nitrogen From the dropping tank, n-butyl methacrylate 50 parts, methyl methacrylate 50 parts, carboxyl group-containing ethylenically unsaturated monomer (g9) 50 parts, benzyl methacrylate 125 parts, ethylenically unsaturated monomer having a side chain (B9) 225 parts, methoxypropyl acetate 30 parts and dimethyl-2,2′-azobisdiisobutyrate 15 parts in advance are mixed dropwise over 2 hours, and then stirred at the same temperature for 3 hours. To finish the reaction.

Thus, a vinyl dispersant (9) having a number average molecular weight of 6300, a side chain number average molecular weight of 650, and a side chain ratio of 42% by weight was obtained.
Example 10
Step [1a-10]: 218.1 parts pyromellitic anhydride, 130.1 parts 2-hydroxyethyl methacrylate, 1,8-diazabicyclo in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer. -[5.4.0] -7-Undecene (0.2 parts) and hydroquinone monomethyl ether (0.3 parts) were charged and reacted at 100 ° C for 5 hours while flowing dry air, and pyromellitic acid was converted to 2-hydroxyethyl methacrylate. Thus, an ethylenically unsaturated monomer (g10 ′) having a carboxyl group added thereto was obtained. By adding 36 parts of water to the obtained ethylenically unsaturated monomer (10 ′) and reacting at 90 ° C. for 5 hours, an acid anhydride group remaining in the ethylenically unsaturated monomer (10 ′) is obtained. Was hydrolyzed. Subsequently, the remaining water was removed under reduced pressure to obtain an ethylenically unsaturated monomer (g10) having a carboxyl group.

  Step [3-10]: 167 parts of methoxypropyl acetate was charged into a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, heated to 110 ° C., purged with nitrogen in the reaction vessel, and then dropped. From the tank, 25 parts of n-butyl methacrylate, 12.5 parts of 2-hydroxyethyl methacrylate, 12.5 parts of an ethylenically unsaturated monomer having a carboxyl group (g10), 50 parts of benzyl methacrylate, macromonomer AB-6 ( 300 parts of a 50% solution prepared by previously dissolving ethylenically unsaturated bond-containing polybutyl acrylate (manufactured by Toagosei Co., Ltd.) in methoxypropyl acetate, 5 parts of methoxypropyl acetate, and dimethyl-2,2′-azobisdiisobutyrate Add 2.5 parts of the mixture mixed in advance over 2 hours, and then add the same temperature for 3 hours. In the end the continued stirring reaction.

Thus, a vinyl dispersant (10) having a number average molecular weight of 8,300, a side chain number average molecular weight of 5,900, and a ratio of 60% by weight was obtained.
(Reference Example 1)
Except for using 30.0 parts of phthalic anhydride instead of trimellitic anhydride in Example 1, the number average molecular weight of the side chain is 950 and the ratio is 54 wt. % Vinyl-based dispersant (S1) was obtained.
(Reference Example 2)
A vinyl dispersant (S2) containing no side chain was obtained in exactly the same manner as in Step [3-1] and Step [ 1b-1 ] in Example 1.
(Reference Example 3)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 320 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 0 parts, methyl methacrylate 40.0 parts, benzyl methacrylate 200 parts, 2-hydroxyethyl methacrylate 60 parts, acid phosphooxyethyl methacrylate 60 parts, methoxypropyl acetate 48 parts, and dimethyl-2,2'-azobisdiisobutyrate A mixed solution in which 24 parts were uniformly mixed in advance was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction. In this way, a vinyl resin intermediate having a number average molecular weight of 3200 was obtained.

In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, the obtained vinyl resin intermediate was 200 parts in solid content, 224 parts of ε-caprolactone, and monobutyltin (IV) oxide 0.1 The vinyl-based dispersant (S3) having a side chain number average molecular weight of 950 and a weight ratio of 53% was obtained.
Example 11
36 g of titanium dioxide as a pigment, 6 g of the dispersant obtained in Example 1, 53 g of methoxypropyl acetate, and 60 g of glass beads (0.8 mm in diameter) were charged into a 140 mL mayonnaise bottle, and Scandex SO400 (hereinafter referred to as Scandex) manufactured by F & FM. And dispersed for 3 hours. The glass beads were removed from this dispersion to obtain a dispersion. The dispersion was allowed to stand at 25 ° C. for 24 hours, and then the viscosity at 25 ° C. at a rotational speed of 10 rad / sec (this was the initial viscosity) Measured) was 55 mPa · s, and the TI value ([viscosity at a rotational speed of 10 rad / sec] ÷ [viscosity at a rotational speed of 1 rad / sec]) was 1.02. In addition, when this dispersion was stored in an oven at 40 ° C. for 1 week, the viscosity (called viscosity with time) was measured in the same manner as described above, and it was 57 mPa · s, and the rate of change in viscosity (viscosity with time ÷ The initial viscosity was 104%.
[Examples 12 to 22]
Dispersions were obtained in the same manner as in Example 11 using the vinyl dispersants obtained in Examples 1 to 10 above at the blending ratios (weight ratios) shown in Tables 3 and 4. Evaluation was performed in the same manner as in Example 11, and the results are shown in Tables 3 and 4. However, the viscosity stability was evaluated as ○ when the rate of change in viscosity before and after storage at 40 ° C. for 1 week was within ± 10%, and × when exceeding ± 10%.

In addition, Pigment Blue 15: 6 having a basic surface described in Example 12 of Table 3 is the following calculation formula:
F = BA
(Wherein, F is the surface surplus functional amount (μmol / g) of the pigment, B is the surface base amount (μmol / g) of the pigment, and A is the surface acid amount (μmol / g) of the pigment. Is)
Pigment Blue 15: 6 of F value (surface excess functional amount of the pigment) calculated from the formula (1) is +140 μmol / g.

Examples 13 to 22 were obtained by reacting a pigment component, anthraquinone, acridone, or triazine with an amine component, or by synthesizing a dye by coupling a compound having an amine component. The basic synergists (1) to (6) shown in FIG.
Basic synergist (1):

CuPc represents a copper phthalocyanine residue;
Basic synergist (2):

CuPc represents a copper phthalocyanine residue;
Basic synergist (3):

Basic synergist (4):

Basic synergist (5):

Basic synergist (6):

(Comparative Examples 1-2)
Dispersions were obtained in the same manner as in Example 11 using the dispersants obtained in Reference Examples 1 and 2 above at the blending ratios (weight ratios) shown in Table 5. Evaluation was performed in the same manner as in Example 11, and the results are shown in Table 5.

By using the dispersant of the present invention, it was confirmed from the Examples that a pigment can be dispersed with a low viscosity and a dispersion having good storage stability can be obtained.

  On the other hand, in the comparative example 1, since the unit which has a carboxyl group does not contain aromatic carboxylic acid, the viscosity was high and the storage stability was bad. Further, in Comparative Example 2, since there was no side chain, the viscosity was increased during dispersion, and separation from the beads was impossible. In Comparative Example 3, since phosphoric acid was used as the acid component, the storage stability was poor. As described above, the prior art dispersants have drawbacks.

  The dispersant according to the present invention can be used effectively for the preparation of pigment dispersions such as pigment dispersions and pigment compositions. Moreover, the said dispersing agent can be efficiently manufactured by the manufacturing method of this invention. Further, the pigment dispersion prepared by the dispersant is a system such as a lithographic, gravure, flexographic, ink jet, or photolitho for applications such as automobiles, painted steel sheets, building materials, cans, color filters, or other electronic materials. Therefore, it can be used for various paints, various printing inks, inkjet inks, resist inks, and the like that can be used.

Claims (8)

A unit (G) represented by the following general formula (1) having 2 or 3 aromatic carboxylic acids and a general formula (6) or (7) having a side chain having a number average molecular weight of 500 to 8000. The vinyl-type dispersing agent characterized by including a unit (B), the ratio of the side chain with respect to all the unit totals being 30-70 weight part, and a number average molecular weight being 1000-50000.
General formula (1):
[In general formula (1),
R ¹ is a hydrogen atom or a methyl group,
X ¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) —, or —CH ₂ O—,
E ^1a is a repeating unit represented by —R ^1a —O—,
E ^1b is a repeating unit represented by —C (═O) —R ^1b —O—,
R ^1a is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ^1b is a linear or branched alkylene group having 4 to 8 carbon atoms,
m1a is an integer of 0 to 10,
m1b is an integer of 0 to 5,
Y ¹ is a monovalent group represented by the following general formula (2) or general formula (3). ]
General formula (2):
[In general formula (2),
Two of A ^{1 to} A ³ are —C (═O) OH,
The other is a hydrogen atom, —C (═O) OH, or —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms),
k is 1 or 2. ]
General formula (3):
[In general formula (3),
Two of A ^{5 to} A ⁷ are —C (═O) OH,
The other is a hydrogen atom, —C (═O) OH, or —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms ) ,
R ² is a direct bond, —CH ₂ —, —O—, —C (═O) —, —C (═O) OCH ₂ CH ₂ OC (═O) —, —C (═O) OCH (OC (═O) CH ₃ ) CH ₂ OC (═O) —, —SO ₂ —, —C (CF ₃ ) ₂ —, a group represented by the following formula (4), or represented by the following formula (5). Group. ]
Formula (4)
Formula (5)
General formula (6):
(In general formula (6),
R ³ is a hydrogen atom or a methyl group,
X ² is a direct bond or a divalent organic residue,
E ^2a is a repeating unit represented by —R ^2a —O— or —O—R ^2a —,
E ^2b is a repeating unit represented by —C (═O) —R ^2b —O— or —O—R ^2b —C (═O) —,
R ^2a is a linear or branched alkylene group having 1 to 4 carbon atoms,
R ^2b is a linear or branched alkylene group having 2 to 10 carbon atoms,
m2a is 0-20,
m2b is 0-20,
X ³ is a direct bond or —O—.
Y ² is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. )
General formula (7)
[In general formula (7),
R ⁴ is a hydrogen atom, a methyl group, or —C (═O) —O—R ¹¹ ,
R ¹¹ is a linear or branched alkyl group having 1 to 18 carbon atoms,
X ⁴ is a direct bond or a divalent organic residue,
R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an aromatic group or —C (═O) —X ⁵ —R ⁷ ;
X ⁵ is —O— or —NH—.
R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkyl group may have an aromatic group substituent;
m3 is 10-100,
Y ³ is a polymerization stopping group of the vinyl polymer. ] The vinyl-type dispersing agent of Claim 1 shown by following General formula (8).
General formula (8)
[In general formula (8),
(L) is a main chain constituent unit represented by the following general formula (9),
General formula (9)
[In general formula (9),
R ⁸ is a hydrogen atom or a methyl group,
R ⁹ is an aromatic group or —C (═O) —X ⁶ —R ¹⁰ ;
X ⁶ is —O— or —NH—,
R ¹⁰ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkyl group may have an aromatic group substituent. ],
[The arrangement of the carboxyl group-containing unit (G), the side chain-containing unit (B), and the main chain constituent unit (L) is not limited to the order, and is represented by the general formula (8). In the vinyl polymer main chain, each unit (G), (B), and (L) is included in any order, and each unit (G), (B), and (L ) Can be included in random or block type,
When the unit (G) having the carboxyl group, the unit (B) having the side chain, and the main chain constituent unit (L) contained in the general formula (8) are present in plural Can be the same or different from each other,
p1, p2, and p3 represent the average number of each structural unit per molecule of the vinyl-based dispersant, p1 is 0.3 or more and 30 or less, p2 is 0.5 or more and 50 or less, and p3 is 6 More than 250. ]   The vinyl dispersant according to claim 2, wherein p1 is more than 3.0 and 20 or less. Two aromatic carboxylic acid or 3 Yes to the following general formula and units (G) represented by (1), represented by the following general formula having a side chain having a number average molecular weight 500 to 8000 (6) or (7) A method for producing a vinyl-based dispersant comprising a unit (B), wherein the ratio of the side chain to the total unit is 30 to 70 parts by weight, and the number average molecular weight is 1000 to 50000. And at least a step [1] of forming an aromatic carboxyl group serving as an anchor portion by reacting an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride with a compound having an acid anhydride reactive group. A method for producing a vinyl dispersant, which is characterized.
General formula (1):
[In general formula (1),
R ¹ is a hydrogen atom or a methyl group,
X ¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) —, or —CH ₂ O—,
E ^1a is a repeating unit represented by —R ^1a —O—,
E ^1b is a repeating unit represented by —C (═O) —R ^1b —O—,
R ^1a is a linear or branched alkylene group having 2 to 8 carbon atoms,
R ^1b is a linear or branched alkylene group having 4 to 8 carbon atoms,
m1a is an integer of 0 to 10,
m1b is an integer of 0 to 5,
Y ¹ is a monovalent group represented by the following general formula (2) or general formula (3). ]
General formula (2):
[In general formula (2),
Two of A ^{1 to} A ³ are —C (═O) OH,
The other is a hydrogen atom, —C (═O) OH, or —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms),
k is 1 or 2. ]
General formula (3):
[In general formula (3),
Two of A ^{5 to} A ⁷ are —C (═O) OH,
The other is a hydrogen atom, —C (═O) OH, or —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms),
R ² is a direct bond, —CH ₂ — , —O— , —C (═O) —, —C (═O) OCH ₂ CH ₂ OC (═O) —, —C (═O) OCH (OC (═O) CH ₃ ) CH ₂ OC (═O) —, —SO ₂ —, —C (CF ₃ ) ₂ —, a group represented by the following formula (4), or represented by the following formula (5). Group. ]
Formula (4):
Formula (5):
General formula (6):
(In general formula (6),
R ³ is a hydrogen atom or a methyl group,
X ² is a direct bond or a divalent organic residue,
E ^2a is a repeating unit represented by —R ^2a —O— or —O—R ^2a —,
E ^2b is a repeating unit represented by —C (═O) —R ^2b —O— or —O—R ^2b —C (═O) —,
R ^2a is a linear or branched alkylene group having 1 to 4 carbon atoms,
R ^2b is a linear or branched alkylene group having 2 to 10 carbon atoms,
m2a is 0-20,
m2b is 0-20,
X ³ is a direct bond or —O—.
Y ² is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. )
General formula (7):
[In general formula (7),
R ⁴ is a hydrogen atom, a methyl group, or —C (═O) —O—R ¹¹ ,
R ¹¹ is a linear or branched alkyl group having 1 to 18 carbon atoms,
X ⁴ is a direct bond or a divalent organic residue,
R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an aromatic group or —C (═O) —X ⁵ —R ⁷ ;
X ⁵ is —O— or —NH—.
R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, and the alkyl group may have an aromatic group substituent;
m3 is 10-100,
Y ³ is a polymerization stopping group of the vinyl polymer. ]   The method for producing a vinyl-based dispersant according to claim 4, comprising a step [2] of forming a unit having a side chain having a number average molecular weight of 500 to 8000.   The method for producing a vinyl-based dispersant according to claim 4 or 5, comprising a step [3] of forming a main chain by polymerizing vinyl.   A pigment dispersion comprising a pigment and the dispersant according to any one of claims 1 to 3. The method further comprises at least one basic synergist selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. The pigment dispersion described.