JP2008200664A - Dispersant, its manufacturing method, and pigment composition using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersant excellent in dispersing properties, resistance against chemicals in a vehicle, and demonstrating an excellent chemical resistance and solvent resistance after the vehicle is heat-cured. <P>SOLUTION: A vinyl polymer main chain (A) includes 0.3 to 3.0 pieces of carboxyl group containing unit (G) represented by formula (1) per one vinyl polymer molecule, and further includes a crosslinking functional group containing unit (I) represented by at least one of general formulae (51)-(55). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is excellent in dispersibility, fluidity, and storage stability, and at the same time, is excellent in chemical resistance of the color-extracted product, and further exhibits excellent chemical resistance and solvent resistance after thermosetting the color-extracted product. The present invention relates to a dispersant capable of producing a dispersion, a production method thereof, and a pigment composition 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 will cause 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 the disperser, and if bad, cause gelation during storage and use It can even be difficult. Furthermore, regarding the surface of the color-extended product, a state failure such as a decrease in gloss and a leveling failure 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 maintain a good dispersion state. The dispersant has a structure of a site that adsorbs to the pigment and a site that has a high affinity for the solvent as the dispersion medium, and the performance of the dispersant is determined by the balance of these two functional sites. Various dispersants are used in accordance with the surface state of the pigment to be dispersed, but an acidic dispersant is 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.

  Dispersants having a phosphoric acid group or a sulfonic acid group as an acidic functional group are known (for example, Patent Document 1 or Patent Document 2). These have high dispersibility and can produce a pigment dispersion having a low viscosity with a small amount of use. However, when storage stability is poor, defects due to phosphoric acid groups or sulfonic acid groups, such as poor compatibility (problems during production), low heat resistance, or low chemical resistance. Problems sometimes arise, and such a dispersant having a phosphoric acid group or a sulfonic acid group is poor in developability to applied inks or paints.

  A dispersant having a carboxylic acid group as an acidic functional group has no problem with a dispersant having a phosphoric acid group or a sulfonic acid group, but tends to be inferior in dispersion ability, and even if the amount used is increased, phosphoric acid It has been difficult to reduce the viscosity as in the case of using a dispersant having a group or a sulfonic acid group.

  In recent years, a dispersant using a carboxylic acid group and having improved ability as a dispersant has been proposed. Examples include block copolymerization of an acrylic resin having a carboxylic acid group, and examples in which polyester, polyether, polyurethane, or the like is grafted to an acrylic resin having a carboxylic acid group (for example, Patent Document 3 or Patent Document 4). .

  Although these have a high dispersion ability compared with a dispersant having a conventional carboxylic acid group, they have a low dispersion ability and a low viscosity compared to a dispersant having a phosphate group or a sulfonate group. In order to make a stable dispersion, it was necessary to use a certain amount.

  On the other hand, Patent Document 5, Patent Document 6, and Patent Document 7 propose a method of mixing a pigment composition with a synergist having an acidic group or a basic group as a substituent in a side chain using a pigment as a base skeleton. . However, this alone does not always provide a satisfactory effect, and it has been proposed to use a dispersant having a counter ion for synergists having the acidic group or basic group as a substituent as described above. (For example, patent document 8 or patent document 9). 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.

Patent Document 8 exemplifies a pigment composition containing a synergist having a basic group as a substituent and a dispersant having a phosphate group. A dispersant having a phosphoric acid group has a certain degree of pigment dispersion ability in combination with a synergist having a basic group as a substituent, but has poor storage stability or a defect derived from phosphoric acid, such as low heat resistance. In some cases, problems may arise due to poor chemical resistance and poor compatibility. The same applies to the dispersant having sulfonic acid. Pigment compositions using such dispersants having phosphoric acid groups or sulfonic acid groups are poor in expandability to applied inks and paints, etc., while conventional dispersants using carboxylic acids are basic. In the pigment composition in combination with the synergist having a group as a substituent, there is no problem in terms of heat resistance, chemical resistance, compatibility, but high viscosity, poor stability, poor pigment fine dispersion, There was a problem.
Japanese Patent No. 2633075 Japanese Patent No. 2747769 JP 2005-194487 A Japanese Patent No. 3049407 JP-A-63-305173 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 dispersant that exhibits excellent dispersibility, and at the same time, excellent chemical resistance of the color-extracted product, and further exhibits excellent chemical resistance and solvent resistance after the color-extracted product is thermally cured. It is.

  The present inventor has been intensively researching the development of a carboxylic acid group-containing dispersant having a high dispersion ability. Introduced into the main chain of the acrylic polymer), it has excellent dispersibility, at the same time, excellent chemical resistance of the developed color, and excellent chemical resistance and solvent resistance after the color developed product is thermally cured. It was found that a dispersing agent that expresses Furthermore, the present inventor has newly found an advantageous method for producing a dispersant having a wide range of structures including the vinyl polymer dispersant.

  In a preferred embodiment of the present invention, a vinyl dispersant (hereinafter sometimes referred to as vinyl dispersant (a)) is represented by the following general formula (1) in the vinyl polymer main chain (A). The carboxyl group-containing unit (G) is contained in an amount of 0.3 to 3.0 on average per molecule of the vinyl polymer, and at least one of the general formulas (51) to (55) It is a vinyl type dispersing agent characterized by including the crosslinkable functional group containing unit (I) represented.

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—,
X ² is a group represented by the general formula: — (— R ^a1 —O—) _m1 −,
(In the formula, R ^a1 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m1 is an integer of 1 to 50.)
X ³ is a group represented by the general formula: — (— C (═O) —R ^b1 —O—) _m2 −,
(In the formula, R ^b1 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m2 is an integer of 0 to 20).
Y ¹ is a group represented by the following general formula (2) or a group represented by the following general formula (3). }

General formula (2)

[In general formula (2),
(I) a combination in which one of A ^{1 to} A ³ is a hydrogen atom and the other two are —C (═O) OH;
(Ii) ^{one of} A ^{1 to} A ³ is —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms), and the other two are — A combination of C (= O) OH,
(Iii) ^{one of} A ^{1 to} A ³ is a group represented by the following general formula (2a), and the other two are a combination of —C (═O) OH, or
(Iv) ^Three of A ^{1 to} A ³ are —C (═O) OH, and k is 1 or 2. ]

General formula (2a)

[In general formula (2a),
X ²¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ²² is a group represented by the general formula: — (— R ^a21 —O—) _m21 −.
(In the formula, R ^a21 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m21 is an integer of 1 to 50.)
X ²³ is a group represented by the general formula: — (— C (═O) —R ^b21 —O—) _m22 −,
(In the formula, R ^b21 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m22 is an integer of 0 to 20).
Z ²¹ is a vinyl polymer main chain (B) containing a group represented by the general formula (21).
The vinyl polymer main chain (A) and the vinyl polymer main chain (B) may be the same main chain or different main chains. ]

Formula (21)

[In General Formula (21), R ²¹ represents a hydrogen atom or a methyl group. ]

General formula (3)

[In general formula (3),
(V) one of A ^{5 to} A ⁷ is a hydrogen atom and the other two are a combination of —C (═O) OH,
(Vi) One of A ^{5 to} A ⁷ is —C (═O) OR ^d (wherein R ^d is an alkyl group having 1 to 18 carbon atoms), and the other two are — A combination of C (= O) OH,
(Vii) one of A ^{5 to} A ⁷ is a group represented by the following general formula (3a), and the other two are a combination of —C (═O) OH, or
(Viii) three of A ^{5 to} A ⁷ are —C (═O) OH;
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 formula (70), or a group represented by formula (71) It is. ]

General formula (3a)

[In general formula (3a),
X ³¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ³² is a group represented by the general formula: — (— R ^a31 —O—) _m31 −.
(In the formula, R ^a31 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m31 is an integer of 1 to 50.)
X ³³ has the general ^{formula: - (- C (= O} ) -R b31 -O-) m32 - with a group represented,
(In the formula, R ^b31 is a linear or branched alkylene group having 4 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms, and m32 is an integer of 0 to 20).
Z ³¹ is a vinyl polymer main chain (C) containing a group represented by the following general formula (31).
The vinyl polymer main chain (A) and the vinyl polymer main chain (C) may be the same main chain or different main chains. ]

General formula (31)

[In General Formula (31), R ³¹ represents a hydrogen atom or a methyl group. ]

Formula (70)

Formula (71)

General formula (51)

[Wherein R ⁵¹ represents a hydrogen atom or a methyl group,
T ¹ is a group represented by —C (═O) — or —C (═O) —OR ^a51 or —Ph ⁵¹ —R ^b51— ,
( ^Wherein , R ^a51 and R ^b51 are each a linear or branched alkylene group having 1 to 8 carbon atoms,
Ph ⁵¹ is a phenylene group. )
T ² is —O— ^{N═CR c51} R ^d51 or a group represented by the formula (72) or the formula (73). ]
(R ^c51 and R ^d51 are each a linear or branched alkylene group having 1 to 8 carbon atoms, or R ^c51 and R ^d51 are integrated to form a cyclic structure having 3 to 8 carbon atoms. ),

Formula (72)

(R ^e51 , R ^f51 , and R ^g51 are each a hydrogen atom or a linear or branched alkylene group having 1 to 8 carbon atoms),

Formula (73)

(N51 is an integer of 1-8.)

General formula (52)

[Wherein R ⁵² represents a hydrogen atom or a methyl group,
R ^a52 is a linear or branched alkylene group having 1 to 8 carbon atoms,
R ^b52 is a linear or branched alkyl group having 1 to 8 carbon atoms. ],

Formula (53)

[Wherein, R ⁵³ represents a hydrogen atom or a methyl group. ],

Formula (54)

[ ^Wherein , R ⁵⁴ and R ^c54 each represent a hydrogen atom or a methyl group,
R ^a54 and R ^b54 are each a linear or branched alkylene group having 1 to 8 carbon atoms. ]

Formula (55):

[ ^Wherein , R ⁵⁵ and R ^d55 each represent a hydrogen atom or a methyl group,
X ^a55 is —C (═O) O—, —C (═O) ^NH— , ^—O— , —OC (═O) — or —CH ₂ O—,
X ^b55 is a group represented by the formula: — (— R ^b55 —O—) _m55 −;
(In the formula, R ^b55 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m55 is an integer of 1 to 50.)
X ^c55 is a group represented by the formula: — (— C (═O) —R ^c55 —O—) _n55 −,
(In the formula, R ^c55 is a linear or branched alkylene group having 4 to 8 carbon atoms, and n55 is an integer of 0 to 20.)
T ⁵ is, -C (= O) - or ^{-R e51 O-C (= O} ) - or ^-R f51 ^{-Ph 51} - is a group represented by.
( ^Wherein R ^e55 and R ^f55 are each a linear or branched alkylene group having 1 to 8 carbon atoms,
Ph ⁵¹ is a phenylene group. )]

In a preferred embodiment of the vinyl dispersant (a) of the present invention, A ^{1 to} A ³ in the general formula (2) are the combination (i), or A ^{5 to} A ⁷ in the general formula (3). Is the combination (v).

In another preferred embodiment of the vinyl dispersant (a) of the present invention, A ^{1 to} A ³ in the general formula (2) are the combination (iii), or A ⁵ to the general formula (3) A ⁷ is the combination (vii).

In still another preferred embodiment of the vinyl dispersant (a) of the present invention, Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is a group represented by the general formula (2). is there.

  In still another preferred embodiment of the vinyl dispersant (a) of the present invention, the vinyl dispersant is represented by the following general formula (4).

General formula (4)

[In general formula (4),
G represents a carboxyl group-containing unit (G) represented by the general formula (1) according to claim 1,
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ is an aromatic group, or —C (═O) —X ⁷ —R ⁷ (where X ⁷ is —O— or —NH—, and R ⁷ is a hydrogen atom or a carbon atom number of 1 to 18 linear or branched alkyl groups, and R ⁷ can have an aromatic group as a substituent).
X ⁴ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ⁵ is a group represented by the formula: — (— R ^a2 —O—) _m3 −,
(Wherein R ^a2 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m3 is an integer of 1 to 50)
X ⁶ is a group represented by the formula: — (— C (═O) —R ^b4 —O—) _m4 −.
(Wherein R ^b2 is a linear or branched alkylene group having 4 to 8 carbon atoms, and m4 is an integer of 0 to 20)
I represents the crosslinkable functional group-containing unit (I) represented by at least one of the general formulas (51) to (55) according to claim 1.
Mainly including the carboxyl group-containing unit (G) in the general formula (4), a hydroxyl group-containing unit (J) containing —X ⁴ —X ⁵ —X ⁶ —H, and —C (R ⁵ ) (R ⁶ ) —. The arrangement of the chain constituent unit (K) and the crosslinkable functional group-containing unit (I) can be included in a random type or a block type,
The carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) contained in the general formula (4) are: In the vinyl polymer main chain represented by the general formula (4), it indicates that they are included in an arbitrary order, and when they are present in plural, they may be the same or different from each other. it can.
p1, p2, p3, and p4 represent the average number of each structural unit per molecule of the vinyl-based dispersant, p1 is 0.3 or more and 3.0 or less, p2 is 0 or more and 180 or less, and p3 is 6 or more and 250 or less, and p4 is 0.1 or more and 180 or less. ]

  In still another preferred embodiment of the vinyl dispersant (a) of the present invention, the number average molecular weight is 500 or more and 40000 or less.

  Another embodiment of the present invention is a pigment composition comprising a pigment and the vinyl dispersant (a).

  In a preferred embodiment of the pigment composition of the present invention, the pigment composition further includes 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. Contains at least one selected basic synergist.

  Another embodiment of the present invention is a method for producing the vinyl dispersant (a).

In the first embodiment of the method for producing a vinyl dispersant of the present invention,
(A) Ethylenically unsaturated monomer (h) having a hydroxyl group and tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) are reacted in advance to produce an ethylenically unsaturated monomer. Process,
(B) A step of copolymerizing the ethylenically unsaturated monomer obtained in the step (A) with another ethylenically unsaturated monomer is included.

In the second embodiment of the method for producing a vinyl dispersant of the present invention,
(C) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer, and (D) a hydroxyl group of the copolymer obtained in the step (C). A step of reacting tricarboxylic acid anhydride (M3) or tetracarboxylic acid dianhydride (M4).

In the third embodiment of the method for producing the vinyl dispersant of the present invention,
(E) While copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer, a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride ( Reacting M4).

In the fourth embodiment of the method for producing a vinyl dispersant of the present invention,
(F) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having a carboxyl group;
(G) To the copolymer obtained in the step (F), an ethylenically unsaturated compound having an epoxy group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) are simultaneously or And reacting in any order.

In the fifth embodiment of the method for producing a vinyl-based dispersant of the present invention,
(H) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having an epoxy group;
(I) A step of reacting an epoxy group of the copolymer obtained in the step (H) with an ethylenically unsaturated compound having a carboxyl group,
(J) including a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) with the hydroxyl group of the copolymer obtained in the step (I).

In the sixth embodiment of the method for producing a vinyl-based dispersant of the present invention,
(K) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group,
(L) An ethylenically unsaturated compound having an isocyanate group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) are simultaneously added to the hydroxyl group of the copolymer obtained in the step (K). Or a step of reacting in any order.

In the seventh embodiment of the method for producing a vinyl-based dispersant of the present invention,
(M) An ethylenically unsaturated monomer obtained by previously reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) is produced. Process,
(N) a step of copolymerizing the ethylenically unsaturated monomer obtained in the step (M) (provided that an unreacted hydroxyl group remains);
(O) The process of making the ethylenically unsaturated compound which has an isocyanate group react with the hydroxyl group of the copolymer obtained by the said process (N) is included.

In the eighth embodiment of the method for producing a vinyl-based dispersant of the present invention,
(P) An ethylenically unsaturated monomer obtained by previously reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) is produced. Process,
(Q) a step of copolymerizing the ethylenically unsaturated monomer obtained in the step (P) with an ethylenically unsaturated monomer having a carboxyl group;
(R) A step of reacting the copolymer obtained in the step (Q) with an ethylenically unsaturated compound having an epoxy group is included.

  In the preferable aspect of each said manufacturing method, the acid anhydride made to react is trimellitic acid anhydride or aromatic tetracarboxylic dianhydride.

  By using the vinyl-based dispersant (a) of the present invention in a pigment composition, it is possible to obtain dispersibility, fluidity, and storage stability at a low use amount, and at the same time, the heat resistance of the color developed product, In addition, chemical resistance can be obtained, and furthermore, excellent solvent resistance and alkali resistance can be obtained after the color-extended product is thermally cured.

In the present invention, the carboxyl group-containing unit (G) represented by the general formula (1) [particularly, the general formula (1) is contained in the vinyl polymer main chain (for example, in the acrylic polymer main chain). Group Y ¹ ] in an average of 0.3 or more and 3.0 or less per molecule of the vinyl polymer, containing a crosslinkable functional group represented by the general formulas (51) to (55) The present invention relates to a vinyl dispersant (a) characterized in that it contains units (I).

In general, pigment dispersants have a structure that has a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and that the performance of the dispersant is determined by the balance of these two functional sites. explained. 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. In the carboxyl group-containing unit (G) represented by the general formula (1), Y ¹ represented by the general formula (2) or the general formula (3) is directly bonded to the ring-constituting carbon atom of the aromatic ring. Have two or three carboxyl groups bonded to each other, and a plurality of carboxyl groups bonded directly to the ring-constituting carbon atoms of this aromatic ring serve as adsorption sites 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 vinyl dispersant (a) according to the present invention, the carboxyl group-containing unit (G) represented by the general formula (1) in one molecule [particularly, the group Y ¹ in the general formula (1)] has an average of 0. It is important to include 3 or more and 3.0 or less. More preferably, it is 0.35 or more and 2.0 or less, and most preferably 0.4 or more and 1.5 or less. When the number is less than 0.3, the number of sites adsorbed on the pigment is small, and as a result, the dispersion ability is lowered. On the other hand, when the number is more than 3.0, there are too many sites to be adsorbed to the pigment, and conversely, the dispersibility may be lowered.

In the general formula (1), from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability, the general formula (1) is the following general formula (1 ′) in which X ¹ is —C (═O) O—. Preferably, R ^a1 is a hydrocarbon group having 1 to 4 carbon atoms (for example, a methylene group, an ethylene group, a linear or branched propylene group, or a linear or branched butylene group). M1 is preferably 1 to 10 (more preferably 1 to 3), R ^b1 is preferably a pentamethylene group, and m2 is preferably 0 to 5 (more preferably). 0-3).

General formula (1 ')

In particular, Y ¹ is a combination in which one of A ^{1 to} A ^{3 in} the general formula (2) is a hydrogen atom and the other two are —C (═O) OH groups, or It is preferable that one of A ^{5 to} A ^{7 in} the general formula (3) is a hydrogen atom and the other two are —C (═O) OH groups.

As another embodiment, ^one of A ^{1 to} A ^{3 in} the general formula (2) is a group represented by the general formula (2a), and the other two are —C (═O) OH. Or one of A ^{5 to} A ^{7 in} the general formula (3) is a group represented by the general formula (3a), and the other two are —C (═O). A combination that is OH is preferred. One embodiment of the vinyl dispersant of the present invention including such a combination can be represented by, for example, the following general formula (4A).

General formula (4A):

[In general formula (4A), the curved portion is a depiction of the vinyl polymer main chain,
R ¹ and X ^{1 to} X ³ have the same meaning as each group in the general formula (1),
R ¹¹ and X ^{11 to} X ¹³ have the same meaning as R ¹ and X ^{1 to} X ³ in the general formula (1), respectively (provided that R ¹¹ and R ¹ , X ¹¹ and X ¹ , X ¹² and X ² , X ¹³ and X ³ are independent of each other),
Y ² is a tetravalent organic residue represented by the following general formula (2 ′) or the following general formula (3 ′),
E ^{1 to} E ⁴ represent the ends of the vinyl polymer main chain. Here, E ¹ terminal or E ² terminal may be combined with E ³ terminal or E ⁴ terminal. However, the E ¹ end and the E ² end are not simultaneously bonded to the same end. ]

General formula (2 ')

[In general formula (2 '), k' is 1 or 2]

General formula (3 ')

[In the general formula (3 ′), R ^{2 ′} has the same meaning as the group R ² in the general formula (3)].

In the general formula (4A), when the E ¹ terminal or the E ² terminal is bonded to the E ³ terminal or the E ⁴ terminal, for example, in the general formula (2a), the vinyl polymer main chain (B) Is the same main chain as the vinyl polymer main chain (A), or in the general formula (3a), the vinyl polymer main chain (C) is the same main chain as the vinyl polymer main chain (A). If it is a chain,
The vinyl polymer main chain contains a main chain constituent unit represented by the following general formula (4B).

General formula (4B)

[Wherein, R ¹ and X ^{1 to} X ³ , R ¹¹ and X ^{11 to} X ¹³ , and Y ² have the same meaning as each group in the general formula (4A),
m41 is 0 or more and 430 or less.
R ⁴¹ and R ⁴² are structural units capable of constituting a vinyl polymer main chain as the main chain structural unit (B) represented by the following general formula (4b), such as general formulas (51) to (55). A crosslinkable functional group-containing unit (I), a hydroxyl group-containing unit (J) represented by the following general formula (4j) or a main chain constituent unit (K) represented by the general formula (4k), or This constitutes the carboxyl group-containing unit (G) represented by the general formula (1). However, in the general formula (1), A ^{1 to} A ^{3 in the} general formula (2) are not groups represented by the general formula (2A), but A ^{5 to} A ⁷ in the general formula (3) are None of them are groups represented by the general formula (3A). ]

General formula (4b)

In the general formula (4A), when neither the E ¹ terminal or the E ² terminal is bonded to the E ³ terminal or the E ⁴ terminal, for example, in the general formula (2a), the vinyl polymer main chain (B) is a main chain different from the vinyl polymer main chain (A), or in the general formula (3a), the vinyl polymer main chain (C) is a vinyl polymer main chain (A). If the main chain is different from
The description of the present specification regarding the vinyl polymer main chain (A) is as follows: Z ²¹ : That is, the vinyl polymer main chain (B) containing a group represented by the general formula (21), or Z ³¹ : The vinyl polymer main chain (C) containing the group represented by the general formula (31) can also be applied as it is according to the technical common sense of those skilled in the art.

Furthermore, in the general formula (1), Y ¹ is preferably a group represented by the general formula (2), and 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 following formula (70). It is preferably a group.

Formula (70)

  The vinyl dispersant (a) according to the present invention includes a carboxyl group-containing unit (G) represented by the general formula (1), a hydroxyl group-containing unit (J) represented by the following general formula (4j), and From the structural units of the main chain structural unit (K) represented by the following general formula (4k) and the crosslinkable functional group-containing unit (I) represented by any of the general formulas (51) to (55) And a block copolymer or a random copolymer.

General formula (4j)

[In General Formula (4j), R ⁴ , X ⁴ , X ⁵ , and X ⁶ have the same meaning as described above.]

General formula (4k)

[In General Formula (4k), R ⁵ and R ⁶ have the same meaning as described above]

Accordingly, the preferred vinyl dispersant (a) according to the present invention is the above general formula (4) or general formula (4a):-[G] p1- [J] p2- [K] p3- [I] p4- (4a)
It is a copolymer represented by these.

  Here, G is a carboxyl group-containing unit represented by the general formula (1), J is a hydroxyl group-containing unit represented by the general formula (4j), and K is the general formula (4k). ), H is a crosslinkable functional group-containing unit represented by any one of the general formulas (51) to (55), and p1 is 0.3 or more and 3.0 or less. (Preferably 0.35 to 2.0, more preferably 0.4 to 1.5), p2 is 0 to 180 (preferably 0.05 to 50), and p3 is 6 to 250 (preferably Is from 10 to 100, and p4 is from 0.1 to 180 (preferably from 0.5 to 100, more preferably from 2 to 50).

  In the general formula (4a), the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) are each block copolymerized. It can exist in a form or a random copolymer form. Furthermore, the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) are a plurality of each in the general formula (4a). Can exist in pieces. In this case, each unit can be the same or different from each other. For example, the main chain structural unit (K) can include structural units having two or more structures.

  In addition, the arrangement of the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) in the general formula (4a) is [G] p1, It does not mean that [J] p2, and [K] p3, [H] p4 are included in this order, and each unit G, J, and K, H can be included in any order. Means.

In the hydroxyl group-containing unit (J) contained in the vinyl dispersant (a) according to the present invention represented by the general formula (4) or the general formula (4a),
X ⁴ is preferably —C (═O) O—,
R ^a2 is preferably a hydrocarbon group having 1 to 4 carbon atoms (for example, a methylene group, an ethylene group, a linear or branched propylene group, or a linear or branched butylene group),
m3 is preferably 1 to 10, more preferably 0 to 3,
R ^b4 is preferably a pentamethylene group,
m4 is preferably 0 to 5, and more preferably 0 to 3.

In the vinyl dispersant (a), as the main chain structural unit (K), R ⁵ is a methyl group, and R ⁶ is —C (═O) —O—CH ₂ —Ar (where Ar is aromatic It is preferable to include a main chain structural unit (K1) which is a group group, particularly a phenyl group. The main chain structural unit (K1) preferably has an average amount of 1 or more and 100 or less per molecule of the vinyl polymer, and the vinyl dispersant (a) of this embodiment has a dispersing ability. Excellent.

Further, in the vinyl dispersant (a), as the main chain structural unit (K), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is —C (═O) —O—R ⁷ (where R ⁷ is preferably a main chain constituent unit (K2) which is a linear or branched alkyl group having 2 to 12 carbon atoms. It is more preferable that the main chain structural unit (K2) coexists with the main chain structural unit (K1) in the vinyl dispersant (a).

  The vinyl dispersant (a) is a crosslinkable functional group represented by any one of the general formulas (51) to (55) in addition to the carboxyl group-containing unit (G) represented by the general formula (1). It is essential to include the content unit (I).

  Thereby, the said vinyl-type dispersing agent (a) by this invention can obtain the outstanding solvent resistance and alkali resistance, after thermosetting the color development thing. This is because the crosslinkable functional group-containing unit (I) is cross-linked by baking, so that the solvent resistance and alkali resistance are remarkably improved.

  The crosslinkable functional group-containing units (I) represented by the general formulas (51) to (55) preferably have an average amount of 0.5 or more and 100 or less per molecule of the vinyl polymer. More preferably, the amount is 2 or more and 50 or less. If it is 0.5 or less, the effect of crosslinking is small, and if it is 100 or more, the hydrophilicity of the vinyl polymer becomes too high and the dispersibility deteriorates.

  Further, the crosslinkable functional group-containing unit (I) represented by the general formulas (51) to (53) may be more effective when combined with a hydroxyl group or a carboxyl group.

  The crosslinkable functional group-containing unit represented by the general formula (51) is more preferably used in combination with a hydroxyl group. The crosslinkable functional group represented by the general formula (51) is a blocked isocyanate, the block is removed at a high temperature, and the isocyanate undergoes a crosslinking reaction with a hydroxyl group.

When the average number of crosslinkable functional group-containing units represented by the general formula (51) is a and the number of hydroxyl group-containing units is b per molecule of the vinyl polymer,
a × b is preferably 2 or more, and more preferably 5 or more.

  Even if the crosslinkable functional group-containing unit represented by the general formula (52) is used alone, a crosslinking effect can be obtained, but it is more preferable to use it together with a carboxyl group. The crosslinkable functional group represented by the general formula (52) is oxetane, and self-polymerizes at a high temperature and crosslinks with a carboxyl group.

When the average number of crosslinkable functional group-containing units represented by the general formula (52) is c and the number of carboxyl group-containing units is d per molecule of the vinyl polymer,
c × d is preferably 2 or more, and more preferably 5 or more.

  The crosslinkable functional group-containing unit represented by the general formula (53) is preferably used in combination with a hydroxyl group, and is preferably used in combination with the crosslinkable functional group-containing unit represented by the general formula (52). In the crosslinkable functional group represented by the general formula (53), the tertiary butyl group is removed at a high temperature to become a carboxyl group. This carboxyl group undergoes a crosslinking reaction with a hydroxyl group at a high temperature, and also undergoes a crosslinking reaction with oxetane.

When the number of crosslinkable functional group-containing units represented by the general formula (53) is e and the number of hydroxyl group-containing units is b on average per molecule of the vinyl polymer, e × b is preferably 2 or more. More preferably.
When the average number of crosslinkable functional group-containing units represented by the general formula (53) is e and the number of carboxyl group-containing units is d per molecule of the vinyl polymer,
e × d is preferably 2 or more, and more preferably 5 or more.

  The terminal of the main chain of the vinyl-based dispersant (a) is a known polymerization method of an ethylenically unsaturated monomer or a structure considered in the polymerization process, for example, a polymerization initiator-derived, a chain transfer agent-derived, a solvent-derived, Alternatively, it may have a chemical structure derived from an ethylenically unsaturated monomer.

  The number average molecular weight of the vinyl dispersant (a) according to the present invention is preferably 500 or more and 40000 or less, more preferably 1000 or more and 20000 or less, and most preferably 1500 or more and 16000 or less. Even if the number average molecular weight is less than 500 or more than 40000, the dispersibility or fluidity may be lowered.

  The said vinyl type dispersing agent (a) by this invention can be manufactured with the following manufacturing methods 1-8, for example.

Manufacturing method 1:
(A) Ethylenically unsaturated monomer (h) having a hydroxyl group and tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) are reacted in advance to produce an ethylenically unsaturated monomer. Process,
(B) The ethylenically unsaturated monomer and another ethylenically unsaturated monomer [any crosslinkable functional group represented by the general formulas (51) to (53) (that is, the general formula (51) To an ethylenically unsaturated monomer having a crosslinkable functional group-containing unit represented by (53) excluding the main chain constituent moiety. ] Is copolymerized.

Manufacturing method 2:
(C) An ethylenically unsaturated monomer (h) having a hydroxyl group is replaced with another ethylenically unsaturated monomer [ethylene having any crosslinkable functional group represented by the general formulas (51) to (53). Contains a polyunsaturated monomer. A step of copolymerizing with
(D) It consists of a step of reacting a hydroxyl group of the copolymer with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4).

Manufacturing method 3:
(E) Ethylenically unsaturated monomer (h) having a hydroxyl group is replaced with another ethylenically unsaturated monomer [ethylene having any crosslinkable functional group represented by the general formulas (51) to (53) Contains a polyunsaturated monomer. ], A process of reacting the hydroxyl group with tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) simultaneously.

Further, when the vinyl dispersant (a) of the present invention contains any of the crosslinkable functional groups having an unsaturated bond represented by the general formula (54) or (55) as the crosslinkable functional group, Production methods 4 to 8 can be exemplified.

Manufacturing method 4:
(F) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having a carboxyl group (preferably together with another ethylenically unsaturated monomer);
(G) To the copolymer obtained in the step (F), an ethylenically unsaturated compound having an epoxy group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) are simultaneously or And the steps of reacting in any order.

  In the said process (G), the ethylenically unsaturated compound which has an epoxy group reacts with the carboxyl group of the copolymer obtained by the said process (F), and has an unsaturated bond shown by General formula (54). A crosslinkable functional group is generated. On the other hand, tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) reacts with the hydroxyl group of the copolymer.

  Moreover, when the vinyl type dispersing agent (a) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional groups, these are used in the step (F). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.

Manufacturing method 5:
(H) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having an epoxy group (preferably together with another ethylenically unsaturated monomer);
(I) A step of reacting an epoxy group of the copolymer obtained in the step (H) with an ethylenically unsaturated compound having a carboxyl group,
(J) It comprises a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) with the hydroxyl group of the copolymer obtained in the step (I).

  In the said process (I), the ethylenically unsaturated compound which has a carboxyl group reacts with the epoxy group of the copolymer obtained by the said process (H), and has an unsaturated bond shown by General formula (54). A crosslinkable functional group is generated.

  Moreover, when the vinyl type dispersing agent (a) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional group, these are used in the step (H). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.

Production method 6:
(K) copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group (preferably together with another ethylenically unsaturated monomer);
(L) An ethylenically unsaturated compound having an isocyanate group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) are simultaneously added to the hydroxyl group of the copolymer obtained in the step (K). Or it consists of the process of making it react in arbitrary orders.

  In the step (L), the ethylenically unsaturated compound having an isocyanate group reacts with the hydroxyl group of the copolymer obtained in the step (K), and is a crosslink having an unsaturated bond represented by the general formula (55). To generate a functional group. On the other hand, tricarboxylic anhydride (M3) or tetracarboxylic dianhydride (M4) also reacts with the hydroxyl group of the copolymer.

  Moreover, when the vinyl type dispersing agent (a) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional groups, these are used in the step (K). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.

Manufacturing method 7:
(M) An ethylenically unsaturated monomer obtained by previously reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) is produced. Process,
(N) Copolymerizing the ethylenically unsaturated monomer obtained in the step (M) (provided that an unreacted hydroxyl group remains) (preferably together with another ethylenically unsaturated monomer) The process of
(O) It comprises a step of reacting an ethylenically unsaturated compound having an isocyanate group with the hydroxyl group of the copolymer obtained in the step (N).

  In the manufacturing method 7, the crosslinkable functional group which has an unsaturated bond shown by General formula (55) is formed in the said process (O). Moreover, when the vinyl type dispersing agent (a) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional groups, these may be used in the step (N). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.

Production method 8:
(P) An ethylenically unsaturated monomer obtained by previously reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) is produced. Process,
(Q) The ethylenically unsaturated monomer obtained in the step (P) is copolymerized with an ethylenically unsaturated monomer having a carboxyl group (preferably together with another ethylenically unsaturated monomer). Process,
(R) It comprises a step of reacting the copolymer obtained in the step (Q) with an ethylenically unsaturated compound having an epoxy group.

  In the manufacturing method 8, the crosslinkable functional group which has an unsaturated bond shown by General formula (54) is formed in the said process (R). Moreover, when the vinyl type dispersing agent (a) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional group, these may be used in the step (Q). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.

  As the ethylenically unsaturated monomer (h) having a hydroxyl group used in the above production method, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used. Although not specifically, a (meth) acrylate monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) ) -Hydroxybutyl (meth) acrylate and hydroxyalkyl (meth) acrylate such as cyclohexanedimethanol mono (meth) acrylate, or a (meth) acrylamide monomer having a hydroxyl group, such as N- (2-hydroxyethyl) ( (Meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydride) N- (hydroxyalkyl) (meth) acrylamide such as xylbutyl) (meth) acrylamide, or vinyl ether monomers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2 -Hydroxyalkyl vinyl ethers such as-(or 3- or 4-) hydroxybutyl vinyl ether, or allyl ether monomers having a hydroxyl group, such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, And hydroxyalkyl allyl ethers such as 2- (or 3- or 4-) hydroxybutyl allyl ether.

  In addition, an ethylenically unsaturated monomer obtained by adding alkylene oxide and / or lactone to the above hydroxyalkyl (meth) acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether Can also be used as an ethylenically unsaturated monomer (h) having a hydroxyl group in the production method used in the present invention. 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 bonding 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.

  Examples of the tricarboxylic acid anhydride (M3) include aliphatic tricarboxylic acid anhydrides, aromatic tricarboxylic acid anhydrides, and polycyclic tricarboxylic acid anhydrides.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzenetricarboxylic acid anhydride), etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride Products), 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 anhydride, 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydrides.

  In addition, in the production method used in the present invention, in one of the tetracarboxylic dianhydrides (M4) described later, one acid anhydride of one molecule is converted to water, an alcohol having 1 to 18 carbon atoms, or 5 to 5 carbon atoms. 18 cycloalcohols (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 cyclodecanol, straight chain Is branched dodecanol 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 Tetracarboxylic acid monoanhydrides and tetracarboxylic acid monoester monoanhydrides that have been ring-opened with an alcohol etc. can also be used as the tricarboxylic acid anhydride (M3) in the production method used in the present invention. In the present specification, an aliphatic tetracarboxylic acid monoester monoanhydride is an aliphatic tricarboxylic acid anhydride, an aromatic tetracarboxylic acid monoester monoanhydride is an aromatic tricarboxylic acid anhydride, a polycyclic tetracarboxylic acid anhydride. The monoester monoanhydride is described as a polycyclic tricarboxylic acid anhydride. Specific examples of these tetracarboxylic anhydride monoester monoanhydrides are obvious to those skilled in the art from the tetracarboxylic dianhydrides described below.

  Examples of the tetracarboxylic dianhydride (M4) include aliphatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and polycyclic tetracarboxylic dianhydrides.

  Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,3-dimethyl. -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3, 5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3- Examples include cyclohexene-1,2-dicarboxylic dianhydride and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

  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) fluorenic dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluoric dianhydride and the like. Can be mentioned.

  Examples of the polycyclic tetracarboxylic dianhydride include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2 , 3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride and the like.

  The production method 1 used in the present invention will be described in more detail.

  In the production method 1 used in the present invention, first, the step (A) of reacting the ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) is performed. Do. This step (A) is preferably carried 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 will not thermally polymerize. More preferably, it is 90 to 130 ° C. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.

  When the ethylenically unsaturated monomer (h) having a hydroxyl group and the tricarboxylic acid anhydride (M3) are reacted in the step (A), the reaction ratio is “the ethylenically unsaturated monomer having a hydroxyl group (h)”. It is preferable that "number of moles / number of moles of tricarboxylic acid anhydride (M3)" is 0.8 or more and 10 or less. More preferably, it is 0.9 or more and 5 or less, and further preferably 0.95 or more and 2 or less. If it is less than 0.8, the tricarboxylic acid anhydride (M3) remains, which is not preferable. If it exceeds 10, a large amount of the ethylenically unsaturated monomer (h) having a hydroxyl group remains, and the amount of other ethylenically unsaturated monomers that can be copolymerized in the subsequent step (B) decreases, which is not preferable.

  When the ethylenically unsaturated monomer (h) having a hydroxyl group and the tetracarboxylic dianhydride (M4) are reacted in the step (A), the reaction ratio is "ethylenically unsaturated monomer having a hydroxyl group (h ) / Mol of tetracarboxylic dianhydride (M4) ”is preferably 0.5 or more and 10.0 or less. More preferably, it is 1.0 or more and 5.0 or less. If it is less than 0.5, a large amount of tetracarboxylic dianhydride (M4) remains, which is not preferable. If it exceeds 10, a large amount of the ethylenically unsaturated monomer (h) having a hydroxyl group remains, and the amount of other ethylenically unsaturated monomers that can be copolymerized in the subsequent step (B) decreases, which is not preferable.

  In the step (A), a catalyst may be used. The catalyst is preferably a tertiary amine compound 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.

  Further, the ethylenically unsaturated monomer (h) having a hydroxyl group and the tetracarboxylic dianhydride (M4) are expressed as "number of moles of ethylenically unsaturated monomer (h) having a hydroxyl group / tetracarboxylic dianhydride". When the reaction is performed at a "mol number of (M4)" less than 2.0, the acid anhydride group remaining at this point is opened with water or an alcohol having 1 to 18 carbon atoms [step (Aa)], unnecessary. Removal of the acid anhydride group can be facilitated.

  Subsequently, in the production method 1, the ethylenically unsaturated monomer synthesized in the step (A) and another ethylenically unsaturated monomer [crosslinkable functional group of any one of the general formulas (51) to (53)] (The ethylenically unsaturated monomer having a group may be included)].

  As another ethylenically unsaturated monomer used in the step (A), an alkyl (meth) acrylate having 1 to 18 carbon atoms which may be substituted with an aromatic group, or N- having 1 to 18 carbon atoms. Alkyl (meth) acrylamide, styrene, ethylenically unsaturated monomer (h) having a hydroxyl group (including those remaining in step (A)), and crosslinkability represented by general formulas (51) to (53) Preferably, an ethylenically unsaturated monomer selected from ethylenically unsaturated monomers having a functional group is copolymerized.

  Examples of unsubstituted alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, linear or branched propyl (meth) acrylate, linear or branched butyl (meth) acrylate, direct 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 or Branched Desi (Meth) acrylate, cyclodecyl (meth) acrylate, linear or branched dodecyl (meth) acrylate, cyclododecyl (meth) acrylate, linear or branched myristyl (meth) acrylate, cyclomyristyl (meth) 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.

  As unsubstituted N-alkyl (meth) acrylamide, 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 (meta ) 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 (meth) 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 may be mentioned. Examples of the alkyl (meth) acrylate 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).

  Examples of the ethylenically unsaturated monomer having a crosslinkable functional group represented by the general formula (51) include Karenz MOI-BM and Karenz MOI-BP (manufactured by Showa Denko).

  Examples of the ethylenically unsaturated monomer having a crosslinkable functional group represented by the general formula (52) include ETERNACOLL OXMA (manufactured by Ube Industries).

  Examples of the ethylenically unsaturated monomer having a crosslinkable functional group represented by the general formula (53) include t-butyl methacrylate and t-butyl acrylate.

  In the step (B), 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 (B), 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 (B), it is preferable to use a solvent. Solvents include acetates such as ethyl acetate, propyl acetate, butyl acetate, ethyl cellosolve acetate and propylene glycol monomethyl ether acetate, ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone, and aromatics such as xylene, toluene and ethylbenzene. Group hydrocarbons and the like can be used.

  If step (Aa) is not performed after step (A), the acid anhydride remaining after step (B) can be ring-opened with water or an alcohol having 1 to 18 carbon atoms [step ( Bb)]. In the step (Aa) or the step (Bb), the number of moles of water to be reacted or the alcohol having 1 to 18 carbon atoms is 0.9 to 5 times (preferably with respect to the number of moles of the remaining acid anhydride. Is preferably 1 to 2 times. If it is less than 0.9 times, a lot of highly reactive acid anhydride groups remain, and if it exceeds 5 times, water or alcohol having 1 to 18 carbon atoms remains, anyway, it has been developed for use in inks and paints. If this is a problem. However, in the case where the water to be reacted or the alcohol having 1 to 18 carbon atoms is reacted more than 1 time with respect to the number of moles of the remaining acid anhydride, the water remaining after the reaction or having 1 to 18 carbon atoms is reacted. The alcohol can be removed by heating or under reduced pressure. The reaction step (Aa) or the step (Bb) is preferably performed at 80 to 150 ° C.

  Next, the production method 2 used in the present invention will be described in detail.

  In the manufacturing method 2 used by this invention, the process (C) of copolymerizing the ethylenically unsaturated monomer (h) which has a hydroxyl group with another ethylenically unsaturated monomer first is performed. As another ethylenically unsaturated monomer, an alkyl (meth) acrylate having 1 to 18 carbon atoms which may be substituted with the aromatic ring exemplified in the step (B) of production method 1, an aromatic ring An ethylenically unsaturated monomer selected from optionally substituted N-alkyl (meth) acrylamide having 1 to 18 carbon atoms, styrene, and an ethylenically unsaturated monomer having a carboxyl group is copolymerized. It is preferable.

  The copolymerization ratio between the ethylenically unsaturated monomer (h) having a hydroxyl group and another ethylenically unsaturated monomer is such that one molecule after polymerization has an average of at least 0.3 to 177 hydroxyl groups. Decided to enter.

  The polymerization conditions such as the type of polymerization initiator, the type of chain transfer agent, the type of solvent, the amount, and the reaction temperature in step (C) are preferably the same as in step (B) of production method 1.

  Then, in the manufacturing method 2, the process (D) which makes tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) react with the hydroxyl group of the copolymer obtained at the process (C) is performed. In the step (D), it is preferably performed at 80 ° C. to 150 ° C. while flowing nitrogen or dry air into the reaction vessel. Here, the catalyst illustrated at the process (A) of the manufacturing method 1 can also be used.

  When tetracarboxylic dianhydride (M4) is used in step (D) of production method 2, and an acid anhydride group remains, water or carbon atoms are obtained by the same method as in step (Bb) of production method 1. The ring can be opened with an alcohol having a number of 1 to 18 [step (Dd)].

  Next, the production method 3 used in the present invention will be described in detail.

  In the production method 3 used in the present invention, an ethylenically unsaturated monomer (h) having a hydroxyl group is copolymerized with another ethylenically unsaturated monomer, and a tricarboxylic acid anhydride (M3) or tetra Carboxylic dianhydride (M4) is reacted simultaneously. The reaction is preferably performed at 80 ° C. to 150 ° C. while flowing nitrogen into the reaction vessel. As a catalyst for the reaction between the hydroxyl group and the acid anhydride, the polymerization initiator shown in Step (A) of Production Method 1 can be used. The polymerization conditions such as the type, the type of chain transfer agent, the type of solvent, the amount, and the reaction temperature are preferably those shown in Step (B) of Production Method 1.

  The other ethylenically unsaturated monomer used in production method 3 is the same as the compound used in step (C) of production method 2. Even in the production method 3, when an acid anhydride group remains, the ring can be opened with water or an alcohol having 1 to 18 carbon atoms by the same method as in the production method 1 (Bb) [step (Ee)]. .

  By these production methods 1 to 3, the vinyl dispersant (a) used in the present invention can be produced. Among these, production method 2 is preferable in that it is easy to control the number of carboxyl group-containing units (G) in one molecule of the dispersant. The number average molecular weight of the copolymer obtained in the step (C) of the production method 2 can be measured in advance, and the amount by which the tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) is reacted according to the value This is because it can be determined. For example, in order to produce the vinyl dispersant (a) by the production method 2, the number average molecular weight of the copolymer obtained in the step (C) is measured, and when the measured value is [X], the tricarboxylic acid When the anhydride (M3) is used, 0.3 to 3.0 mol of tricarboxylic acid anhydride (M3) may be reacted with the resin [X] g. On the other hand, when tetracarboxylic dianhydride (M4) is used, 0.15 mol or more and 1.5 mol or less of tetracarboxylic dianhydride (M4) may be reacted with resin [X] g. . This is because the tetracarboxylic dianhydride (M4) has two acid anhydride groups, so the tricarboxylic acid anhydride (M3) is used to bridge the copolymer bimolecules obtained in step (C). This is because half the amount is sufficient.

  Further, in the case of using tetracarboxylic dianhydride (M4) in the step (D), when the number of hydroxyl groups contained in one molecule of the copolymer obtained in the step (C) is 1.1 or more, Ratio of the total amount <OH> of hydroxyl groups contained in the copolymer and the total amount <AH> of acid anhydride groups contained in the tetracarboxylic dianhydride (M4): The value of <OH> / <AH> is 0 It is preferably less than .9 or 1.1 or more. When the value of <OH> / <AH> is in the range of 0.9 or more and less than 1.1, the vinyl dispersant (a) may exceed the upper limit of the preferred number average molecular weight of the present invention of 40000.

  When the vinyl dispersant (a) used in the present invention is produced by the production method 1 or 3, the number average molecular weight [Y] of the vinyl dispersant (a) finally obtained and the tricarboxylic acid anhydride ( M3) or tetracarboxylic dianhydride (M4) charged from the number of moles charged, as a result, the vinyl dispersant (a) is 0.3 mol or more and 3.0 mol or less with respect to [Y] g. The tricarboxylic acid anhydride (M3) or the tetracarboxylic acid dianhydride (M4) may be reacted.

  When the vinyl dispersant (a) is produced by the production method of the present invention, when using the tricarboxylic acid anhydride (M3), an aromatic tricarboxylic acid anhydride is preferable, and a trimellitic acid anhydride is more preferable. Of the above, when tetracarboxylic dianhydride (M4) is used, aromatic tetracarboxylic dianhydride is preferably used, more preferably pyromellitic dianhydride, ethylene glycol dianhydride trimellit. Acid ester, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.

  When producing the vinyl dispersant (a) in any of the production methods 1 to 3, the other ethylenically unsaturated monomer having 1 to 12 unsubstituted carbon atoms which may have a branch Alkyl (meth) acrylate, benzyl (meth) acrylate, ethylenically unsaturated monomer (h) having a hydroxyl group if necessary, styrene if necessary, ethylenically unsaturated monomer having a carboxyl group if necessary The body is preferably copolymerized. Furthermore, 1 to 50 unsubstituted alkyl (meth) acrylates having 1 to 12 carbon atoms, which may have a branch in one molecule of the vinyl dispersant (a), and 1 to 1 benzyl (meth) acrylate. Preferably 50 are copolymerized.

  In addition, the vinyl dispersant (a) used in the present invention can be copolymerized with various ethylenically unsaturated monomers other than those exemplified so far as long as the dispersibility is not hindered. An ethylenically unsaturated monomer having a thermally crosslinkable group such as an isocyanato group, a block isocyanato group, an alkoxysilyl group, or a 3- to 5-membered cyclic ether group can be copolymerized.

  By using a starting material appropriately selected from the listed starting materials, the vinyl dispersant (a) can be prepared by the manufacturing method used in the present invention.

  By using the vinyl dispersant (a) and the pigment (P), the pigment composition of the present invention is obtained. Here, by using the vinyl dispersant (a), a pigment composition having excellent dispersibility, fluidity, and storage stability is obtained.

  As the pigment (P) used in the present invention, various pigments used in inks and the like can be used. Such 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. , Anthanthrone pigment, Indanthrone pigment, Flavanthrone pigment, Pyranthrone pigment, Diketopyrrolopyrrole pigment, etc. More specific examples are shown by the generic names of Color Index: 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, 1 9, 185, 206, 207, 209, 220, 221, 238, 242, 254, 255, 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, Pigment Orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74, and the like. However, it is not limited to illustration.

  Also used are metal oxides such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, silica, and inorganic pigments such as cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, and carbon black. be able to. As the carbon black, any carbon black such as neutral, acidic and basic can be used.

  The vinyl-based dispersant of the present invention is not limited to the above-mentioned pigments, and is used for dispersing solid fine particles including metal fine particles such as gold, silver, copper, platinum, iron, cobalt, nickel, and / or alloys thereof. Can do.

  The pigment composition of the present invention further includes at least one base 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 is preferable that a sex synergist (Y) is included.

  Here, the pigment derivative is obtained by introducing a specific substituent into the organic pigment residue described in the color index. In the present invention, a pigment derivative having a basic group is used.

  By including the basic synergist (Y), a pigment composition that is difficult to disperse without the basic synergist (Y) (especially in the case of an organic pigment) is also a pigment composition having excellent dispersibility, fluidity, and storage stability. Can be preferable. With the synergistic effect of the vinyl dispersant (a) and the basic synergist (Y), the pigment (P) can be effectively made into a pigment composition excellent in dispersibility, fluidity and storage stability.

  The basic synergist (Y) that can be used in the pigment composition of the present invention includes 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 Selected from the group of

  The basic group of the basic synergist (Y) that can be used in the pigment composition of the present invention is represented by the following general formula (61), general formula (62), general formula (63), and general formula (64). At least one group selected from the group consisting of

General formula (61)

[Wherein, X ^{61 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
p ₆₁ represents an integer of 1 to 10.
R ^a61 , R ^b61 : each independently an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group, an ^optionally substituted phenyl group, or a combination of R ^a61 and R ^b61 And an optionally substituted heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. ]

Formula (62)

[ ^Wherein R ^a62 and R ^b62 each independently ^represents an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group, an ^optionally substituted phenyl group, or R ^a62 and R ^b62 together. And represents an optionally substituted heterocyclic ring containing a further nitrogen atom, oxygen atom or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. ]
General formula (63)

[Wherein, X ^{63 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
R ^{a63 represents an optionally} substituted alkyl group, an ^optionally substituted alkenyl group, or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ^b63 , R ^c63 , R ^d63 , R ^e63 : each independently represents a hydrogen atom, an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group, or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred. ]

General formula (64)

[Wherein, X ^{64 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
Y ⁶⁴ represents —NR ^a64 —Z ⁶⁴ —NR ^b64 — or a direct bond.
R ^a64 and R ^b64 each independently represent a hydrogen atom, an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.
Z ⁶⁴ represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted phenylene group. As for carbon number of an alkylene group and an alkenylene group, 1-8 are preferable.
P ⁶⁴ : represents a substituent represented by the following general formula (65) or a substituent represented by the following general formula (66).
Q ^{64 represents a} hydroxyl group, an alkoxyl group, a substituent represented by the general formula (62) or a substituent represented by the general formula (63). ]

Formula (65):

[Wherein, r ₆₅ represents an integer of 1 to 10.
R ^a65 , R ^b65 : each independently an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group, an ^optionally substituted phenyl group, or a combination of R ^a65 and R ^b65 And an optionally substituted heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. ]

General formula (66):

[ ^Wherein R ^{a66 represents an optionally} substituted alkyl group, an ^optionally substituted alkenyl group or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ^b66 , R ^c66 , R ^d66 , R ^e66 : each independently represents a hydrogen atom, an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred. ]

In a preferred form as the substituent represented by the general formula (61), X ⁶¹ is —SO ₂ — or C (═O) —, p ₆₁ is 1 to 5 (more preferably 2 to 4), R ^a61 and R ^b61 are each independently a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, or R ^a61 and R ^b61 and a nitrogen atom in the formula Together form morpholine.

In a preferred form of the substituent represented by the general formula (62), R ^a62 and R ^b62 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.

A preferable form of the substituent represented by the general formula (63) is that X ⁶³ is —CH ₂ NHC (═O) CH ₂ —, and R ^a63 is a methyl group, an ethyl group, an n-propyl group, or iso-propyl. A group, n-butyl group or iso-butyl group, and R ^b63 , R ^c63 , R ^d63 and R ^e63 are hydrogen atoms.

In a preferred form as the substituent represented by the general formula (64), X ⁶⁴ is a direct bond or SO ₂ —, Y ⁶⁴ is a direct bond or NH—Z ⁶⁴ —NH—, and Z ⁶⁴ is a phenylene group. Q ⁶⁴ is a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group, P ⁶⁴ is a substituent represented by the general formula (8), and X ^{65 in} P ⁶⁴ is —SO ₂ —. or C (= O) - and it is, ^{r 65} in the ^{P 64} is 1-5 (more preferably 2-4), and independently ^{R a65} and ^{R b65} in the ^{P 64,} respectively, a methyl group, This is the case of ethyl group, n-propyl group, iso-propyl group, n-butyl group and iso-butyl group.

  Examples of the nitrogen atom used to form the substituents represented by the formulas (61) to (66) include 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-butyl Propylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyl oct Decylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, 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-diisobutylamino Pentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, 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-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Isonicopetic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoly N-aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentyl And piperazine.

  Organic dyes constituting pigment derivatives having basic groups include, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrones , Indanthrone, pyranthrone, violanthrone, anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes It is a dye such as a dye or a metal complex dye. In addition, an anthraquinone derivative having a basic group and an acridone derivative having a basic group are alkyl groups such as methyl and ethyl groups, amino groups, nitro groups, hydroxyl groups or methoxy groups, alkoxy groups such as ethoxy groups, chlorine, etc. It may have a substituent such as halogen.

  Triazines constituting triazine derivatives having basic groups are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro Group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) And may have a substituent such as a phenylamino group (which may be substituted with an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen, or the like). It is also a good 1,3,5-triazine.

  The pigment derivative, anthraquinone derivative and acridone derivative having a basic group can be synthesized by various synthetic routes. For example, after introducing a substituent represented by formula (11) to formula (14) into an organic dye, anthraquinone or acridone, the substituent represented by formula (61) to formula (66) is reacted with the above substituent. Amine component to be formed, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine It can be obtained by reacting 2-ylamino] aniline or the like.

Formula (11): —SO ₂ Cl
Formula (12): -C (= O) Cl
Formula (13): —CH ₂ NHC (═O) CH ₂ Cl
Formula (14): —CH ₂ Cl

  During the reaction of the substituents represented by the formulas (11) to (14) and the amine component, a part of the substituents represented by the formulas (11) to (14) is hydrolyzed to produce chlorine atoms. May be mixed with those substituted with a hydroxyl group. In that case, the substituent represented by the formula (11) or the formula (12) is a sulfonic acid group or a carboxylic acid group, respectively, but any of them may be a free acid, or a 1-3 valent metal or the above-mentioned Or a salt with a monoamine.

  Further, when the organic dye is an azo dye, the substituent represented by the formula (61) to the formula (66) is previously introduced into the diazo component or the coupling component, and then the coupling reaction is performed, thereby performing the azo type. Pigment derivatives can also be produced.

  The triazine derivative having a basic group can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by formula (61) to formula (66) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  In the pigment composition of the present invention, the blending amount of the basic synergist (Y) is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 5 parts by weight with respect to 100 parts by weight of the pigment (P). 25 parts by weight. When the basic synergist (Y) is less than 1 part by weight relative to 100 parts by weight of the pigment (P), the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and light resistance may be deteriorated. The blending amount of the vinyl dispersant (a) is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 75 parts by weight, and most preferably 1.0 to 100 parts by weight of the pigment (P). ~ 50 parts by weight. If the vinyl dispersant (a) is less than 0.1 parts by weight with respect to 100 parts by weight of the pigment (P), the dispersibility may deteriorate, and if it exceeds 100 parts by weight, the dispersibility may also deteriorate. is there.

  The pigment composition of the present invention is dispersed in a varnish by mixing various solvents, resins, additives, etc. as necessary, and dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor or the like. Thus, a pigment dispersion obtained can be prepared. The pigment (P), basic synergist (Y), vinyl-based dispersant (a), other resins and additives may be dispersed after mixing all the components. Only basic synergist (Y), only basic synergist (Y) and vinyl dispersant (a), or pigment (P), basic synergist (Y) and vinyl dispersant (a) It is also possible to disperse only and then add another component to carry out dispersion again.

  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, 3-roll mill, etc., solid dispersion with 2-roll mill, etc., or pigment You may perform the process of a basic synergist (Y) and / or a vinyl-type dispersing agent (a) to (P). 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 pigment dispersion. Examples of various solvents that can be used in the pigment dispersion include organic solvents and water. Moreover, when using for an active energy ray hardening-type composition, you may use an active energy ray-curable liquid monomer and liquid oligomer as a medium instead of a solvent.

  Examples of resins that can be used in the pigment dispersion include petroleum resin, casein, shellac, rosin-modified maleic acid resin, rosin-modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, and chlorinated 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 resin , Silicone resin, fluorine resin, drying oil, synthetic drying oil, styrene-modified maleic acid, polyamide resin, chlorinated polypropylene, butyral resin, vinylidene chloride resin, and the like.

  In general, when a pigment dispersion is used for application as a colored coating film, the resin component often contains a resin as a main component in addition to the pigment dispersant. This is because the pigment dispersant generally has a low film forming property, and when only the pigment dispersant is used as the main component of the above pigment dispersion, the appearance of the coating film is deteriorated or the wetting to the substrate is repelled. Sometimes. This is the case in the case of a pigment dispersant having a main skeleton of polycaprolactone, polyethylene oxide or the like, such as BYK-111 (manufactured by BYK Chemie), which is a commercially available dispersant.

  The vinyl dispersant (a) of the present invention has a very high film forming property and can be used without using other resins as the resin used in the pigment dispersion.

  Therefore, it can be used more as a pigment dispersant than the usual addition amount. Furthermore, since the vinyl type dispersing agent (a) of the present invention has a crosslinkable functional group, a colored coating film having high solvent resistance can be obtained without adding a curing agent.

  The pigment dispersion is used in non-aqueous, aqueous or solvent-free paints, gravure ink, offset ink, ink jet ink, color filter ink, black matrix ink, digital paper ink, plastic colorant, etc. it can. Of these, ink jet ink, color filter ink, and black matrix ink are suitable. Particularly for color filter inks and black matrix inks, for example, inks suitable for many printing methods such as photolithography, lithographic printing, intaglio printing, letterpress printing, screen printing, and ink jet printing. Can be suitably used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not specifically limited to an Example. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”. The number average molecular weight is a polystyrene equivalent molecular weight when using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector and using THF as a developing solvent.

<< Synthesis Example 1 >>
(1) Process (C)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 28.5 parts, benzyl methacrylate 48 parts, 2-hydroxyethyl methacrylate 3.5 parts, ETERRNACOLL OXMA (Ube Industries) 20 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 The liquid mixture which mixed the part uniformly beforehand was dripped over 2 hours, and stirring was continued at the same temperature for 3 hours after that, and reaction was complete | finished.
Thus, a vinyl resin intermediate (X1) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule was obtained.

(2) Process (D)
In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (X1) in terms of solid content, 5.1 parts of trimellitic anhydride, and dimethylbenzylamine 0. 1 part was charged and reacted at 100 ° C. for 6 hours (Step D of Example 2).
Thus, the vinyl dispersant (A1) having a number average molecular weight of 4000 and an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0. )

<< Synthesis Example 2 >>
(1) Process (C)
A certain vinyl-based resin intermediate (X1) was obtained by the same method as in Synthesis Example (1).
(2) Process (D)
In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl-based resin intermediate (X1) in solids, 2.9 parts of pyromellitic anhydride, and dimethylbenzylamine were added in an amount of 0.1%. 1 part was charged and reacted at 100 ° C. for 6 hours.
Thus, a vinyl dispersant (A2) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )

<< Synthesis Example 3 >> to << Synthesis Example 8 >>
In the same manner as in Examples 1 and 2, vinyl resin intermediate (X3) to vinyl resin intermediate (X8) were synthesized to obtain vinyl dispersant (A3) to vinyl dispersant (A8).

<< Synthesis Example 9 >>
(1) Step (A)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is charged with 218 parts of pyromellitic dianhydride, 130 parts of 2-hydroxyethyl methacrylate, and 0.3 part of hydroquinone monomethyl ether, and dry air is allowed to flow. The mixture was reacted at 100 ° C. for 5 hours to obtain an ethylenically unsaturated monomer (a12 ′) in which pyromellitic acid was added to 2-hydroxyethyl methacrylate.
(2) Process (Aa)
36 parts of water was added to the ethylenically unsaturated monomer (a12 ′) obtained in the preceding item (1) and reacted at 90 ° C. for 5 hours, thereby remaining in the ethylenically unsaturated monomer (a12 ′). The acid anhydride group to be hydrolyzed. Subsequently, the remaining water was removed under reduced pressure to obtain an ethylenically unsaturated monomer (a12).
(3) Process (B)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was replaced with nitrogen. 23.3 parts, 48 parts of benzyl methacrylate, 8.7 parts of ethylenically unsaturated monomer (a12), 20 parts of ETERRNACOLL OXMA (manufactured by Ube Industries), 40 parts of methoxypropyl acetate, and dimethyl-2,2′-azo A mixed solution in which 6 parts of bisdiisobutyrate 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, the number average molecular weight is 4000, and the average number of copolymerized ethylenically unsaturated monomers (a12) per molecule (that is, the average number of carboxyl group-containing units (G)) is 1.0. A vinyl dispersion resin (A12) was obtained.

<< Synthesis Example 10 >> to << Synthesis Example 12 >>
In the same manner as in Example 12, ethylenically unsaturated monomer (a13) to ethylenically unsaturated monomer (a15) were synthesized to obtain vinyl dispersant (A13) to vinyl dispersant (A15). It was.

<< Synthesis Example 13 >>
(1) Process (F)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 32.6 parts, benzyl methacrylate 54.8 parts, 2-hydroxyethyl methacrylate 4.0 parts, methacrylic acid 8.6 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 parts Was added dropwise over 2 hours, and stirring was continued at the same temperature for 3 hours to complete the reaction.
Thus, a vinyl resin intermediate (F1) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule was obtained.

(2) Process (G)
In a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (F1) in solid content, 14.2 parts of glycidyl methacrylate, and 0.3 part of dimethylbenzylamine Was allowed to react at 100 ° C. for 8 hours while flowing dry air.

  After confirming that the acid value was 5 or less, a vinyl resin intermediate (G1) was obtained. At this time, the site where glycidyl methacrylate was reacted with methacrylic acid was 20 parts in total, 28.5 parts of n-butyl methacrylate, 48 parts of benzyl methacrylate, and 3.5 parts of 2-hydroxyethyl methacrylate. Yes.

  A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of a vinyl resin intermediate (G1) in solid content and 2.9 parts of pyromellitic dianhydride, and dried air was added. The reaction was carried out at 100 ° C. for 6 hours while flowing.

  Thus, a vinyl dispersant (A15) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )

<< Synthesis Example 14 >>
(1) Step (H)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 30.8 parts, benzyl methacrylate 51.9 parts, 2-hydroxyethyl methacrylate 3.8 parts, glycidyl methacrylate 13.5 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 parts Was added dropwise over 2 hours, and stirring was continued at the same temperature for 3 hours to complete the reaction.
Thus, a vinyl resin intermediate (F3) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule was obtained.

(2) Step (I)
In a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (F3) in solids, 8.2 parts of methacrylic acid, and 0.3 parts of dimethylbenzylamine Was allowed to react at 100 ° C. for 8 hours while flowing dry air.
After confirming that the acid value was 5 or less, a vinyl resin intermediate (G3) was obtained. At this time, the site | part which made methacrylic acid react with glycidyl methacrylate is 20 parts of the whole, n-butyl methacrylate 28.5 parts, benzyl methacrylate 48 parts, and 2-hydroxyethyl methacrylate 3.5 parts. Yes.

(3) Process (J)
A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of vinyl resin intermediate (G3) in solid content and 2.9 parts of pyromellitic dianhydride, and dried air The reaction was carried out at 100 ° C. for 6 hours while flowing.
Thus, a vinyl dispersant (A17) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )

<< Synthesis Example 15 >>
(1) Process (K)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 32.0 parts, benzyl methacrylate 53.9 parts, 2-hydroxyethyl methacrylate 14.2 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 parts mixed in advance The liquid was added dropwise over 2 hours, and then stirring was continued at the same temperature for 3 hours to complete the reaction.
Thus, a vinyl resin intermediate (F2) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule was obtained.

(2) Step (L)
A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 100 parts of vinyl resin intermediate (F2) in solids and 12.2 parts of Karenz MOI (manufactured by Showa Denko) and dried. The reaction was carried out at 100 ° C. for 8 hours while flowing air.
After confirming that the acid value was 5 or less, a vinyl resin intermediate (G2) was obtained. At this time, the site | part which made Karenz MOI (made by Showa Denko) react with 2-hydroxyethyl methacrylate is 20 parts of the whole, 28.5 parts of n-butyl methacrylate, 48 parts of benzyl methacrylate, 2-hydroxyethyl It is 3.5 parts of methacrylate.

  A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is charged with 100 parts of a vinyl resin intermediate (G2) in solids, 2.9 parts of pyromellitic dianhydride, and dimethylbenzyl 0.1 parts of amine was charged and reacted at 100 ° C. for 6 hours while flowing dry air.

  Thus, the vinyl dispersant having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. (A16) was obtained.

<< Synthesis Example 16 >>
(1) Process (M)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is charged with 218 parts of pyromellitic dianhydride, 130 parts of 2-hydroxyethyl methacrylate, and 0.3 part of hydroquinone monomethyl ether, and dry air is allowed to flow. The mixture was reacted at 100 ° C. for 5 hours to obtain an ethylenically unsaturated monomer (m18 ′) in which pyromellitic acid was added to 2-hydroxyethyl methacrylate.
(2) Process (Ma)
36 parts of water was added to the ethylenically unsaturated monomer (m18 ′) obtained in the preceding item (1) and reacted at 90 ° C. for 5 hours, thereby remaining in the ethylenically unsaturated monomer (m18 ′). The acid anhydride group to be hydrolyzed. Subsequently, the remaining water was removed under reduced pressure to obtain an ethylenically unsaturated monomer (m18).

(3) Process (N)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was replaced with nitrogen. 33.3 parts, benzyl methacrylate 48 parts, ethylenically unsaturated monomer (m18) 8.7 parts, 2-hydroxyethyl methacrylate 10 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutene A mixed solution in which 6 parts of tylate were previously mixed uniformly was dropped over 2 hours, and then the stirring was continued at the same temperature for 3 hours to complete the reaction.
Thus, the number average molecular weight is 4000, and the average number of copolymerized ethylenically unsaturated monomers (m18) per molecule (that is, the average number of carboxyl group-containing units (G)) is 1.0. A vinyl-based dispersion resin (N1) was obtained.

(4) Step (O)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of a vinyl-based resin intermediate (N1) and 11.9 parts of Karenz MOI while flowing dry air. The reaction was carried out at 100 ° C. for 8 hours.
After confirming that the acid value was 5 or less, the reaction was terminated. Thus, a vinyl dispersant (A18) having a number average molecular weight of 4500 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0. )

<< Synthesis Example 17 >>
(1) Process (P)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is charged with 218 parts of pyromellitic dianhydride, 130 parts of 2-hydroxyethyl methacrylate, and 0.3 part of hydroquinone monomethyl ether, and dry air is allowed to flow. The mixture was reacted at 100 ° C. for 5 hours to obtain an ethylenically unsaturated monomer (p19 ′) in which pyromellitic acid was added to 2-hydroxyethyl methacrylate.
(2) Process (Pa)
By adding 36 parts of water to the ethylenically unsaturated monomer (p19 ′) obtained in the preceding item (1) and reacting at 90 ° C. for 5 hours, the ethylenically unsaturated monomer (p19 ′) remains. The acid anhydride group to be hydrolyzed. Subsequently, the remaining water was removed under reduced pressure to obtain an ethylenically unsaturated monomer (p19).

(3) Process (Q)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was replaced with nitrogen. 35.3 parts, benzyl methacrylate 48 parts, ethylenically unsaturated monomer (p19) 8.7 parts, methacrylic acid 8 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 The liquid mixture which mixed the part uniformly beforehand was dripped over 2 hours, and stirring was continued at the same temperature for 3 hours after that, and reaction was complete | finished.
Thus, the number average molecular weight is 4000, and the average number of copolymerized ethylenically unsaturated monomers (a19) per molecule (that is, the average number of carboxyl group-containing units (G)) is 1.0. A vinyl dispersion resin (Q1) was obtained.

(4) Step (R)
In a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (N1) and 13.2 parts of glycidyl methacrylate were charged, and dry air was allowed to flow. The reaction was carried out at 100 ° C. for 8 hours.
After confirming that the acid value was 5 or less, the reaction was terminated. Thus, a vinyl dispersant (A19) having a number average molecular weight of 4500 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0. )

<< Production Example 1 >>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 48.5 parts, 48 parts of benzyl methacrylate, 3.5 parts of 2-hydroxyethyl methacrylate, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate were previously mixed uniformly. The solution 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 (X11) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule was obtained.

In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl-based resin intermediate (X11) in solids, 5.1 parts of trimellitic anhydride, and dimethylbenzylamine in an amount of 0. 1 part was charged and reacted at 100 ° C. for 6 hours (Step D of Example 2).
Thus, a vinyl dispersant (B1) having a number average molecular weight of 4000 and an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0. )

<< Production Example 2 >> to << Production Example 4 >>
In the same manner as << Production Example 1 >>, vinyl-based dispersant (B2) to vinyl-based dispersant (B4) were obtained.

<< Production Example 5 >>
In Step D, except that the vinyl resin intermediate (X1) was reacted with 2.6 parts of succinic anhydride instead of reacting 5.1 parts of trimellitic anhydride with respect to 100 parts of solid content, << Synthesis was performed in the same manner as in Synthesis Example 1 to obtain a vinyl-based dispersant (B5).

<< Production Example 6 >>
Except for reacting 5.1 parts of trimellitic anhydride with 3.8 parts of phthalic anhydride instead of reacting 5.1 parts of trimellitic anhydride with respect to 100 parts of solid content of vinyl resin intermediate (X1) in Step D, << Synthesis was performed in the same manner as in Synthesis Example 1 to obtain a vinyl dispersant (B6).

<< Examples 1-17 and Comparative Examples 1-8 >>
Table 1 and Table 2 show the weights of the vinyl dispersants (a) obtained in Examples 1 to 17, titanium oxide (manufactured by Wako Pure Chemical Industries), solvent, and glass beads (0.8 mm) as pigments. (G) A 140 mL glass bottle was charged in a ratio (all based on solid content), and placed in a shaker (Scandex SO400 manufactured by F & FM) (hereinafter referred to as Scandex) and dispersed for 3 hours. After 24 hours at 25 ° C., the following tests were conducted.
Furthermore, the acrylic resin obtained in Production Examples 1 to 6, or the commercially available dispersant (Comparative Example 7), the solvent, and the glass beads (0.8 mm) in weight (g) ratios shown in Table 3 (all (Based on solid content) was charged into a 140 mL glass bottle and dispersed with a scandex for 3 hours. After 24 hours at 25 ° C., the following tests were conducted.

(1) Viscosity measurement About the obtained dispersion, the viscosity at 25 degreeC was measured with the rotation speed of 10 rad / sec with the cone plate type | mold viscosity meter using the cone plate of diameter 60mm and angle 0 degree 59 minutes. The results are shown in Tables 1 to 4.
(2) Storage stability over time The obtained dispersion was stored in a thermostat at 50 ° C. for 1 week and accelerated with time, and then the viscosity of the pigment dispersion after time was the same as in (1) “Viscosity measurement” in the previous section The viscosity change rate before and after storage at 50 ° C. for 1 week was calculated and evaluated in two stages according to the following criteria.
○: When the viscosity change rate is within ± 10% and no sediment is formed.
X: When the viscosity change rate exceeds ± 10%, or when a precipitate is generated even when the viscosity change rate is within ± 10%.
(3) Solvent resistance The obtained dispersion was coated on an aluminum plate with a bar coater # 3 and baked in a 230 ° C. oven for 5 minutes. This was immersed in MEK for 15 minutes, and the appearance was visually determined.
○: When there is no particular change in appearance.
Δ: A slight change in appearance is observed.
X: When there is a significant change in the appearance, such as loss of surface gloss.

As described above, the dispersion in which titanium oxide, which is an inorganic pigment, is dispersed using the vinyl dispersant (a) of the present invention has low viscosity and good storage stability with time. On the other hand, when a comparative carboxyl group-containing vinyl resin was used, the solvent resistance was poor or the viscosity was high, and some of the storage stability over time was poor (Comparative Examples 1 to 6). In addition, when a commercially available phosphate ester-containing dispersant (manufactured by Big Chemie; Disperbyk-111) included in the definition of claims of Patent Document 1 is used (Comparative Example 7), a dispersion having a relatively low viscosity is obtained. However, the storage stability with time was poor and the solvent resistance was also poor.

[Production Example 1 of basic synergist (Y)]
After 50 parts of copper phthalocyanine as a pigment component was chlorosulfonated, it was reacted with 15 parts of N, N-diethylaminopropylamine as an amine component to obtain 62 parts of basic synergist (Y1). The basic synergist (Y1) is represented by the following structural formula.

CuPc represents a copper phthalocyanine residue.

[Production Example 2 of Basic Synergist (Y)]
After chloromethylating 50 parts of copper phthalocyanine as a pigment component, it was reacted with 40 parts of dibutylamine as an amine component to obtain 95 parts of basic synergist (Y2). The basic synergist (Y2) is represented by the following structural formula.

CuPc represents a copper phthalocyanine residue.

[Production Example 3 of basic synergist (Y)]
After chloroacetamidomethylation of 50 parts of quinacridone as a pigment component, it was reacted with 40 parts of N-methylpiperazine as an amine component to obtain 103 parts of a basic synergist (Y3). The basic synergist (Y3) is represented by the following structural formula.

[Production Example 4 of Basic Synergist (Y)]
A basic synergist (Y4) was obtained by the same method as in Production Example 1 using diphenyl diketopyrrolopyrrole as the dye component and N-aminopropylmorpholine as the amine component. The basic synergist (Y4) is represented by the following structural formula.

[Production Examples 5 to 6 of basic synergist (Y)]
The following basic synergists (Y5) to basic synergists (Y6), that is, pigment derivatives and anthraquinone derivatives, by the same method as in Production Examples 1 to 4 of the basic synergists (Y1) to (Y4) And an acridone derivative was obtained.

Basic synergist (Y5):

Basic synergist (Y6):

  In the same manner as in Production Examples 1 to 6 of the basic synergists (Y1) to (Y6), by reacting the pigment component, anthraquinone, acridone or triazine with the amine component, or cupping the compound having the amine component Various basic synergists (Y) can be produced by synthesizing dyes by ring reaction.

Example 18
As a pigment (P), 9 parts of Pigment Blue 15: 3, 1 part of basic synergist (Y1), 5 parts of vinyl dispersant (A1) and 45 parts of methoxypropyl acetate were charged into a glass bottle (the amount charged) All were done on a solids basis). After predispersing with a disper, 60 parts of zirconia beads having a diameter of 0.5 mm were charged as a dispersion medium, and main dispersion was performed with scandex to obtain a pigment dispersion.

  The viscosity of the obtained pigment dispersion was measured with a B-type viscometer, and the performance of the dispersion was evaluated based on the viscosity. The viscosity at 6 rpm was 15.0 mPa · s. Further, the obtained pigment dispersion was stored in a thermostat at 50 ° C. for 1 week and accelerated with time, and the change in viscosity of the pigment dispersion before and after aging was measured to determine the storage stability. The viscosity at 6 rpm was 15.5 mPa · s and the rate of change was 3%.

  The obtained dispersion was coated on an aluminum plate with a # 5 bar coater and baked at 200 ° C. for 1 hour to obtain a colored coating film. This was immersed in tetrahydrofuran for 1 hour, and the appearance was visually determined. There was no change in the appearance of the colored coating film, and the solvent resistance was good.

  Furthermore, this colored film was immersed in a 5% strength saline solution for 24 hours to evaluate chemical resistance. There was no change in the appearance of the colored coating film before and after the immersion in the saline solution, and the chemical resistance was good.

<< Examples 19 to 33 and Comparative Examples 8 to 26 >>
Using the components shown in Tables 4 to 7 below (all the amounts charged were based on solid content), pigment dispersions were obtained in the same manner as in Example 11, and evaluated in the same manner as described above. did. The lower the viscosity, the better.

Moreover, the evaluation criteria of the rate of change in viscosity after being stored in a thermostat at 50 ° C. for 1 week and accelerated over time are as follows.
○: When the viscosity change rate is within ± 10% and no sediment is formed.
X: When the viscosity change rate exceeds ± 10%, or when a precipitate is generated even when the viscosity change rate is within ± 10%.

The obtained dispersion was coated on an aluminum plate with a # 5 bar coater and baked at 200 ° C. for 1 hour to obtain a colored coating film. This was immersed in tetrahydrofuran for 1 hour, and the appearance was visually determined.
○: When there is no particular change in appearance.
X: When the appearance is changed, for example, the surface is no longer glossy.

Furthermore, this colored film was immersed in a 5% strength saline solution for 24 hours to evaluate chemical resistance.
○: When there is no particular change in appearance.
X: When the appearance is changed, for example, the surface is no longer glossy.

  Moreover, DB111 is a commercially available dispersing agent (Bic Chemie make: Disperbyk-111). As the alkyd resin, “Phthalkid 133-60” manufactured by Hitachi Chemical Co., Ltd. was used.

In Examples 18 to 23 using Pigment Blue 15: 3, since the vinyl dispersant (a) according to the present invention is used, the viscosity is low, the viscosity stability is good, and the solvent resistance is good. Recognize. On the other hand, in Comparative Example 13 where the vinyl dispersant (a) according to the present invention was not used, the viscosity was high, and in Comparative Example 8 using the comparative vinyl resin (B), the solvent resistance was poor. . Further, in Comparative Example 14 in which neither the basic synergist (Y) nor the vinyl dispersant (a) according to the present invention was used, the viscosity became high at the time of dispersion with Scandex, and separation from the beads was impossible.

  Also in Examples 24 to 33 and Comparative Examples 17 to 26 using other pigments, the excellent effects of the vinyl dispersant (a) and the pigment composition of the present invention were evident.

  The dispersant according to the present invention can be effectively used, for example, for the preparation of pigment dispersions and pigment compositions. Moreover, the said dispersing agent can be efficiently prepared with the manufacturing method of this invention.

  As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims (17)

In the vinyl polymer main chain (A), the carboxyl group-containing unit (G) represented by the following general formula (1) has an average of 0.3 or more and 3.0 or less per molecule of the vinyl polymer. And a crosslinkable functional group-containing unit (I) represented by at least one of the general formulas (51) to (55).

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—,
X ² is a group represented by the general formula: — (— R ^a1 —O—) _m1 −,
(In the formula, R ^a1 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m1 is an integer of 1 to 50.)
X ³ is a group represented by the general formula: — (— C (═O) —R ^b1 —O—) _m2 −,
(In the formula, R ^b1 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m2 is an integer of 0 to 20).
Y ¹ is a group represented by the following general formula (2) or a group represented by the following general formula (3). }

General formula (2)

[In general formula (2),
(I) a combination in which one of A ^{1 to} A ³ is a hydrogen atom and the other two are —C (═O) OH;
(Ii) ^{one of} A ^{1 to} A ³ is —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms), and the other two are — A combination of C (= O) OH,
(Iii) ^{one of} A ^{1 to} A ³ is a group represented by the following general formula (2a), and the other two are a combination of —C (═O) OH, or
(Iv) ^Three of A ^{1 to} A ³ are —C (═O) OH, and k is 1 or 2. ]
General formula (2a)

[In general formula (2a),
X ²¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ²² is a group represented by the general formula: — (— R ^a21 —O—) _m21 −.
(In the formula, R ^a21 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m21 is an integer of 1 to 50.)
X ²³ is a group represented by the general formula: — (— C (═O) —R ^b21 —O—) _m22 −,
(In the formula, R ^b21 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m22 is an integer of 0 to 20).
Z ²¹ is a vinyl polymer main chain (B) containing a group represented by the general formula (21).
The vinyl polymer main chain (A) and the vinyl polymer main chain (B) may be the same main chain or different main chains. ]
Formula (21)

[In General Formula (21), R ²¹ represents a hydrogen atom or a methyl group. ]

General formula (3)

[In general formula (3),
(V) one of A ^{5 to} A ⁷ is a hydrogen atom and the other two are a combination of —C (═O) OH,
(Vi) One of A ^{5 to} A ⁷ is —C (═O) OR ^d (wherein R ^d is an alkyl group having 1 to 18 carbon atoms), and the other two are — A combination of C (= O) OH,
(Vii) one of A ^{5 to} A ⁷ is a group represented by the following general formula (3a), and the other two are a combination of —C (═O) OH, or
(Viii) three of A ^{5 to} A ⁷ are —C (═O) OH;
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 formula (70), or a group represented by formula (71) It is. ]
General formula (3a)

[In general formula (3a),
X ³¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ³² is a group represented by the general formula: — (— R ^a31 —O—) _m31 −.
(In the formula, R ^a31 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m31 is an integer of 1 to 50.)
X ³³ has the general ^{formula: - (- C (= O} ) -R b31 -O-) m32 - with a group represented,
(In the formula, R ^b31 is a linear or branched alkylene group having 4 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms, and m32 is an integer of 0 to 20).
Z ³¹ is a vinyl polymer main chain (C) containing a group represented by the following general formula (31).
The vinyl polymer main chain (A) and the vinyl polymer main chain (C) may be the same main chain or different main chains. ]
General formula (31)

[In General Formula (31), R ³¹ represents a hydrogen atom or a methyl group. ]

Formula (70)


Formula (71)



General formula (51)

[Wherein R ⁵¹ represents a hydrogen atom or a methyl group,
T ¹ is a group represented by —C (═O) — or —C (═O) —OR ^a51 or —Ph ⁵¹ —R ^b51— ,
( ^Wherein , R ^a51 and R ^b51 are each a linear or branched alkylene group having 1 to 8 carbon atoms,
Ph ⁵¹ is a phenylene group. )
T ² is —O— ^{N═CR c51} R ^d51 or a group represented by the formula (72) or the formula (73). ]
(R ^c51 and R ^d51 are each a linear or branched alkylene group having 1 to 8 carbon atoms, or R ^c51 and R ^d51 are integrated to form a cyclic structure having 3 to 8 carbon atoms. ),
Formula (72)

(R ^e51 , R ^f51 , and R ^g51 are each a hydrogen atom or a linear or branched alkylene group having 1 to 8 carbon atoms),
Formula (73)

(N51 is an integer of 1-8.)

General formula (52)

[Wherein R ⁵² represents a hydrogen atom or a methyl group,
R ^a52 is a linear or branched alkylene group having 1 to 8 carbon atoms,
R ^b52 is a linear or branched alkyl group having 1 to 8 carbon atoms. ],
Formula (53)

[Wherein, R ⁵³ represents a hydrogen atom or a methyl group. ],
Formula (54)

[ ^Wherein , R ⁵⁴ and R ^c54 each represent a hydrogen atom or a methyl group,
R ^a54 and R ^b54 are each a linear or branched alkylene group having 1 to 8 carbon atoms. ]

Formula (55):

[ ^Wherein , R ⁵⁵ and R ^d55 each represent a hydrogen atom or a methyl group,
X ^a55 is —C (═O) O—, —C (═O) ^NH— , ^—O— , —OC (═O) — or —CH ₂ O—,
X ^b55 is a group represented by the formula: — (— R ^b55 —O—) _m55 −;
(In the formula, R ^b55 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m55 is an integer of 1 to 50.)
X ^c55 is a group represented by the formula: — (— C (═O) —R ^c55 —O—) _n55 −,
(In the formula, R ^c55 is a linear or branched alkylene group having 4 to 8 carbon atoms, and n55 is an integer of 0 to 20.)
T ⁵ is, -C (= O) - or ^{-R e51 O-C (= O} ) - or ^-R f51 ^{-Ph 51} - is a group represented by.
( ^Wherein R ^e55 and R ^f55 are each a linear or branched alkylene group having 1 to 8 carbon atoms,
Ph ⁵¹ is a phenylene group. )] The vinyl system according to claim 1, wherein A ^{1 to} A ³ in the general formula (2) are the combination (i), or A ^{5 to} A ⁷ in the general formula (3) is the combination (v). Dispersant. The vinyl type according to claim 1, wherein A ^{1 to} A ³ in the general formula (2) are the combination (iii) or A ^{5 to} A ⁷ in the general formula (3) are the combination (vii). Dispersant. Y ¹ carboxyl group-containing unit represented by the general formula (1) (G) is a group represented by the general formula (2), the vinyl dispersion agent according to any one of claims 1-3. The vinyl dispersant according to any one of claims 1 to 4, wherein the vinyl dispersant is represented by the following general formula (4).
General formula (4)

[In general formula (4),
G represents a carboxyl group-containing unit (G) represented by the general formula (1) according to claim 1,
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ is an aromatic group, or —C (═O) —X ⁷ —R ⁷ (where X ⁷ is —O— or —NH—, and R ⁷ is a hydrogen atom or a carbon atom number of 1 to 18 linear or branched alkyl groups, and R ⁷ can have an aromatic group as a substituent).
X ⁴ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ⁵ is a group represented by the formula: — (— R ^a2 —O—) _m3 −,
(Wherein R ^a2 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m3 is an integer of 1 to 50)
X ⁶ is a group represented by the formula: — (— C (═O) —R ^b4 —O—) _m4 −.
(Wherein R ^b2 is a linear or branched alkylene group having 4 to 8 carbon atoms, and m4 is an integer of 0 to 20)
I represents the crosslinkable functional group-containing unit (I) represented by at least one of the general formulas (51) to (55) according to claim 1.
Mainly including the carboxyl group-containing unit (G) in the general formula (4), a hydroxyl group-containing unit (J) containing —X ⁴ —X ⁵ —X ⁶ —H, and —C (R ⁵ ) (R ⁶ ) —. The arrangement of the chain constituent unit (K) and the crosslinkable functional group-containing unit (I) can be included in a random type or a block type,
The carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) contained in the general formula (4) are: In the vinyl polymer main chain represented by the general formula (4), it indicates that they are included in an arbitrary order, and when they are present in plural, they may be the same or different from each other. it can.
p1, p2, p3, and p4 represent the average number of each structural unit per molecule of the vinyl-based dispersant, p1 is 0.3 or more and 3.0 or less, p2 is 0 or more and 180 or less, and p3 is 6 or more and 250 or less, and p4 is 0.1 or more and 180 or less. ]   The vinyl dispersant according to any one of claims 1 to 5, wherein the number average molecular weight is 500 or more and 40000 or less.   The pigment composition containing a pigment and the vinyl-type dispersing agent as described in any one of Claims 1-6.   Furthermore, it contains 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. 8. The pigment composition according to 7. (A) Ethylenically unsaturated monomer (h) having a hydroxyl group and tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) are reacted in advance to produce an ethylenically unsaturated monomer. Process,
(B) The process as described in any one of Claims 1-6 including the process of copolymerizing the ethylenically unsaturated monomer obtained by the said process (A), and another ethylenically unsaturated monomer. A method for producing a vinyl dispersant. (C) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer, and (D) a hydroxyl group of the copolymer obtained in the step (C). The manufacturing method of the vinyl-type dispersing agent as described in any one of Claims 1-6 including the process with which a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) is made to react. (E) While copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer, a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride ( The manufacturing method of the vinyl type dispersing agent as described in any one of Claims 1-6 including the process with which M4) is made to react. (F) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having a carboxyl group;
(G) To the copolymer obtained in the step (F), an ethylenically unsaturated compound having an epoxy group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) are simultaneously or The manufacturing method of the vinyl type dispersing agent as described in any one of Claims 1-6 including the process made to react in arbitrary orders. (H) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having an epoxy group;
(I) A step of reacting an epoxy group of the copolymer obtained in the step (H) with an ethylenically unsaturated compound having a carboxyl group,
(J) Any one of Claims 1-6 including the process of making tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) react with the hydroxyl group of the copolymer obtained by the said process (I). The manufacturing method of the vinyl type dispersing agent as described in one term. (K) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group,
(L) An ethylenically unsaturated compound having an isocyanate group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) are simultaneously added to the hydroxyl group of the copolymer obtained in the step (K). Or the manufacturing method of the vinyl-type dispersing agent as described in any one of Claims 1-6 including the process made to react in arbitrary orders. As the vinyl dispersant,
(M) An ethylenically unsaturated monomer obtained by previously reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) is produced. Process,
(N) a step of copolymerizing the ethylenically unsaturated monomer obtained in the step (M) (provided that an unreacted hydroxyl group remains);
(O) The vinyl-type dispersion | distribution as described in any one of Claims 1-6 including the process of making the ethylenically unsaturated compound which has an isocyanate group react with the hydroxyl group of the copolymer obtained by the said process (N). Manufacturing method. (P) An ethylenically unsaturated monomer obtained by previously reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) is produced. Process,
(Q) a step of copolymerizing the ethylenically unsaturated monomer obtained in the step (P) with an ethylenically unsaturated monomer having a carboxyl group;
(R) The vinyl-based dispersant according to any one of claims 1 to 6, comprising a step of reacting the copolymer obtained in the step (Q) with an ethylenically unsaturated compound having an epoxy group. Production method.   The method for producing a vinyl dispersant according to any one of claims 9 to 16, wherein the acid anhydride to be reacted is trimellitic acid anhydride or aromatic tetracarboxylic dianhydride.