TW200829618A - Polyester dispersing agent and a process for producing the same, and pigment composition prepared therefrom - Google Patents

Abstract

Disclosed is a polyester dispersant which is produced by reacting a hydroxyl group in a vinyl polymer (a) having two hydroxyl groups in one terminal region thereof and optionally a hydroxyl group in a polyol compound c other than the vinyl polymer (a) with an acid anhydride group in an anhydrous tetracarboxylic acid (b) and optionally an acid anhydride group in an anhydrous tricarboxylic acid (d), wherein the vinyl polymer (a) is produced by the radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule. Also disclosed is a process for producing the polyester dispersant. The polyester dispersant shows excellent dispersion property, fluidability and storage stability even when used in a small amount. The polyester dispersant is suitable for an offset ink, a gravure ink, a resist ink for a color filter, an inkjet ink, a coating, a colored resin composition and the like.

Description

200829618 IX. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a dispersion method of a polyester dispersant material and a coloring resin composition, which is excellent in field stability and storage stability, and a pigment composition using the same [Prior Art] More specifically, it relates to a polyester dispersant suitable for coating and can produce a non-assembled, fluid, and a manufacturer thereof. In general, when manufacturing inks and the like, it is difficult to stabilize and high-concentration. The manufacturing process or the product itself creates various problems. For example, the dispersion of the pigment of the fine particles shows high viscosity, and it is difficult to "removal or transport the product by the government machine, and even worse, the gelation occurs in the preservation (4), resulting in difficulty in use. On the surface of the color, there will be a decrease in gloss, poor dyeing, etc. In addition, when different types of pigments are used in the mixed mouth, the color separation due to agglomeration, and especially the phenomenon of falling, sometimes the color of the color display will not appear. In general, a dispersing agent is used in order to maintain a dispersed state in a good manner. The dispersing agent has a structure in which a portion adsorbed to a pigment and a portion having a high affinity with a solvent as a dispersing medium have a high affinity. The performance of the dispersant is determined by the balance of the two functional parts. Various dispersants are used corresponding to the surface state of the pigment as the dispersion, and generally, the pigment is dispersed on the surface having an alkaline surface. In this case, the acidic functional group serves as an adsorption site for the pigment. A dispersant containing a carboxylic acid as an acidic functional group is disclosed, for example, in Patent Document 1 and Patent Document 2 Patent Document 3, Patent Document 4 312XP/Invention Manual (Replenishment)/97-01/96125528 5 200829618, etc. However, in order to manufacture the adhesive, if it is used, the resistance of the coating film may be increased:: The degree of dispersion is low and the dispersion of the dispersion must be used in large quantities. However: it is not good because it is considered to diffuse into inks, paints, etc., and the text is degraded, etc. = Li Wen 1] Japanese Patent (4) Zhao Bulletin 61 — 61623

[Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. (Problems to be Solved by the Invention) The purpose of the present invention is to provide a dispersing agent for obtaining a pigment dispersion excellent in dispersibility, fluidity, and storage stability at a low usage amount. Further, the purpose of the present month is ' Providing polyester dispersion suitable for lithographic inks, gravure inks, color filter 2 photoresist inks, inkjet inks, paints, colored resin compositions, etc., and which can achieve non-aggregation, excellent fluidity, dispersion and stability. (Means for Solving the Problem) The present invention relates to a polyester dispersant which comprises a base in a single terminal region of B: 2 in a vinyl p〇lymer (a) And reacting with an acid anhydride group in the tetrabasic acid anhydride (b), wherein the ethylene type polymer (a) is in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, and ethylene ( Ethylene-unsaturated monomer undergoes free radical polymerization 312XP/Invention Manual (Supplement)/97_〇1/96125528 6 200829618 The present invention also relates to a dispersing agent which is a vinyl type polymer having two hydroxyl groups in a single terminal region t ( a) a hydroxyl group of t, and a hydroxyl group in the polyol compound (c) other than the above-mentioned ethylene type polymer (a), which is formed by reacting an acid anhydride group in the tetrazoic anhydride (b), η, the above ethylene type polymer (a) is a method in which a ethylenically unsaturated monomer is subjected to radical polymerization in the presence of a compound (al) having a ruthenium 2 (10) group and a thiol group in the molecule, and is formed by the present invention. A polyester dispersant which is a hydroxyl group of a vinyl type polymer (a)* having two hydroxyl groups in a single terminal region, an acid anhydride group in a tetracarboxylic anhydride (b), and an acid anhydride group in a tricarboxylic anhydride (d) The ethylene-based polymer (a) is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and a thiol group in the molecule. Further, the present invention relates to a polyester dispersant which has a single terminal region I) domain containing 2 a hydroxyl group in a hydroxyl group-containing vinyl polymer (&), and a polyol compound other than the above-mentioned ethylene type polymer (a) (hydroxyl group in the phantom, and an acid anhydride group and a tricarboxylic anhydride in the tetracarboxylic anhydride (b) (d) is formed by reacting an acid anhydride group in which the ethylenic polymer (a) is an ethylenically unsaturated monomer in the presence of a compound (al) having two mercapto groups and one thiol group in the molecule. Further, the present invention relates to a polyester dispersant which is a hydroxy group in a compound (ai) containing two hydroxyl groups and one thiol group in the molecule, and a four-rebel 312XP/invention In the presence of the compound (a2) which is formed by the reaction of the acid anhydride group in the acid anhydride (b), the ethylenically unsaturated monomer is subjected to radical polymerization to form a product (supplement)/97-01/96125528 7 200829618. Further, the present invention relates to a polyester dispersant which is a compound (al) containing two hydroxyl groups and one thiol group in a molecule, and a polyol compound (c') containing no thiol group. The hydroxyl group is formed by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a3) formed by reacting an acid anhydride group in a tetracarboxylic anhydride. Further, the present invention relates to a polyester dispersant which is a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule, and an acid anhydride group in the tetracarboxylic anhydride (b) and The ethylenically unsaturated monomer is produced by radical polymerization of the ethylenically unsaturated monomer in the presence of the compound (a4) formed by the reaction of the acid anhydride group in the tricarboxylic anhydride (d). Further, the present invention relates to a polyester dispersant which is a compound (a 1) which has two mercapto groups and one thiol group in the molecule, and a polyhydric alcohol compound (c' which does not contain a thiol group. The hydroxyl group in the group, in the presence of the compound (a5) formed by the reaction of the anhydride group in the tetracarboxylic anhydride (b); and the anhydride group in the tricarboxylic anhydride (d), 'frees the ethylenically unsaturated monomer. Generated by base polymerization. In a preferred embodiment of the polyester dispersant of the present invention, the weight average molecular weight is from 2,000 to 35,000 and the acid value is from 5 to 200. In a preferred aspect of the polyester dispersant of the present invention, the tetracarboxylic anhydride (b is represented by the following formula (1) or formula (2), and the formula (1) 312XP / invention specification (complement) Piece)/97-01/96125528 8 200829618 [Chemical 1]

[In the formula (1), k is 1 or 2. ] General formula (2) [Chemical 2]

[In the general formula (2), Qi is a direct bond, -0---C0---COOCH2CH2OCO-, (-S〇2-, -C(CF3)2-, with the formula: [Chemical 3]

The base expressed, or the formula: 312XP / invention manual (supplement) / 97-01/96125528 9 200829618 [Chemical 4]

The basis of the representation. The monomer of the polyester dispersant of the present invention is subjected to radical polymerization: the human's ethylenically unsaturated average molecular weight is from 1 〇〇〇 to 10,000. The weight of the hard part is flatter than the polyester dispersant of the present invention, and the A d爻 season is also used to make the ethylenic unsaturated: the ethylene polymer part obtained by radical polymerization. The transfer temperature is -50 to 70 ° C. In the anamorphic sample, 20% by weight of the ethylenically unsaturated monolithic granules is used in the preferred embodiment of the polyester dispersant of the present invention. Body weight%. In a preferred embodiment of the polyester dispersant of the present invention, the ethylenically unsaturated monomer contains a monomer represented by the following formula (3). Further, the present invention relates to a pigment composition comprising the above polyester dispersant and a pigment. Further, the present invention relates to the above pigment composition, which comprises a pigment derivative containing an organic group, an anthracene derivative containing a basic group, and a basic 312ΧΡ/invention specification (supplement)/97-01/ 96125528 10 200829618 II, 2: At least one of a group consisting of a ketone organism and a triterpenoid organism having an assay group, and a basic derivative selected. Further, the present invention relates to a pigment dispersion obtained by dispersing the above pigment composition in a varnish. Further, the present invention relates to a method for producing a polydispersant dispersant, which comprises the step of ilk. Step A contains a combination of two (four) and one thiol groups in the molecule, and in the presence of D, the ethylenicity is not The saturated monomer is subjected to radical polymerization to produce an ethylene type polymer (4) having two hydroxyl groups in the terminal region; and a wide B1' to react the above ethylene type polymer with a tetracarboxylic acid anhydride (oxime). Further, the present invention relates to a method for producing a dispersant described below, which comprises the following steps: Step A2, comprising two meridians in a molecule! a thiol group-containing compound (radical polymerization of an ethylenically unsaturated monomer in the presence of alk to produce an ethylene type polymer (a) having a terminal hydroxyl group having two hydroxyl groups; and B2, the above ethylene type polymer ( a), a tetracarboxylic anhydride hydrazine), and a polyol compound (6) other than the above ethylene type polymer (a) are reacted. Further, the present invention relates to a method for producing a polyester dispersant, which comprises the steps of: Step A3, in the presence of a compound it (Γ^) containing two base groups and one thiol group in the molecule, The ethylenically unsaturated monomer is subjected to radical polymerization, and the ethylene-type polymer (a) having a hydroxyl group in the end of the bat phase; and the B3, the ethylene-type polymer (a) and the tetracarboxylic anhydride ( b), and the reaction of the tricarboxylic anhydride (d). 312XP/Invention Manual (Supplement)/97_〇1/96125528 11 200829618 The present invention relates to a method for producing a polydispersant described below, which comprises the following steps: The material dA4 contains two warp groups and a knife in the knife. In the presence of a thiol group, the ethylenically unsaturated monomer is subjected to radical polymerization, a: an ethylene type polymer having a hydroxyl group in the terminal region (4); and vB4 is a vinyl polymer (&;), tetracarboxylic anhydride hydrazine), a polyol compound (4) other than the above-mentioned ethylene type polymer (a), and a tri-hectoric anhydride (d). Further, the present invention relates to a method for producing a polyester dispersant, which comprises the steps of: Step B5, a hydroxyl group and a tetracarboxylic anhydride in a compound (al) having two hydroxyl groups and one thiol group in a molecule; The acid anhydride group in (b) is reacted to produce the compound (a2); and in the step A5, the ethylenically unsaturated monomer is subjected to radical polymerization in the presence of the above compound (a2). Further, the present invention relates to a method for producing a polyester dispersant described above, which comprises the steps of: Step B6, preparing a base in a compound (al) having two hydroxyl groups and one thiol group in a molecule, and containing no The base group of the thiol group-containing polyol compound (c,) is reacted with an acid anhydride group in the tetracarboxylic anhydride (b) to produce a compound (a3); and the step A6 is carried out in the presence of the above compound (a3) to give ethylene. The unsaturated monomer undergoes radical polymerization. Further, the present invention relates to a method for producing a polyester dispersant described below, and the package 312XP/invention specification (supplement)/97-01/96125528 12 200829618 includes the following steps: Step B7, wherein the molecule contains two hydroxyl groups and a hydroxyl group in a thiol group-containing compound (al), which is reacted with an acid anhydride group in the tetracarboxylic anhydride (b) and an acid anhydride group in the tricarboxylic anhydride (d) to produce a compound (a4); and - a step A7 In the presence of the above compound (a4), the ethylenic unsaturated and the monomer are subjected to radical polymerization. Further, the present invention relates to a method for producing a polyester dispersant described below, which comprises the steps of: (Step B8, a hydroxyl group or a tetracarboxylic acid in a compound (al) having two hydroxyl groups and one thiol group in the molecule; The acid anhydride group in the acid anhydride (b), the hydroxyl group in the thiol group-free polyol compound (c,), and the acid anhydride group in the tricarboxylic anhydride (d) are reacted to produce the compound (a5); and the step A8, In the presence of the above compound (a5), the ethylenically unsaturated monomer is subjected to radical polymerization. In a preferred aspect of the process of the present invention, the tetracarboxylic anhydride (b) is subjected to the following formula (1) or Expressed by the formula (2): General formula (1) [Chemical 5]

312XP/Invention Manual (Supplement)/97-01/9612552έ 13 200829618 [In the general formula (1), k is 1 or 2. General formula (2) [chemical 6] ( ο η

(2) [In the general formula (2), Qi is a direct bond, -0---C0---COOCH2CH2OCO-, -S〇2_, -C(CF3)2-, with the formula: [Chem. 7]

The base expressed, or the formula: [Chem. 8]

312XP / invention manual (supplement) / 97-01/96125528 14 200829618 based on the basis. In a preferred embodiment of the invention, the benzyl acrylate contained in the ethylenically unsaturated monomer is from 20% by weight to 70% by weight based on the total amount of the monomers. In the preferred embodiment of the present invention, the ethylenically unsaturated monomer contains a monomer represented by the following formula (3): General formula (3) [Chemical 9]

(3) [In the formula (3), 'R is a carbon atom number group. 1 to 4 linear or branched burning (inventive effect) π hunting = using the poly 8 dispersing agent of the present invention, can provide a conventionally unavailable (c dispersibility, fluidity, storage stability a pigment composition. Further, i is a pigment dispersion suitable for a lithographic ink, a gravure ink, a color resist ink, an inkjet ink, a paint, a colored resin composition, and a dispersibility excellent in non-aggregation and fluidity. And stability, and also have storage stability and high stability over time. VIII [Embodiment]: Generally, the pigment dispersant has a high affinity for the portion adsorbed on the pigment and the solvent for the preparation. The structure is characterized by the U-like properties of the two parts. That is, in order to express the dispersibility, the properties of the 312XP/invention specification (supplement)_961922528 200829618 adsorbed on the pigment and the solvent as a dispersing medium are dispersed. The affinity is very important. The tetracarboxylic anhydride (1}) used in the present invention can react with a hydroxyl group to form an ester bond, and can retain a pendant carboxyl group on the resulting polyester backbone. One end region) contains 2 hydroxyl polyol compounds · [10]

HO—one OH

B (wherein A is the end region, β is the ethylene-based polymer portion), and the "a" of the four-reasteric anhydride having the core part of the meaning is "(1) a&gt The reaction step of the tetracarboxylic anhydride and the polyol compound in the case of b, (ii) a = b, or (iii) a < b is shown in the following formula (should be in the following formulas (4) to (6). In the reaction steps (4) to (6), n is the number of repeating units. In the following reaction step (6), if the residual oxime anhydride group in the product is hydrolyzed, the product of the reaction step is based on the structure. In the formula

The Xl moiety has 2 or 3 carboxyl groups, and the plurality of carboxyl groups will effectively serve as adsorption sites for the pigment. Reaction step formula (4): (i)a>b 312XP/invention specification (supplement)/97-01/96125528 16 200829618 [Chem. 11]

Reaction step (5): (ii) a=b [Chemical 12]

Reaction step (6): (iii) a <b [Chemical 13] Ο

HD—A—简+ B COOI! 8 , Ο ο ΗΟΟ€χ 1 ~0—Gn 1 ο \〇Dn reward e’

I ο

Q

HjO r/

.GOOH

:HQ〇0 O ° I B

/^OOM HGOCv 〇c4-〇-Λ-G-Cx .COOH

V ln I V 〇—A 一 ^ 八 V \ B / \

M fO-e COOH HOOC COOH

I 〇B 312XP/Invention Manual (Supplement)/97-01/96125528 17 200829618 Dispersibility, fluidity, and storage stability, so the anti-money base after the reaction of the polyester dispersant of the present invention Do not divide Xl into (four) anhydride and the reconsideration base after peeping. a linear or branched trivalent aliphatic hydrocarbon group of a terminal compound of A and an acid field group (preferably having 1 to 8 carbon atoms) (the ethylene type polymer portion will be added later) Description). The two hydroxyl groups contained in the single terminal region may be bonded to the same carbon atom or may be bonded to different carbon atoms. The preferred core portion Xi is a reaction residue which is reacted with a polycarboxylic acid compound represented by the following formula (1) or formula (2). General formula (1) [Chemical 14]

(1) [In the formula (1), k is 1 or 2. ] General formula (2) [Chem. 15] 312XP / invention manual (supplement) / 97-01/96125528 18 200829618

[In the general formula (2), Qi is a direct bond, -0---CO---COOCH2CH2OCO-, -S〇2-, -C(CF3)2-, with the formula: [Chem. 16]

The base or expression of the formula: [chemical]

The basis of the representation. In the polyester dispersant of the present invention, a single-terminal region containing two vinyl-based polymers (a) and a tetracarboxylic anhydride (b) are reacted, thereby allowing the above reaction 312XP/invention specification (supplement) /97-01/96125528 19 200829618 = a plurality of sulfhydryl groups bonded to the core portion χι in the product of the formula (4) function as a pigment adsorption portion, and the ethylene polymer portion is used as a solvent affinity portion. The role. Further, in the polyester dispersant of the present invention, a compound (al) containing two hydroxyl groups and one thiol group can be initially reacted with a tetracarboxylic anhydride to produce a compound containing no ethylene-based polymer portion B ( A2) to (a5), and then: the thiol group remaining in the above compounds (a2) to (a5) is used as a chain transfer agent (the radical polymerization is carried out, whereby the ethylene type polymer portion B is introduced to obtain the same structure The resin may be formed in the first step B5 to B8 in a plurality of carboxyl groups bonded to the core portion Χι in the product of the above reaction step (4) to act as a pigment adsorption portion, and to be used in the subsequent step. The ethylene-type polymer portion B introduced in the steps A5 to A8 functions as a solvent affinity portion. As shown in the following reaction step formulas (7) to (10), in the first steps B5 to B8 described above, the polyester main layer can be used. The carboxyl group remains on the side chain, and the ethylene type polymer portion b can be introduced in steps A5 to A8. Further, in the following reaction steps (7) to (10), s and t are The number of repeating units, HO-D-0H is a thiol-free polyol compound ( c,). The H〇-d-〇h may also be the above polyol compound BA-(〇H) 2. Step B5 and step A5 [make a compound (al) containing 2 hydroxyl groups and 1 thiol group Four oxic anhydride (b) reaction 'and then introduction of ethylenically unsaturated monomer>: Reaction step (7) 312XP / invention specification (supplement) /97-01/96125528 20 200829618 [Chemistry 18]

ο Ο Q C H〇—Z—〇H -f 〇{ \c SH

.COOH /V/

Xl o

HOOC VH?

OH

SH vinyl monomer L H0 leaf j Z—0—8, /COOH A 〇~°4r|—OH vinyl polymer part

Forget, type oc' polymer I part OH: Μ Μ and step A6 [make 2 bases and! Reaction of a thiol group of tetrahydro acid liver (8) and a thiol group-free polyol compound (C), followed by introduction of an ethylenically unsaturated monomer]: Reaction step (8) eve [Chem. 19] HO—D——OH +

HO—Z-OH \ in , / \ /

C C Ο 乙烯 Vinyl monomer H0t] Z—0—c

HOOC Ο HO ten Z——O——C I,) Ethylene 〇C polymer x/Cs〇^D-

^C〇〇H

/C〇〇H

HOOC

HOOC _0 Seven D-

C—〇j-[D—0—C \〇〇H

• OH

-OH Step B7 and Step A7 [Reacting a compound (al) containing two (four) and i carbon alcohol groups, a tetracarboxylic anhydride (13), and a tricarboxylic anhydride (d), followed by introduction of an ethylenically unsaturated monomer Situation]··· 21 312XP/Invention Manual (supplement)/97-01/96125528 200829618 Reaction step formula (9) [Chem. 20] 〇〇Η

,COOH HO—Z—OH + Ο; Χι /T \ / \ / I V c SH 〇 〇 Ο

HO-fz—Ο—Q

, COOH HOOC, /COOH SH / \ I /X2 HOOC C-θή^Ζ—Ο—CO SH Χί 0 Γ Γ •0—C\ /COOH 1 Ethylene polymer-Λ / HOOC :1 , c—0· 0 part vinyl monomer

HOOC, COOH ethylene type polymer partial step B8 and step A8 [make a compound (al) containing two hydroxyl groups and one thiol group, a tetracarboxylic anhydride (b), a thiol group-free polyol compound (c '), and the reaction of the tricarboxylic anhydride (d), followed by the introduction of ethylenically unsaturated monomers]: Reaction step (10) 22 312XP / invention instructions (supplement) / 97-01 / 96125528

X 200829618 [Chem. 21] HO—Z—OH + HO ——D-OH +

I

SH I 〇 HOH-Z——O——C, o—Cv ΓΟΟΗ '1 , SH /

X o

O-C, /COOH In this way, a plurality of pendant carboxyl groups can be formed to function as a pigment adsorbing portion, and further, step A5 can be carried out by radical polymerization using a residual thiol group as a chain transfer agent. The ethylene-type polymer portion produced in ~A8 functions as a solvent affinity portion. In the present specification, the "ethylene-based polymer portion obtained by radically polymerizing an ethylenically unsaturated monomer" means continuous without a portion derived from a tetracarboxylic anhydride (b) or a tricarboxylic anhydride (d). In part, usually, a plurality of ethylene-type polymer portions B are contained in one molecule constituting the polyester dispersant of the present invention. The weight average molecular weight of the ethylene-based polymer portion B obtained by radically polymerizing the ethylenically unsaturated monomer is preferably from 1,000 to 10,000, more preferably from 2,000 to 8,000, still more preferably from 2,000 to 6,000. Good for 3000 ~ 5000. This portion B will be a part having affinity with a solvent as a dispersion medium. If the weight average molecular weight of the ethylene-based polymer portion B is less than 312XP/invention specification (supplement)/97-01/96125528 200829618, the steric repulsion effect produced by the solvent affinity portion becomes small, and the prevention = is difficult to be 'dispersed' The situation where the stability becomes insufficient. Further, the absolute amount of the solvent affinity portion may increase, and the dispersibility effect may decrease. Further, in the case where the viscosity of the dispersion is increased, the olefinic type accepting compound (a) is easy to adjust the molecular weight to the above range, and the affinity of the agent is also good. The glass transition temperature of the ethylene-based polymer portion B obtained by radically polymerizing the ethylenically unsaturated monomer is preferably -50 to 7 (rc, from the viewpoint of higher dispersibility of the pigment). More preferably, it is -5 〇 to 4 (rc. In the present specification, the Tg (glass transition temperature) of the ethylene type polymer portion B obtained by radical polymerization of an ethylenically unsaturated monomer is used in the following Fox form. The calculated value. Further, a skeleton derived from a compound having two hydroxyl groups and one thiol group in the molecule is also present in the ethylene type polymer (a), but is removed from the calculation of the calculated glass transition temperature in the following calculation. 1/Tg= (Wl/Tgl)+ (W2/Tg2)+ ...+ (Wn/Tgn) ^ In the above formula, Tg is the glass transition temperature of the entire ethylene polymer portion b, and W1 to Wn are used. The weight fraction of the monomers, Tgl to Tgn, represents the glass transition temperature of each homopolymer (in absolute temperature "K"). The Tg of the main homopolymer used in the calculation is exemplified below. n-Butyl acrylate:- 45 ° C (228 K) decyl acrylate · 8 ° C (281 K) n-butyl methacrylate: 20 ° C (293 K) mercapto propylene Benzyl ester·· 54°C (327 K) Lauryl methacrylate··65°C (208 K) 312XP/Invention manual (supplement)/97-01/96125528 24 200829618 Methyl methacrylate: l〇 5 ° C (378 Κ) Hydroxyethyl methacrylate: 55 ° C (328 Κ) 2-hydroxypropyl methacrylate: 26 ° C (299 Κ) Propionic acid: 105 ° C (378 Κ) 曱Acrylic acid: 130 ° C (403 Κ) Styrene: 10 (TC (373 Κ) If calculated by the above method, use 1 part of butyl methacrylate and 100 parts of benzyl methacrylate. The ethylenic unsaturated monomer " the radical-polymerized ethylene-based polymer portion has a glass transition temperature of 36.1 ° C. A single-end region containing two hydroxyl-containing ethylene-type polymers, in addition to the present invention In addition to the method of radically polymerizing an ethylenically unsaturated monomer in the presence of a compound containing two hydroxyl groups and a thiol group in the molecule, it may be obtained by the following method. [1] The single-end region contains i (A) Acrylic-based resin, with 3 amines and 2 secret compounds, (4) Kelvin method = 1 single-end region A method of epoxidizing a carboxylic acid-based resin with a compound containing i of a latex base and a base; [3] comprising a single-end region containing a slow-acid group and two mesogenic groups The method for adding a compound is as follows [4] using a method of extracting human roots from two bases, using a starting agent, a starting agent for polymerization, a radical polymerization, or atom transfer polymerization. . Transfer-type free radical polymerization (active radicals, although by using these methods, it is possible to synthesize a resin having a 312XP/invention specification (supplement)/97-01/96125528 200829618 base in a single-end region, but the reaction requires multiple stages. 2曰±|More than a month, or it is difficult to control the number of cases. Therefore, in terms of productivity, the ethylene residue and monomer are free in the presence of a compound containing a group and a thiol group. The method of base polymerization is optimal. First, the steps of producing an ethylene-based polymer U containing 2 gamma-glucone and an oxime-based group are described. The single-end region contains two trans-type polymer (4), which can be obtained by radically polymerizing an ethylenically unsaturated monomer in the presence of a compound containing a 2 (tetra) group and one thiol in the molecule. Mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethylq, 3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl^, ^ Propylene glycol, 2-sulfoethyl-2-ethyl-1,3-propanediol and the like. As a compound containing two thiol groups and a thiol group in the molecule, for example, ' 可 魏 Weiwei-U-methyl diol, Buweiji, PEG, 3-mercapto-1,2-propanediol (thioglycerol) , 2_巯基^,^ propanediol, 2_ 〇 with the molecular weight of the target ethylene type polymer (a), a compound containing 2 hydroxyl groups and 1 thiol group in the mixed molecule, and an ethylenically unsaturated monomer, and optionally mixed The polymerization initiator is heated and the ethylene type polymer (a) can be obtained. Preferably, 1 to 30 parts by weight of a compound containing two hydroxyl groups and one thiol group is used for blocking polymerization or solution polymerization, more preferably 3 parts by weight based on 1 part by weight of the ethylenically unsaturated monomer. It is preferably 2 to 12 parts by weight, more preferably 5 to 9 parts by weight, even more preferably 2 parts by weight. The reaction temperature is 40 to 150 ° C, preferably 50 to 11 ° C. Water 5 days, with respect to 1 part by weight of the ethylenically unsaturated monomer, any 3 UXP/invention specification (supplement)/97-01/96125528 26 200829618 using 0.001~5 parts by weight of polymerization initiation The azo compound and the organic peroxide are taken. As an even;; can be used jujube 9 9,7 > as a case of a horse-like compound, ", occasional; two-wind double isobutyronitrile, 2, 2, azobis (2-methylbutyl) Nitrile), di-, carbonitrile, 2, 2, azobis (2,4-enhanced 2 azobis(2,4-dimethyl-4-methoxybis(2-methyl) C-, 4,4'-azobis(4-cyanopenta-)2'2-azobis(2-hydroxymethylpropionitrile), 2,2,_azobis-(2 - := (2-base) propyl chloro], etc. As an example of the organic peroxide, there are exemplified by = formazan, tert-butyl peroxybenzoate, cumene hydroperoxide, di-carbon 9 acid, Di-n-propyl acrylate diacetate, oxidized cadaveric sputum- 夂-ethoxyethyl vinegar, perchloric acid neodecanoic acid third butyl vinegar, permethicic acid third cis cis, peroxidation (3 , 5,5_trimethylhexanide), peroxy-propionamidine, diethylperoxide, etc. These polymerization initiators may be used singly or in combination of two or more kinds. The polymerization solvent may be ethyl acetate, n-butyl vinegar acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, and hexane. In particular, the polymerization solvent may be used in combination of two or more kinds. The ethylenically unsaturated monomer 'for example, (meth)propionic acid (meth) acrylate, vinegar, (曱) Base) acrylic propylene vinegar, (methyl) = isopropyl enoate, n-butyl (meth) acrylate, isobutyl acrylate (meth) acrylate, third butyl vinegar (meth) acrylate, (methyl) Acrylic acid 2-ethylhexyl vinegar, cyclohexyl (meth)acrylate, octadecyl (decyl) acrylate, lauryl (mercapto) acrylate, tetrahydrofuranyl (meth) acrylate, (meth) acrylate 312XP /Invention manual (supplement)/97-01/96125528 200829618 decyl ester, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy ethyl (meth) acrylate, phenoxy diethylene Alcohol (meth) acrylate, oxalate butyl ketone (methyl) propyl acetoacetate, methyl lactopolypropylene glycol (meth) acrylate vine, ethoxy polyethylene glycol (fluorenyl) acrylate, etc. Alkoxy polyalkylene glycol (meth) acrylates; (meth) acrylamide, and N, N-dimethyl ( Base) acrylamide, N,N-diethyl(meth)acrylamide, n-isopropyl(meth)acrylamide, diacetone (meth)acrylamide, propylene porphyrin, etc. Substituted (fluorenyl) acrylamides; (mercapto)acrylic acid N,N-dimethylamine f-ethyl ester, (meth)acrylic acid N,N-diethylaminoethyl ester, etc. (meth) acrylates; and nitriles such as (meth) acrylonitrile. Examples of the monomer which can be used in combination with the above acrylic monomer include styrene such as styrene or α-methylstyrene. Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyl esters such as vinyl acetate and vinyl propionate. Further, an ethylenically unsaturated monomer having a carboxyl group may be used in combination. The ethylenically unsaturated monomer having a carboxyl group may be selected from the group consisting of acrylic acid, methyl acrylic acid, itaconic acid, maleic acid, fumaric acid, butyric acid, etc., or the present invention. Among the above-mentioned ethylenically unsaturated monomers exemplified, it is preferred to use 20% by weight to 70% by weight of (meth) acrylonitrile 9 and more preferably 30 to 60% by weight. If it is less than 20% by weight, the solvent affinity becomes low, and the chargeability may not be obtained. If the 70-part two-body rejection effect, the pigment dispersion effect, and the summer %, the knot base interacts with the pigment, resulting in _ Under the condition of dispersion & 312XP/ 嘱 嘱 ( 补 97 97 97 97 97 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 125 W q, & is a monomer represented by the formula (3). The monomer of the formula (3) represented by the following formula (3) is preferably a formula (St (four), more preferably 2 〇 to 70 weight: good. The monomer's solvent affinity is better, and the pigment dispersibility is changed to general formula (3) [Chem. 22]

(3) In the formula (3), R is a linear or branched alkyl group having a carbon number of 丨 to 4. The description of the steps B1 to B4 for reacting a single-end region containing two vinyl group-containing polymers ((a) with a tetracarboxylic anhydride (b). The polyester dispersant of the present invention is made by The single-end region obtained in the steps A1 to A4 is obtained by reacting two radicals of the ethylidene-type polymer (a) with an acid anhydride group of the tetracarboxylic acid anhydride (b) (steps b1 to b4). The tetracarboxylic anhydride (b) used in the present invention may, for example, be hydrazine, 2,3,4-butanetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride or 1,3-. Dimercapto-1,2,3,4-cyclobutanetetracarboxylic anhydride; [,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-diweiylcyclopentyl acetic anhydride, 3, 5, 6 - Tricarboxy-low-box-burning-2-acetic anhydride, 2,3,4,5-tetramethylenetetracarboxylic anhydride, 5-(2,5-di-oxytetrazole 3UXP/invention specification (supplement) /97-01/96125528 29 200829618 Nitrogen-based base)_3—Methyl_3_cyclohexene dicarboxylic anhydride, bicyclo[2, 2, 2]-oct-7-ene_2, 3, 5, 6_ Aliphatic tetracarboxylic acid such as tetracarboxylic anhydride, tetrazoic anhydride, ethylene glycol dip-triphenyl phthalate, propylene glycol hydrazine, triacetic anhydride, butanediol Triacetic anhydride S, 3, 3, 4, 4,-diindole, ketone tetracarboxylic anhydride, 3, 3, 4, 4, _ diphenyl sulfone tetracarboxylic anhydride, hydrazine, 4, $ 8 naphthalene tetramethyl Anhydride, 2, 3, 6, 7-naphthalene tetracarboxylic anhydride, 3, 3, 4, 4, diphenyl ether tetra-hydroxamic anhydride, 3'3', 4'4,-dimethyldiphenyl stone Tetracarboxylic anhydride, 3,3,4,4-tetraphenylnonanetetracarboxylic anhydride, hydrazine, 2,3,4-furan tetracarboxylic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Diphenyl sulfide anhydride, hydrazine (3,4-dicarboxyphenoxy) diphenyl sulfone anhydride, 4,4, bis(3,4_-dicarboxyphenyl = phenyl)diphenylpropane anhydride, 3, 3, , 4, 4, a perfluoroisopropylidene dibenzoic anhydride, 3, 3,4, 4'-biphenyltetracarboxylic anhydride, bis(phthalic acid)phenyl oxide =, para-phenylene Bis(triphenylphthalic acid) anhydride, meta-phenyl-bis(triphenylphthalic acid) anhydride, bis(triphenylbenzenedifluoride)-4,4,-dibenzophenone anhydride, double (triphenyl phthalic acid) - 4, 4, _ diphenylmethane liver, 9, 9 double (3 4 _ tetyl phenyl) anhydride, 9, 9 bis [4 - (3, 4- two Retinophenoxy)phenyl] anhydride, 3, 4-di-reverse-1,2,3,4-tetrahydro-naphthalene a carboxylic acid anhydride such as sulphate or 3,4-dicarboxy-1,2,3,4-tetradec-6-methyl-1-naphthalene succinic anhydride. The tetracarboxylic anhydride used in the present invention is not limited to the above. The compound to be exemplified may have any structure as long as it contains two carboxylic anhydride groups, and the like may be used singly or in combination. Further, from the viewpoint of low viscosity of the pigment dispersion, the tetracarboxylic anhydride of the present invention is preferably an aromatic tetracarboxylic acid anhydride, and more preferably a tetracarboxylic anhydride containing two or more aromatic rings. Further, 312XP/Invention Manual (Supplement)/97-01/96125528 30 200829618 A compound containing one carboxylic anhydride group or a compound containing three or more decanoic acid groups in the molecule may be used in combination. Preferably, a compound containing a phthalic anhydride group in the molecule and a compound containing one carboxylic anhydride group in the molecule are used in combination, and more preferably a tricarboxylic acid anhydride. The carboxyl group bonded to the core portion X4 of the product represented by the following reaction step (11) is 2, which can be stabilized by dispersion. Further, in the following reaction step (11), Η0-Υ'-0Η is a polyol compound. Reaction step (11) f [Chem. 23]

HO—Y,——OH + 2 I

Te—oh' OC—CMi HO—HQ—CO 〇C—〇—Y, one 〇c〇

The -OH is a tricarboxylic acid anhydride. First, an aliphatic tricarboxylic anhydride or an aromatic tricarboxylic anhydride can be mentioned. Examples of the aliphatic tricarboxylic anhydride include, for example, 3-carboxymethylglutaric anhydride, i'2,4-butyring sulphonate 2-anhydride, cis-propene oxime-tricarboxylic acid-1, 2~anhydride, l,3,4-cyclopentanetricarboxylic anhydride, etc. As an aromatic tricarboxylic acid, for example, benzenetricarboxylic anhydride (1,2,3_the present tricarboxylic anhydride, phthalic anhydride oxime, 2,4_stuppyral acid needle), etc. 1,2,4-naphthalene three (four) liver, ", 5-naphthalene tricarboxylic anhydride, 2,3,e: naphthalene dicarboxylic anhydride, 1,2,8-naphthalene tricarboxylic anhydride, etc.), 3,4,4, Diphenyl ketone trisuccinic anhydride, 3, 4, 4'-biphenyl tricarboxylic acid oxime, 3, 4, 4, _ biphenyl trioleic acid 312XP / invention manual (supplement) / 97-01/96125528 31 200829618 Anhydride, 2, 3'2,-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, 3,4'4'-biphenylsulfone tricarboxylic anhydride, etc. In the case of the acid anhydride, in the above, the aromatic tricarboxylic acid anhydride is particularly preferable. In the present invention, in the step B2 and the step B4, the polyol compound (c) other than the above ethylene type polymer (a) can be used in an arbitrary ratio. By using the polyol compound (6) other than the above-mentioned ethylenic polymer (a), the density of the slow acid group or the ratio of the solvent-soluble portion can be easily adjusted. In the present invention, < Polyhydric alcohol compound other than ethylene polymer (a) (C) ", those known can be used, e.g., the knife can be used for industrial polyol compound 3 ~ 4 groups of packets. Among them, only the representative ones are exemplified as belonging to the following groups (1) to (7). For example, (1) B-Saigongyiyi, propylene glycol, 1,3-propanediol, [4-butanol, 1,3-butanediol, 15-5-6, -_ Hongshan, Lb yizhi, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, hydrazine, decyl bisphenol A, hydrogenated bisphenol A, hydroxy trimethyl 'Production... based on acetic acid vinegar, trimethylolethane, trimethylolpropanol; private glycerin, or dibasic yeast (2) such as polyoxyethylene glycol, polyoxypropylene dimer oxypropylene polyoxygen Butanediol, helium two "ethylene polyoxybutylene glycol, various polydecanediols; ... dilute polyoxypropylene polyoxybutylene glycol (3) from the above various polyols, fish tetrahydrofuran, B θ ~ Compounds containing (%) ether linkages of % oxime, propylene oxide, coffee, phenylepoxypropyl or propylpropyl, butyl epoxide f7 A-propyl propyl propyl propyl ether The ring-opening polymerization—3 is modified by the shellfish 4 scale polyols; 312XP/invention specification (supplement)/97-〇1/96125528 ^ 200829618 (4) from the above various polyols of the species above, and the plural (four) The poly(S) which is obtained by co-condensation is a polyhydric alcohol. Use a succinic acid (tetra), adipic acid, 癸^' acid, 壬^-acid, Zhengxu-Tian two people ^, Wenyu Ben-carboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cis Butenoic acid, anti-Wenhan" / cloth - acid, methyl maleic acid, itaconic acid, glutaconic acid, [2 5-hex, P ^ , , ζ, decane dicarboxyl Acid, 1,4-cyclohexane-rebel acid, 1,2,4-benzene-tribasic acid, 1 2 5-& deficiency and 1, B, 3 dicarboxylic acids, U, 4 - cyclohexane a polybasic alcohol obtained by burning three resorcinic acids or 2,5,7~naphthalene, and a polyhydric alcohol obtained from a typical polycarboxylic acid of Φ u 々丁熳虹寺; (5) One or more kinds of lactone-based polyester polyols obtained by polycondensation reaction of various internal hydrazines such as £_caprolactone, pentane vinegar or 3-mercapto-occupanyl vinegar, or a lactone-modified polyester polyol obtained by a polycondensation reaction of the above various polyols, polycarboxylic acids, and various lactones; (6) in the synthesis of a polyester polyol, such as a bisphenol a type Epoxy compound, hydrogenated bisphenol A epoxy compound, monohydric and/or polyhydric alcohol ^ Epoxy-modified polyester polyol obtained from one or more kinds of various epoxy compounds of oxypropyl ether or monobasic acid and/or polyacrylic acid glycidyl ester; (7) Polyester polyamine Alcohol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, argonized castor oil derivative, acrylic copolymer containing hydroxyl group, containing a fluorine-containing compound of a hydroxyl group or a hydrazine resin containing a hydroxyl group, etc. Of course, the polyol compound (c) other than the above-mentioned ethylene type polymer (a), which is optionally added as shown in the above (1) to (7), may be used alone. The two or more kinds may be used in combination, and the weight average molecular weight thereof is preferably 4〇~loooo, more preferably 312XP/invention specification (supplement)/97-01/96125528 33 200829618 100~2000, and more preferably 100~ 1〇〇〇. As the catalyst for producing the polyester dispersant of the present invention, a catalyst can be used. As the catalyst, a tertiary amine compound is preferable, for example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine or N-methyloxan 1,8-di.丫 Bicyclo-[5.4.〇]_7_undecene, ^―2^-[4.3.0]-5-decene, etc. & % The polyester dispersant of the present invention can be produced only from the raw materials mentioned so far, but in order to avoid the problem that the viscosity becomes high and the reaction becomes uneven, it is preferable to use a solvent. The solvent used can be used as known. For example, (iv), methyl ethyl ketone, methyl isobutyl _, cyclohexyl, acetic acid ethyl acetate, acetic acid butyl g, toluene, xylene, acetonitrile and the like can be given. For the reaction: the solvent to be used may be used as a part of the product by distillation or the like after the completion of the reaction. ^Removal, the polyester dispersant of the present invention can be obtained by using an ethylene type polymer (a) having two hydroxyl groups in a single terminal region, a tetracarboxylic anhydride (b), and any addition of a "c-vinyl polymer" ( The polyol compound (c) other than a) is obtained by a reaction. The molar ratio of the acid anhydride group in the tetracarboxylic anhydride (b), the ethylene type polymer (&), and the hydroxyl group in the "polyol compound (c) other than the above ethylene type polymer (a)" is preferably (13)/[(&)+((:)] = 〇.3~1.2, more preferably (8)/[(a)+ (c)] = 〇.4~;1, and thus better ( b) /[(4)+(6)] =〇.5~1.〇, especially good for (13)/[(&)+((:)] = 〇.6~〇.8. (b) /[(+化)];; In the case of the reaction, the remaining acid anhydride group can be hydrolyzed using a necessary amount of water. If it is less than 3, the acid needle residue as a pigment adsorption portion becomes less. In the case of the resin, the acid value of the resin 312XP / invention manual (supplement) / 97-01/96125528 34 200829618 is also low. Also, if it exceeds 12, the target + f · The residue remains in the polyester, and the enthalpy::: the stability of the storage is problematic. Further, the amount of water necessary for the hydrolysis of the acid anhydride group remaining is increased, and the solubility of the solvent is deteriorated. Further, the dispersant of the present invention The acetylated polymer (4), the tetrabasic acid anhydride (8), and the arbitrarily added single-terminal region can be added. Further, the polyol compound (4) other than the oxime, and the tricarboxylic acid anhydride (4) are reacted to obtain an acid anhydride group in the tetrahydrous anhydride (8) and the tribasic acid (4), and the ethylidene polymer (a) and in addition to U). The molar ratio of the radical in the polyol compound (c) is preferably [(8), more preferably [(8) ten (10) / (6) + (4) is hl, and more preferably [(b) + U)] / [ (a) + (c)] = 0.5~1〇, especially preferably [(b)+ (4)]/[(4) + (c)] = 〇· 6~〇· 8 〇 combined with tetracarboxylic anhydride (b) and three The molar ratio of the tetracarboxylic anhydride (b) to the tricarboxylic anhydride (d) when the carboxylic anhydride (d) is used as the acid anhydride is preferably (b) / [(d)] = 〇i 〜10, more preferably (b) ) /[(d)] = 0.i5~4, especially preferably (b)/[(d)] = 0 · 3 〜2 〇 The reaction temperature is from 50 ° C to 180 ° C, preferably 80 ° It is carried out within the range of C~14〇°C. When the reaction temperature is 50 ° C or lower, the reaction rate may be slow. When the temperature is 180 C or more, the carboxyl group may undergo an esterification reaction, and the acid value may decrease to cause gelation. When the reaction is stopped, it is preferred to react until the absorption of the acid anhydride by the infrared absorption disappears. However, after the acid value is measured and it is confirmed that 95% or more of the acid anhydride has been half-esterified, the reaction is stopped. The weight average molecular weight of the obtained polyester dispersant is preferably from 2 〇〇〇 to 35,000 'more preferably from 4,000 to 25,000' and further preferably from 6 〇〇〇 to 20,000, 312 XP / invention specification (supplement) / 97-01 /96125528 35 200829618 Especially good for 7000~15〇〇〇. If the texture of the pigment composition is lowered/not full, then the viscosity of the pigment composition is increased. The acid value of the dispersing agent is ～150, and further preferably 15~lnn, more preferably 10 full 5, then Β±#, 尤 especially good is 20~80. If the acid value is not exceeded, if the adsorption capacity exceeds 2, the pigment dispersibility is lowered and (10)', the interaction between the resins becomes strong, and the viscosity of the pigment composition is increased. The same can be used for the dispersing agent of the same structure as the steps B5 to Β8 and the steps Α5 to Α8, and the above steps Β5 to Β8 are the intramolecular two = thiol-based thiol-based compound (8), tetracarboxylic acid. Acid Xuan (8), the reaction of the ""ol compound (〇, and the triaxial axis), the step of the compound (10), the above steps A5 to a8 in the presence of the above compound (a2), and the remaining compound ((2) a step of performing radical polymerization of a thiol group as a bond transfer agent. A compound (8) having two hydroxyl groups and one thiol group in the molecule and a tetracarboxylic anhydride (b), and optionally a thiol group-free plural Steps B5 to B8 in which the alcohol compound (c) and, in some cases, the compound (a?) to (a5) are produced by reacting with the tricarboxylic acid anhydride (d). The compounds (a2) to (a5) are usable and stepwise. A1 to A4 are obtained by the same method, and the above steps A1 to A4 are a compound (al) and a tetracarboxylic anhydride (b) containing two hydroxyl groups and one thiol group in the molecule, and (a) Steps other than the polyol compound (c) and further reacting with any added tricarboxylic anhydride (d) The tetracarboxylic anhydride (b) and the tricarboxylic anhydride (d) 312XP / invention specification (supplement) / 97-01/96125528 36 200829618 in the anhydride group, and the molecule contains two hydroxyl groups and one thiol group The molar ratio of the hydroxyl group in the compound (al) and the thiol group-free polyol compound (c,) is preferably [(b) + (d)] / [(a) + (c,)] = (K3 to 1.2, more preferably [(b)+(d)]/[(a)+(c')] = 〇.4 〜1·1, and more preferably [(b) + (d)] /[(a) + (c')] = 〇· 5 〜1· 〇, especially good for [(b) + (d)]/[(a)+ (c')] = 〇. 6 〇·· In the case of (b) / [(a) + (c, > 1 reaction, the remaining acid anhydride group may be hydrolyzed by using a necessary amount of water.

Next, in the presence of the above compounds (a2) to (a5), steps A5 to A8 in which the ethylenically unsaturated monomer is subjected to radical polymerization using the remaining thiol groups in the compounds (a2) to (a5) are used. Description. The remaining thiol group obtained by the same method as the steps m to a4 for producing the ethylene type polymer (a) having two hydroxyl groups in the single terminal region is used as a chain transfer agent, and the target knife is known as a knife. Correspondingly, the polymerization initiator is optionally mixed with the ethyl ether unsaturated monomer and added with #, thereby obtaining a #dispersant. 1 part by weight of the compound (al) containing 2 (tetra) group and 1 thiol group in the molecule used in the steps B5 to B8, and 3 to 1 part by weight of the ethylic acid saturating single Bulk polymerization or solution polymerization. More preferably, it is 8 to Μ by weight, and more preferably 10 to 20 parts by weight. The reaction temperature is 4 〇 150 ° C, preferably 50 〜 11 (rc. As the ethylenically unsaturated monomer used, since it is reacted with the acid liver group in the step ~ B8, it can be used not only in the foregoing The unsaturated body shown may also contain a site I having reactivity with a squid. For example, an ethylenically unsaturated monomer having a hydroxyl group may be mentioned. 312XP/Invention Manual (Supplement)/97_〇1/ 96! 25528 37 200829618 The hydroxyl group-containing ethylenically unsaturated monomer used in the above production method may be any one as long as it is a single body containing a hydroxyl group and containing an ethylenically unsaturated double bond, and specifically, Illustrative of a thiol-containing acrylate-based monomer, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3)-hydroxypropyl (meth) acrylate, (fluorenyl) 2 (or 3 or 4)-hydroxybutyl acrylate, and (meth)acrylic acid hydroxyalkanoic acid such as cyclohexanedimethanol mono(indenyl) acrylate; or (meth)acrylamide monomer containing hydroxyl group , for example, N-(2-hydroxyethyl)(meth)acrylamide, N_(2-hydroxypropyl) (A) N-(pyridyl)(methyl)propanamine such as acrylamide or N-(2-butylbutyl)(methyl) acrylamide; or a compound, for example, 2-hydroxyethylethylene ether, 2-(or (i)hydroxypropylvinyl bond 2 (or 3- or 4-)-butylbutylethene-based acetophenone ether; or a warp group Allyl (tetra) monomer, for example, 2-isoethyl ethyl propyl ether 1 2-(or 3-) hydroxypropyl allyl ether, 2 (or 3 or 4 hydroxy hydroxy allylic ether) Isohydroxyalkyl allyl ether. Further, the above hydroxyalkyl (meth) acrylate, N_(hydroxyalkyl) (meth) propylene H is thiolated or thiol ally. The ethylenically unsaturated monomer obtained by addition ring reduction and/or lactone can also be used as a combination of a vinyl group containing a radical and a monomer in the coating method used in the present invention. , ', 2'3- or 1,3-epoxy butyl sinter and the two types of conjugated forms of the two types of alkylene oxides may be Helmets. The lactone can be used as the 312XP/ which is substituted by the burning group of the carbon number of the carbon 6 BRIEF DESCRIPTION OF THE INVENTION (Spread)/97-〇1/96125528 38 200829618 Caprolactone and these lactones. Two or more types of combined systems. It may also be an addition of alkylene oxide and hydrazine. The various pigments J used for the time-scattering are exemplified by the ink-seeking material, the non-capacitance, and the like, such as soluble azo pigment η, / 1 material, phthalocyanine pigment, 啥 ° 丫 _ pigment, H flower酉 酉 酉 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 II# ' ^^^-thanthrone)!. , forest pigment, yellow ketone pigment, dermophenone pigment, diketone quinone, pigment, etc. Further, if a specific example is indicated by the generic name of the dye index, Out: Pigment Black 7, Pigment Blue 6, 15, 5, 1, 15, 3, 15 4 15 · 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 97 , 122, 144, 146, l49, i66, i68, m, 254, 255 yellow 12, 13 109 , 110 148 , 150 178 , 179 , 185 , 206 , 207 , 209 , 220 , 221 , 238 , 242 , pigment purple 19, 23, 29, 30, 37 40, 50, pigments 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 117, 120, 125, 128, 137, 138, 139, 147, 151, 154, 155, 166, 168, 180, 185, Pigment Orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 7 Bu 74 and so on. However, it is not limited to the illustration. Also 'can also be used: titanium oxide, iron oxide, antimony pentoxide, zinc oxide, antimony oxide and other metal oxides, cadmium sulfide, calcium carbonate, barium carbonate, sulfuric acid lock, clay, talc, chrome, carbon black and other inorganic pigments . In the case of carbon black, all carbon blacks such as neutral, acidic, and alkaline can be used. The pigment composition of the present invention 312XP/invention specification (supplement)/97-01/96125528 39 200829618 is not limited to the above pigments, for example, 'can be used containing gold, silver, copper, turning, iron, diamond, nickel, and / 4 or more solid particles of metal fine particles such as alloys. Further, preferably, in the pigment composition using the dispersant of the present invention, the step contains a pigment derivative containing a basic group, a base containing a basic group, and an acridine containing a basic group. At least one basic derivative selected from the group consisting of a ketone derivative and a group containing a basic group of three or two organisms. Here, the term "pigment derivative" refers to a compound in which a specific substituent is introduced into the above-mentioned dye index, and in the present invention, a group containing a basic group is used. By having a basic derivative, it is possible to obtain a pigment which is difficult to disperse in the absence of a basic derivative (in particular, in the case of an organic pigment), and also a pigment composition excellent in dispersibility, fluidity, and storage stability. good. The basic derivative used in the pigment composition of the present invention is derived from a pigment derivative containing a basic group, an anthracene derivative containing a basic group, an acridone derivative containing a basic group, and The group selected for the basic group of trimorphine derivatives. The basic group ' of the basic derivative which can be used in the pigment composition of the present invention is a group consisting of groups represented by the following general formulae (6), (7), (8) and (9) At least one selected base. General formula (6) [Chem. 24] 312XP/Invention manual (supplement)/97-01/96125528 40 200829618 R1 / X~NHCCH2)m-N (6)

V General formula (7) [Chem. 25] E1 / ——CH^N (7) R2 General formula (8) [Chem. 26]

CH-CH R7 V (8) General formula (9) [Chem. 27] 312XP/Invention manual (supplement)/97-01/96125528 41 200829618

(9) In the above formulae (6) to (9), X, X1 is bonded to < represents -so;, a CO-, -CH2NHCOCH2-, -CH2- or straight m represents an integer of 1 to 10. /, 2R each independently represents a heterocyclic group which can be substituted with an alkyl group, an alkenyl group, a phenyl group, or an R group. Wherein the above heterocyclic ring may further contain = nitrogen: oxygen or a sulfur atom. The carbon number of the base and the base is preferably from 1 to 10. Represents a burnt group, an alkenyl group or a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 1 Å. And R, R and R7 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably 丨~5. Y represents -NR8-Z-NR9- or a direct bond. —R and R each independently represent a hydrogen atom, an alkyl group, an alkenyl group or a phenyl group which may be substituted. The carbon number of the alkyl group and the alkenyl group is preferably from 1 to 5. Z represents an alkyl group, an alkenyl group, or a phenyl group which may be substituted. The carbon number of the alkyl group and the dilute group is preferably from 1 to 8. P represents a substituent represented by the formula (10) or a substituent represented by the formula (11). Q represents a hydroxy group, an alkoxy group, a substituent represented by the formula (1〇) or a substituent represented by the formula 312ΧΡ/^_ίί ( ()) / 97·01/96125528 42 200829618 (11). General formula (10) [28]

L General formula (11) [Chem. 29]

R4 R5 CM—

CH

(10) N-R3

CM^CH (11) R7 is a propyl group, a butyl group, a pentyl group, a propyl group or a propylene group in the above formula. The alkyl group of R1 to 5 may, for example, be a methyl group, an ethyl group or a hexyl group. Further, as the base of the riding, there may be mentioned ethylene as the z-bean in the above formula, the pomelo, the methylene group, the ex-ethyl group, the propyl group, the butyl group, and the like. Further, it is an extended alkenyl group, a propylene group or the like. Ethylene is extracted as the methoxy group of Q in the above formula, and examples thereof include methoxy group, ethoxy 312XP/invention specification (supplement)/97_〇1/96(2) like 43 200829618 base, propoxy group, butoxy Base. Further, examples of the functional group which may be substituted include an iS group, a cyano group, an alkoxy group, an amine group, a hydroxyl group, a nitro group, and an epoxy group. Examples of the amine component used to form the substituent represented by the formula (6) to the formula (9) include didecylamine, diethylamine, N,N-ethylisopropylamine, and N,N-. Ethyl propylamine, n,N-mercaptobutylamine, N,N-methylisobutylamine, n,N-butylethylamine, N,N-tert-butylethylamine, diisopropylamine, dipropylamine, N,N-second butyl propylamine, dibutylamine, di-second butylamine, diisobutylamine, N,N-, isobutyl-t-butylamine, diamylamine, diisoamylamine, dihexyl Amine, bis(2-ethylhexyl)amine, dioctylamine, N,N-decyl octadecylamine, diamine, diallylamine, N,N-ethyl-1,2-dimercaptopropylamine, N,n-decylhexylamine, dioleylamine, distearylamine, N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-dimethylaminopentylamine , n,N-diaminobutylamine, N,N-diethylaminoethylamine, N,N-diethylaminopropylamine, N,N-diethylaminohexylamine, N,N-diethyl Aminobutylamine, N,N-diethylaminopentylamine, n,N-dipropylaminobutylamine, N,NI)dibutylaminopropylamine, N,N-dibutylaminoethylamine, n,N -dibutylaminobutylamine, N,N-diiso Aminopentylamine, N,N-decyl-laurylpropylamine, N,N-ethyl-hexylaminoethylamine, N,N-distearate ethylamine, N, dioleylamine , N,N-distearrylamamine, piperidine, 2-mercaptopiperidine, 3-mercaptopiperidine, 4-mercaptopiperidine, 2,4-dimercaptopiperidine, 2, 6 - Dimercaptopiperidine, 3, 5-dimethylpiperidine, 3-piperidinol, 2-piperidinic acid, iso-piperidinic acid, methyl iso-piperidinecarboxylate, iso-3 - Ethyl piperidine, 2-piperidineethanol, abbreviated bite, 3-meridyl ratio of 17 bites, N-aminoethylpyrazine, N-aminoethyl-4-indolyl 17 定, aminoethyl ester, Ν-aminopropyl oxime, Ν-aminopropyl 312 ΧΡ / invention specification (supplement) / 97-01/96125528 44 200829618 yl-2-methylpiperidine, N _Aminopropyl-4_methylpiperidine, N-aminopropyl morpholine, N-methylpiperidin, N-butylpiperidin, N-decyl-high-piperidin, bucyclopentylpiper , 1-amino-4-methylpiperidin, bucyclopentylpiped, and the like. The organic dye constituting the pigment derivative containing a basic group is, for example, a diketone-based succinyl dye, an azo-based dye such as azo, disazo or polyazo, or a phthalocyanine-based dye. Aminodiquinone, pyridoxine, yellow ketone, decyl ketone, indanthrene, dermatanone, purpura _ 蒽 系 色素 色素 色素 奎 奎 奎 奎 奎 奎 奎 奎 奎 奎 奎 奎 奎 色素 色素 色素 色素 色素 色素 色素 色素 色素 色素Pigments such as pigments, flower pigments, sulfur powders, isoporphyrin pigments, isoindolinone dyes, quinophthalone pigments, Shilin pigments, and metal complex dyes. Further, an anthracene derivative containing a basic group and an acridone derivative containing a basic group include a group such as a methyl group, an ethyl group, an amine group, a nitro group, a hydroxyl group or a methoxy group, an ethoxy group, etc. A substituent such as a halogen such as an oxy group or a chlorine. Further, the tris-constituting the trimorphine derivative containing a basic group is a 1,3,5-triazine which may have a substituent, and the substituent is an alkyl group (methyl group, ethyl group, butyl group, etc.), an amine group. , alkylamino (dimethylamino, diethylamino, dibutylamino, etc.), nitro, hydroxy, alkoxy (methoxy, ethoxy, butoxy, etc.), halogen (gas, bromine, etc.), phenyl (which may be substituted by alkyl group, amine group, alkyl amine group, nitro group, hydroxyl group, alkoxy group, halogen, etc.), and phenylamino group (which may be alkyl group, amine group) , alkylamino group, nitro group, hydroxyl group, alkoxy group, self-reagent, etc.), etc. The basic group-containing pigment derivative, anthracene derivative, and bittenone derivative of the present invention can be synthesized through various synthetic routes. . For example, the organic dye, hydrazine or acridone can be introduced by the formula (丨2) to (15), which is represented by the formula 312XP/invention specification (supplement)/97-01/96125528 45 200829618 And reacting with the above-mentioned substituent to form an amine component having a substituent represented by the general formulae (6) to (9), and the amine component is, for example, N,N-dimethylaminopropylamine, N-methyl group, diethylamine or 4-[4-carbyl-6-[3-(dibutylamino)propylamino]-1,3,5-tris-2-amino-amino] Amines, etc. Formula (12) -SO2CI Formula (13) -C0C1 Formula (14) -CH2NHC0CH2C1 Formula (15) -CH2C1 When the substituent represented by the formula (12) to (15) is reacted with the above amine component, It may be mixed with one of the substituents represented by the general formulae (12) to (15) to partially hydrolyze, and the gas atom may be substituted by a hydroxyl group. In this case, the substituent represented by the formula (12) or the formula (13) respectively becomes a sulfonic acid group or a dicarboxylic acid group, and each of them may be in a state of a free acid, and may also be a value of 1 to 3 a metal or a salt of the above monoamine. In the case where the organic dye is an azo dye, the substituent represented by the general formulae (6) to (9) may be introduced into a diazo component or an even component in advance, and then a coupling reaction may be carried out to produce the same. An azo pigment derivative. The above-mentioned tri-negative derivative containing an assay group can be synthesized via various synthetic routes. For example, cyanuric chloride can be used as a starting material to make at least one gas of the trimeric gasification atmosphere and an amine component forming a substituent represented by the formula (6) to formula (9), for example, N, N. - a reaction such as diammonium propylamine or N-mercaptopiped, followed by reaction of residual chlorine of trimeric vaporized cyanide with various amines or alcohols, and the like.曰 312XP / Invention Manual (Supplement) / 97-01/96125528 46 200829618 In the pigment composition of the present invention, the amount of the test derivative is preferably 10 parts by weight based on 100 parts by weight of the pigment. More preferably, it is 〇 heavy, and the portion is preferably 5 to 25 parts by weight. Further, the blending of the polyacetal dispersing agent 1 is preferably 1 part by weight to 1 part by weight, more preferably 2 to 175 parts by weight, and most preferably 5 to 15 parts by weight, based on 1 part by weight of the pigment. The pigment composition of the polyester dispersant of 夂^明 'mixes the resin, additives, etc. as needed' to be dispersed by a horizontal sand mill, a vertical sand mill, a machine, a grinder, etc. A pigment dispersion obtained by dispersing dioxins. For pigments, test:: dispersion:, other resins, additives, can be mixed after all the ingredients = two can first disperse only pigments and test derivatives, or first only disperse alkaline dihalide powder, or only disperse the pigment first , test derivatives and poly 'political 4, which _ people add other ingredients to disperse again. Etc.: Si sand mill, vertical sand mill, ring bead mill, pulverizer before the first eight: Γ Γ 'You can also use the kneading machine, three-roll mill and other ink mills into the knife = use, use double _ Mills, etc. for the processing of fixed organisms, and / or money-based vinegar Π two: quality (four) machine, ball mill, mill, stone mill, super = body. As can be used? V or a mixer can be used to produce pigment dispersion solvents, water, and the like. Further, it is used for active energy ray hardening; second: a liquid monomer which is a main organic active energy ray-hardenable liquid or a medium of a solvent which is a solvent. ^The object can also be used as a substitute for 'a resin which can be used as the pigment dispersion of the present invention'. 312 ΧΡ / invention specification (supplement) / 97-01/96125528 47 200829618 L two-way protein, shellac , rosin modified cis-butyl diacid resin, : _ wax, cellulose, acetic acid - butyric acid cellulose, cyclized rubber, gasified rubber, oxidized rubber, hydrochloric acid rubber, lysine, alkyd Resin, vinegar wax, unsaturated polyester resin, cavity-based resin, epoxy resin, = type resin, vinyl chloride, amine urethane resin containing vinyl chloride __ vinyl acetate Acrylic resin, methacrylic resin, polycarbamic acid m Wei resin, fluororesin, drying oil, synthetic drying oil: styrene modified maleic acid, polyamine resin, chlorinated polypropylene, butadiene plate The tree is biased by the moon and the vinyl chloride resin. Further, the polyester dispersant of the present invention can also be used as a binder resin for a pigment dispersion. The pigment dispersion of the present invention can be used for nonaqueous, aqueous or solventless coatings, gravure inks, lithographic inks, inkjet inks, inks for color calendering sheets, inks for digital papers, coloring of plastics, and the like. (Examples) Hereinafter, the present invention will be specifically described using the examples, but the present invention is not particularly limited to the examples. Further, in the examples, "parts" means "parts by weight", and the table is not "% by weight". Further, the weight average molecular weight was a TSK gel g column (manufactured by Tosoh Corporation), a GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC - 81120 GPC), and THF (tetrahydrofuran,

Tetrahydro uran) is a polystyrene-converted molecular weight when developing a solvent. (Example 1) In the reaction vessel equipped with a gas guiding tube, a thermometer, a condenser, and a mixer, 200 parts of methyl methacrylate is added. Butyl vinegar, replaced by gas. Reverse 312XP / Invention Manual (supplement) /97-01/96125528 48 200829618 The container should be added to 8 f]. Wide % ..., main (10) C, adding 12 parts of 3-mercapto-propanediol, reacted for 12 hours. It was confirmed by solid content measurement that 95% had reacted. Next, add 12 injures of pyromellitic anhydride, 224 parts of cyclohexanone, and 40 parts of 〇· 40 丫 丫 ϋ〇 ϋ〇 -7-7-de-thin, which is confirmed by 12 (rc reaction J 牯 疋 acid value) 98% or more of the acid anhydride has been half-esterified, and the reaction is terminated to obtain a polyacetal dispersant (=dispersant 1; the same below) having an acid value of 4 28 and a weight average molecular weight of #58. (Examples 2 to 6) The raw materials and the amounts of addition shown in Table 1 were synthesized in the same manner as in Example 1 to obtain a polyester dispersant. (Example 7) A gas introduction tube, a thermometer, a condenser, and a (four) machine were provided. The reaction capacity = t, add 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate, and replace with nitrogen. Heat the reaction vessel to 8 (rc, add to 12 parts of 3--sulfo-i , 2 - propylene glycol dissolved in 1 part of 2, 2, an azobisisonitrile solution was reacted for 1 hr. By confirming the determination of 95% of the reaction, adding 19 parts of pyromellitic anhydride, 231 parts of cyclohexanone, and 4 parts of ruthenium as a catalyst, 8 - diindole bicyclo_[5·4〇]_7_undecene, reacted at 120 C for 7 hours. The acid value was determined to confirm 98%. The above anhydride was half-ester, and the reaction was terminated to obtain a polyester dispersant having an acid value of 43 and a weight average molecular weight of 85 Å. (Example 8) The materials and the amounts shown in Table 1 were used, and Example 7 Synthesis was carried out in the same manner to obtain a polyester dispersant. 31 Move/Invention Manual (Supplemental Gifts / (2) Grade 49 200829618 (Example 9) With a gas introduction tube, a thermometer, a condenser, a scrambler Reaction capacity: Add '100 parts of n-butyl methacrylate and 1 part of methacrylic acid vinegar, replace with nitrogen. Heat the reaction volume ii to 12 parts of 3, ki-u-propylene glycol Dissolved in 1 part 2, 2, - diene double-different m reaction j 〇 hours. Confirmed by the solid part determination, the Na reaction added 37 wounds BPDA, 255 parts of cyclohexanone, and 〇. 4 parts as a touch Uj丫 double ring _[5.4 ()]_7_ 十-稀, after 12 generations of reaction ^ then, add 5 parts of neopentyl glycol, determine the acid value and confirm that 98% of the anhydride has been half esterified 'end reaction' A polyester dispersant having an acid value of 56 and a weight average molecular weight of 9,300 was obtained. (Example 1 〇~1 7 ) The materials shown in Table 1 The addition amount was the same as that of Example 7, and the synthesis was carried out to obtain a polyacetal dispersant. (Examples 18 to 22) Phase: The raw material and the amount of addition which were not used, and Example 9 The synthesis was carried out in the same manner to obtain a polyester dispersant. (Examples 23 to 27) Description: The raw material and the addition amount were carried out in the same manner as in Example 7 to obtain a polyester dispersant. 28) In the apparatus: add ν human tube, thermometer, condensation 11, reaction reagent ester of the mixer, and replace it with 2100 parts of n-butyl methacrylate and 100 parts of n-butyl acrylate. Heat the reaction vessel to 8 (TC, added to 12 3_«__/97 612 612 fiber 50 200829618 parts of 3-mercapto-1,2-propanediol dissolved in 〇·1 part 2, 2,-azo diiso A solution of butyronitrile was reacted for 10 hours. It was confirmed by solid content measurement that 95% had been reacted. 4 parts of PMA, 26 parts of trimellitic anhydride, 242 parts of cyclohexanone, and 0.40 parts of catalyst were added. 8-diindole bicyclo-[5·4· __ ene, reacted at 120 C for 7 hours. The acid value was determined and it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated to obtain an acid value of 71. Polyvinyl acrylate dispersing agent of 5800 (Examples 29 and 30) A polyester dispersant was obtained in the same manner as in Example 28 except that the raw materials and the amounts of addition described in Table 1 were used. Example 31) In a reaction vessel equipped with a gas tube, a thermometer, a condenser, and a (four) machine, 100 parts of n-butyl methacrylate and 1 part of n-butyl acrylate were added and replaced with nitrogen. Heating to 80t, added to 12 parts of 3: thiol-i, 2-propanediol dissolved in 1 part of 2, 2, _ azobisiso m reaction 1G / j, by solid form Confirmed that 95% has been reacted with L plus 12 parts of pMA, 21 parts of trimellitic acid liver 'part of cyclohexanone, and 0. 40 parts of catalyst as 8_two SI: value at W counter.... , Chasing the second measurement of the acid value and breaking the QRG / (Examples 32 to 34) Knife 1 is the polyacetal dispersant. 32Γ22nd original: and 'except for the synthesis of the example, obtained Polyester dispersant. 312XP/Invention manual (supplement) gland (4) 6125528 200829618 (Example 35) In the reaction volume with gas introduction tube, thermometer, condenser, and agitator, add 12 parts of 3-weiki-1,2 - Propylene glycol, 19 parts of PMA, and 31 parts of cyclohexanone, and replaced with nitrogen. The inside of the reaction vessel was heated to 1 Torr (rc, reaction for 7 hours. The acid value was measured to confirm that 98% or more of the anhydride had been half esterified) Cool the internal temperature to 70 ° C, add 1 〇 0 parts of fluorenyl n-butyl acrylate and 100 parts of benzyl methacrylate, add 2 parts of dissolved 〇 · 5 parts 2, 2 - A solution of azobisisobutyronitrile in cyclohexanone was reacted for 1 hr. The polymerization was confirmed to be 95% by solid fractionation, and the reaction was terminated. The acid value was 43, and the weight was obtained. A polyester dispersant having a molecular weight of 9 Å. (Examples 36 to 38) A polyester dispersant was obtained in the same manner as in Example 35 except that the materials and the amounts shown in Table 1 were used. (Example 39) In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, '12 parts of 3-mercapto-1,2-propanediol, 37 parts of PMA, 11 parts of neopentyl glycol, and 60 parts of cyclohexanone were replaced with nitrogen. The inside of the reaction vessel was heated to 100 ° C and allowed to react for 7 hours. After determining the acid value and confirming that the anhydride above 98 °/◦ has been half-esterified, the internal temperature was cooled to 7 (rc, 8 parts of methyl methacrylate, 80 parts of butyl acrylate, 4 parts of thiol acrylate). 2-Hydroxypropyl vinegar' was added to 200 parts of a solution of 2,2,-azobisisobutyronitrile dissolved in hexanone to react for 1 hour. It was confirmed by solid content measurement that the polymerization had been carried out 95%. The reaction was terminated, and a polyester dispersant having an acid value of 73 and a weight average molecular weight of 13,000 was obtained. 312 XP/Invention Manual (Supplement)/97-01/96125528 52 200829618 (Examples 40 to 42) Table 1 The raw material and the amount of addition were synthesized in the same manner as in Example 35 to obtain a polyester dispersant. (Example 43) A reaction gas source called a gas introduction official, a thermometer, a condenser, and a mixer Add '12 parts of 3 - I 1 . Knife 0 - 1 - 2-propanediol, 12 parts of PMA, 11 parts of trimellitic anhydride, and q qm p ua and "know hexanone, and replace with nitrogen. The reaction vessel was heated to 1 GG ° C for 7 hours. After determining the acid value and confirming that 98% or more of the phthalic anhydride was half esterified, Cool the crucible in the system, add 8 〇, part of methyl methacrylate, 8 parts of butyl acrylate, 20 parts of decyl propylene I 5 acetonitrile, and 2 parts of 2-hydroxypropyl methacrylate, add 200 The solution was prepared by dissolving 0.5 part of 2,2'-azobisisobutyronitrile in cyclohexanone solution and reacting for 1 〇. The solid content was confirmed to be 95%, and the reaction was terminated. 53. A polyester dispersant having a weight average molecular weight of 1 Å. (Examples 44 to 46) The synthesis was carried out in the same manner as in Example 35 except that the materials and the amounts shown in Table 1 were used. Polyester dispersant. (Example 47) Grab the reaction volume with gas guide, thermometer, condenser, mixer. Add 12 parts of 3-mercapto-1,2-propanediol, 15 parts of PMA, 11 parts of new penta The diol, 14 parts of trimellitic anhydride, and 52 parts of cyclohexanone were replaced with nitrogen. The reaction vessel was heated to 丨〇〇t for 7 hours. The acid value was determined to confirm that more than 98% of the anhydride had been esterified. After the process, the internal temperature is cooled to 312XP / invention manual (supplement) /97-01/96125528 53 200829618 70 C, join 8 0 parts of methyl methacrylate, and 1 part of butyl acrylate, 2 〇 injury of f-acrylic acid 2~ propyl vinegar, 200 parts of dissolved 〇 · 5 parts of 2, 2'-azobisisobutyronitrile The cyclohexanone solution was reacted for 1 hour. It was confirmed by solid-state separation that the polymerization had proceeded 95%, and the reaction was terminated. A polyester dispersant having an acid value of 63 and a weight average molecular weight of 9 Å was obtained. 48~50)

In the same manner as in Example 35 except that the raw materials and the amounts of additions shown in Table 1 were used, a polydispersant was obtained. The raw materials and properties of the dispersant obtained in the "X column 134" are shown in Tables 1 and 6 and the polyester dispersant materials and properties obtained in the examples 35 to 50 are shown in Tables 5 and 6. 312XP/Invention Manual (Supplement)/97-01/96125528 54 200829618 [Table 1] Raw material Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Synthetic resin dispersing agent 1 Dispersing agent 2 Dispersing agent 3 Dispersing agent 4 Dispersing agent 5 Dispersing agent 6 Dispersing agent 7 Dispersing agent 8 Dispersing agent 9 N-butyl methacrylate 200 100 100 90 100 100 100 100 100 E-sweet Monomer benzyl methacrylate methacrylate lauryl methacrylate methyl 100 100 100 100 100 100 100 100 methacrylate methacrylate butyl acrylate 10 thiol polymerization starter 3-mercapto-1,2- Propylene glycol 2-mercapto-2-methyl-1,3-propanediol 12 12 12 12 25 40 12 12 12 Polymerization initiator 2,2,-azobisisobutyronitrile 0.1 0.1 0.1 Ethylene polymer (a) Mw 4000 4000 3600 3900 2500 1900 3500 4200 4200 Ethylene polymer (a) glass transition temperature CC) 20 36 36 41 36 36 36 36 36 PMA 12 12 19 19 40 65 19 Tetracarboxylic anhydride (b) BPDA 26 37 BPAF neopentyl glycol 5 polyol (C) DMBA C1015N C201 5N tricarboxylic acid needle (4) trimellitic anhydride solvent cyclohexanone 224 224 231 231 265 305 231 238 255 Catalyst DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acid value 28 28 43 71 78 109 43 42 56 Mw 5800 5800 8100 8300 6300 6400 8500 9000 9300

312XP/Invention Manual (Supplement)/97-01/96125528 55 200829618 [Table 2] Raw Material Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Synthesis Tree Lunar Dispersant 10 Dispersant 11 Dispersant 12 Dispersant 13 Dispersant 14 Dispersant 15 Dispersant 16 Dispersant 17 Dispersant 18 n-butyl decyl acrylate 100 160 60 100 100 100 1 〇〇 ethylenically unsaturated monomer Benzyl methacrylate methacrylate laurate methyl methacrylate 100 40 140 100 100 100 100 100 methacrylate butyl acrylate 100 200 thiol polymerization from 3-mercapto-1,2-propanediol 2 - mercapto-2-mercapto-1,3-propane 12 12 12 12 12 12 5 60 60 initiator 2, 2'-azo double 0.1 0.1 polymerization initiator isobutyronitrile 0.1 0.1 0.1 0.1 0.1 0.1 0.1 B-type polymer (a) Mw 4200 3900 4000 3800 4100 3850 9100 1050 1100 Ethylene polymer (a) glass transition temperature (°C) 36 26 46 29 8 36 36 36 36 PMA 19 19 19 19 24 8 97 143 Tetracarboxylic anhydride (b) BPDA BPAF 41 Multi-fermented (C) neopentyl glycol DMBA C1015N C2015N 39 Tricarboxylic acid trimellitic anhydride (d) Solvent cyclohexanone 253 231 231 231 231 236 213 357 443 Catalyst DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acid Value 39 43 43 76 43 53 19 140 200 Mw 9100 9000 9100 8800 9300 9600 20400 2200 2300 56 312XP / invention specification (supplement) /97-01/96125528 200829618 [Table 3] Raw material embodiment IS Example 2C Example 21 Example 22: Example 23 Example 24 Example 25 Example 26 Example 27 Synthetic resin dispersant 19 Dispersant 20 | Dispersant 21 Dispersant 22 Dispersant 23 Dispersant 24 Dispersant 25 Dispersant 26 Dispersant 27 N-butyl methacrylate 100 100 100 100 100 160 60 60 Benzyl methacrylate 100 100 100 100 100 Lauryl methacrylate 60 Ethylene unsaturated monomer methyl methacrylate 140 Methyl methacrylate 40 40 Butyl acrylate 140 100 thiol polymerization from 3-sulfenyl-1,2-propanediol 5 12 12 12 12 12 12 12 starter 2-mercapto-2- Base-U-propylene glycol 14 polymerization initiator 2,2'-azobisisobutyronitrile 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1% of ethylene type polymer (a) Mw 8500 4200 3800 4200 4100 3500 3500 3500 3500 Glass transition temperature (°C) of polymer (a) 36 36 36 36 36 18 -29 -43 75 PMA 57 39 39 29 20 19 19 19 19 Tetracarboxylic anhydride (b) BPDA BPAF Neopentyl glycol DMBA 41 15 Multiple Alcohol (C) C1015N 111 C2015N 111 Tricarboxylic acid trimellitic anhydride.. Anhydride (d) Solvent cyclohexanone 303 265 251 241 220 231 231 231 231 Catalyst DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acid value 148 96 55 42 44 43 43 43 43 Mw 22500 8000 12000 9400 9500 8500 9200 9500 8800 312XP/Invention Manual (Supplement)/97-01/96125528 57 200829618 [Table 4] Raw material Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Synthetic resin dispersant 28 Dispersant 29 Dispersant 30 Dispersant 31 Dispersant 32 Dispersant 33 Dispersant 34 N-butyl methacrylate Benzyl olefinate lauryl methacrylate 100 100 100 100 100 100 100 Ethylene unsaturated mono g methacrylate methyl methacrylate decyl acrylate 100 100 100 100 100 100 100 thiol polymerization initiator 3-sulfonyl-1,2-propanediol 2-weiry-2-methyl-1,3-propanediol 12 12 12 12 12 12 12 Polymerization initiator 2, 2,-azobisisobutyronitrile 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ethyl polymer (a) Mw 3700 3700 3700 3700 3800 4200 4100 Ethylene polymer (a) glass transition temperature (°C) -17 -17 -17 -17 -4 -17 -4 PMA 4 17 9 12 11 Tetracarboxylic anhydride (b) BPDA BPAF 39 39 Neopentyl glycol 3 Polyol (C) DMBA C1015N C2015N 106 211 3 Tricarboxylic anhydride (d) Trimellitic anhydride 26 2 16 21 33 33 19 Solvent Cyclohexanone 242 231 238 245 357 456 245 Catalyst DBU 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Acid value 71 43 60 74 74 58 68 Mw 5800 8400 7100 7500 9800 12000 6500 312XP / invention manual (supplement) / 97-01/ 96125528 58 200829618

[Table 5] Raw material Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Synthetic resin dispersant 35 Dispersant 36 Dispersant 37 Dispersant 38 Dispersant 39 Dispersant 40 Dispersion Agent 41 Dispersant 42 Thiol-based polymerization initiator 3-mercapto-1,2-propanediol 12 12 25 8 12 12 12 12 Tetracarboxylic anhydride (b) PMA BPDA 19 19 40 12 37 37 28 37 BPAF neopentyl glycol 11 Polyol (C) C-1015N C-2015N 106 53 212 Tricarboxylic anhydride (d) Trimellitic anhydride n-butyl decyl acrylate 100 90 90 benzyl methacrylate decyl acrylate lauryl 100 100 80 80 100 B Dilute unsaturated monomethyl methacrylate 80 80 80 butyl methacrylate 80 80 80 80 80 hydroxyethyl methacrylate 40 20 2-hydroxypropyl methacrylate 10 40 40 40 10 20 2,2'-azobisisobutyronitrile 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Solvent cyclohexanone 232 232 266 220 261 356 294 462 Glass transition temperature of ethylene type polymer part (°c) 36 36 6 14 14 1 36 1 7 Acid value 42 43 77 29 73 54 49 41 Mw 9100 11000 8200 18500 13000 22000 15000 23000 312XP / invention manual (supplement) /97-01/96125528 59 200829618

[Table 6] Raw material Example 43 Example 44 Example 45 Example 46 Example 47 Example 48 Example 49 Camper! R Π Synthetic resin dispersant 43 Dispersant 44 Dispersant 45 Dispersant 46 Dispersant 47 Dispersion Agent 48; Dispersant 49 Dispersant 50 Thiol-based polymerization initiator 3-mercapto-1,2-propanediol 12 12 12 12 12 12 12 12 PMA 12 19 15 31 25 Tetracarboxylic anhydride (b) BPDA 8 QQ BPAF 31 neopentyl glycol 11 polyol (c) C-1015N 106 C-2015N 212 212 tricarboxylic anhydride (d) trimellitic anhydride 11 8 10 1 7 14 27 22 22 n-butyl methacrylate 90 90 Benzyl methacrylate 100 100 Lauryl methacrylate ethylenically unsaturated monomethyl methacrylate 80 80 80 80 80 80 butyl methacrylate acrylate 80 80 100 100 80 80 hydroxyethyl methacrylate 20 20 曱2-hydroxypropyl acrylate 20 20 10 20 20 40 10 40 Polymerization initiator 2,2'-azobisisobutyronitrile 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Solvent cyclohexanone 236 240 231 250 253 377 472 480 B Glass transition temperature (°C) of the polymer portion 17 17 36 6 6 14 36 14 Acid value 53 60 39 46 63 84 55 53 Mw 10000 14000 8400 13000 9100 22000 32500 31000 312XP / invention manual (supplement) / 97- 01/96125528 60 200829618 PMA: pyromellitic anhydride (manufactured by Daicel Chemical Industry Co., Ltd.) BPDA: 3, 3', 4, 4'-biphenyltetracarboxylic anhydride (manufactured by Mitsubishi Chemical Corporation) 6卩8? :9,9-bis(3,4-dicarboxyphenyl)sebacic anhydride (manufactured by Chem. Co., Ltd.) DMBA: Methyl butyric acid (Perstorp) C-1 015N: Bifunctional polycarbonate Ester polyol, trade name Kuraray Polyol C-1015N (value 112 mgKOH/g, manufactured by Kuraray Co., Ltd.) C-2015N: difunctional polycarbonate polyol, trade name Kuraray Polyol C-2015N (value 56 mgKOH) /g, manufactured by Kuraray Co., Ltd.) DBU : 1,8-di-bicyclo-[5·4·0]-7-fluorene-ene (manufactured by San-apro Co., Ltd.) (Comparative Example 1) with a mixer and reflux 025 parts of dimethyl terephthalate, 420 parts of propylene glycol, 21. 2 parts of glycerin, 0.2 parts of zinc acetate, and 0. 025 were added to a 4-neck flask of a cooling tube, a gas introduction tube, a thermometer, and a dropping funnel. The tetrabutyl orthotitanate is subjected to a vinegar exchange reaction at 160 to 220 ° C while stirring under a nitrogen stream. After 95% (175 g) of the theoretical amount of decyl alcohol is removed, the flask is gradually taken out. The mixture was subjected to a reaction under reduced pressure at 1 to 3 torr at 240 ° C for 3 hours to obtain a polyester having a hydroxyl group at the terminal, followed by decompression in a flask with nitrogen. In addition, gradually cooled to 200 ° C. After reaching 200 ° C, 65 parts of succinic anhydride was added for 1 hour to obtain an acid value of 40, weight average molecule 312XP / invention specification (supplement) / 97-01/96125528 61 200829618 12000 polyester dispersant (=Comparative dispersant 丨; the same applies hereinafter) (Comparative Example 2) Add 75 to a 4-neck flask equipped with a mixer, a reflux cooling tube, a gas guide f, a thermometer, and a dropping funnel. Cyclohexanone, 17 8 parts of neopentyl glycol, and 31.9 parts of pyromellitic anhydride, heated to 15 〇 16 〇. 〇: reacted under nitrogen for 5 hours. When the resin acid value reached 334 or less Cooling, adding 249.7 parts of ε-caprolactone, 〇.6 parts of tetrabutyl titanate, and stirring at 150 ° C for 5 hours. At the time when the heating residue reached 76% or more (cooling, adding 625 parts of cyclohexanone) A polyester dispersant having an acid value of 54 and a weight average molecular weight of 12,900 was obtained. Further, the polyester dispersant prepared in Comparative Example 2 corresponds to the polyester dispersant described in the above Patent Document 2. (Comparative Example 3 ) with mixer, reflux cooling tube, gas inlet tube, thermometer, drop In a 4-neck flask of a funnel, a mixture of 25·4 g of 1,2,4,5-benzenetetracarboxylic acid, (39·〇g of 2-ethylhexanol, and 50 mL of diphenylbenzene) was added thereto. 0.2 g of tetrabutyl titanate was added thereto, and the mixture was heated under reflux for 18 hours in a nitrogen stream (Tc was heated and refluxed for 18 hours, and the generated moisture was separated by a Dean-Stark trap. After completion of the reaction, diphenylbenzene was removed under reduced pressure at 150 °C. A polyester dispersant having an acid value of 96·0 gKOH/g and a light brown color was obtained. Further, the polyester dispersant prepared in Comparative Example 3 corresponds to the polyester dispersant disclosed in Patent Document 1 above. (Comparative Example 4) In a 4-necked flask equipped with a stirrer, a reflux cooling tube, a gas introduction tube, a thermometer, a drop 312XP/invention manual (supplement)/97-01/96125528 62 200829618 liquid funnel, 19·8 parts were added. Benzene, 2·1 parts of octanol, 77·9 wound ε-caprolactone, and 16 parts of tetrabutyl vinegar titanate, heated to 15〇1 60 ° C for 5 hours under nitrogen atmosphere, confirming heating residue After the substance reached 78% or more, it was cooled to obtain a polyester monool. 31.86 parts of the synthesized polyester monool and hydrazine·98 parts of trimellitic anhydride were added, and the reaction was carried out under a nitrogen atmosphere at 150 to 160 °C. When the acid value of the resin reaches 22.7 or less, 2.55 parts of YED122 (manufactured by Nippon Epoxy Co., Ltd., trade name: alkylphenol monoepoxypropyl ether, epoxy equivalent of 250) is added, and the phase is carried out at the same temperature. The reaction is carried out. When the acid value of the resin reaches 1.1 or less, 1.96 parts of trimellitic anhydride is added, and the reaction is carried out at the same temperature. When the acid value of the resin reaches 38.7 or less, 5. 丨 ΕΜ ΕΜ 22 is added at the same temperature. In the reaction, when the acid value of the resin reaches 18 or less, 3 92 Torr of trimellitic anhydride is added to carry out the reaction at the same temperature, and the mixture is cooled at the following time, and 53.6 parts of xylene is added to obtain an acid value of 58.9, and the weight average molecular weight is 58.9. The polyester vinegar (dispersing agent) of 11 〇 G 。. Further, the polyester viscous dispersing agent prepared in the comparative example 4 corresponds to the polyester dispersing agent disclosed in the above Patent Document 3. (Comparative Example 5) (〇· 18 mol) Phosphorus oxychloride was dissolved in 70 parts of tetrahydrofuran, placed in a reaction vessel, and cooled to -5 f). Wide. # 1 η η8η 1 Μ Dm I m Make 0 parts of PlaXel FM4 ( Daicel I. 16.7 g (〇.17 rib 1) triethylamine and hydrazine. 1 part p-Benzene::= solution 15G parts of four M s, put the dropping funnel. - While blowing dry nitrogen, side ^ PWHA solution. Drop, two: two solutions 'drop the above night dripping through the sputum and keep -45~-5 (TC, drop the knot 312XP/Invention Manual (Supplement)/97-01/96125528 63 200829618 After the bundle is kept at -45 ° C for 1 hour and 20 minutes. After that, the temperature is raised to Gt:, and 15 drops of water and 37.9 parts of triethylamine are dissolved by dropping. The solution of tetrahydrofuran was added to iv. After the completion of the dropwise addition, the mixture was stirred under ice cooling for 15 hours to complete hydrolysis of the p-ci bond. Thereafter, the triethylammonium chloride precipitated was separated by filtration under 3 Torr. The tetrahydrofuran was removed under reduced pressure, and the known solid was washed with a 〇·3 N aqueous solution of hydrochloric acid, and then washed several times with benzene, and then dried under reduced pressure at room temperature to obtain a polyester dispersant containing a phosphate group at the end. The polyester dispersant which was obtained in the comparative example 5 corresponds to the polyester oxime dispersant described in the above Patent Document 4. [Production Example 1 of the pigment derivative (Y) containing an organic group] 50 parts of the pigment After the component of copper phthalocyanine is chlorosulfonated, with 14 parts of N, N- as an amine component The guanamine propylamine is reacted to obtain 62 parts of the pigment street organism (Y1) containing the test group. The pigment derivative containing a basic group (Υ1) [/30] (/ GuPc-S〇2NH(CH2)3N^ GH3 ch3

CuPc represents a copper phthalocyanine residue. [Production Example 2 of a pigment derivative (γ) containing a basic group] 50 parts of copper phthalocyanine as a dye component is subjected to chloromethylation, and then reacted with 40 parts of dibutylamine as an amine component to obtain 95 parts of a pigment derivative (Y2) containing a basic group. Pigment derivative containing basic group (Y2) [Chem. 31] 312XP/Invention manual (supplement)/97-01/96125528 64 200829618

CuPc

CHsN: , C4H9

CuPc represents a copper enantiomeric residue. [Production Example 3 of Pigment Derivative (Y) Containing Basic Group] 50 parts of wow fluorenone as a dye component was subjected to hydrazine hydrazide, and 40 parts of hydrazine as an amine component were The methyl piperene is reacted to obtain (103 parts of a pigment derivative containing a basic group (Υ3). A pigment derivative containing a basic group (Υ3) [Chem. 32]

[Production Example 4 of a Pigment Derivative Containing a Basic Group] Diphenyldionepyrrolopyrrole was used as a dye component, and hydrazine-aminopropyl porphyrin was used as an amine component, and was used in the same manner as in Production Example 1. In the method, a pigment derivative (Υ4) containing a basic group is obtained. Pigment derivative containing basic group (Υ4) [Chem. 33] 312ΧΡ/Invention manual (supplement)/97-01/96125528 65 200829618

[Production Examples 5 to 10 of the pigment derivative (Y) containing a basic group] The pigment derivative shown below was obtained by the same method as the production examples 1 to 4 of the above-described basic group-containing pigment derivative (Υ). An anthracene derivative, an acridone derivative or a tristimulus derivative. [Chemical Formula 34] A pigment derivative containing a basic group (Υ5) 〇 II /C2h5 2

II 颜料 Pigment derivative containing basic group (Y6) [Chem. 35] 312XP / invention manual (supplement) / 97-01/96125528 66 200829618

N I (3⁄43⁄4

Cl Ns. ^0.

0 丫 Ν' G! Yan 5

-SO test

Ri^ nh(ch2)3n( 4 9 c4H9y pigment derivative containing basic group (Y7) [Chem. 36] HO CONH(CH2)3N: x2h5, C2H5

Pigment derivative containing a basic group (Y8) [Chem. 37]

-I %,0=0 0 I

312XP/Invention Manual (Supplement)/97-01/96125528 67 200829618 Pigment derivative containing basic group (Y9) [Chem. 38] Ο II /CH3 颜料 Pigment derivative containing basic group (Υ10) [Chem. 39 ]

/CHa, 〇% (Examples 51 to 59) <Production of Pigment Composition> As shown in Table 7, the pigments (C·I·Pigment Blue 15··3) and the aggregates synthesized in Examples 1 to 9 were prepared. The ester dispersant, the pigment derivative (Y1) containing the test group synthesized in Production Example 1, and cyclohexanone were added to 100 parts of zirconia beads having a diameter of 2 mm, and dispersed by a paint conditioner for 3 hours. Pigment composition. (Comparative Examples 6 and 7) <Production of Pigment Composition> 312XP/Invention Manual (Supplement)/97-01/96125528 68 200829618 The polyphenols containing the rebel group synthesized in Comparative Examples 1 and 2 were used, except A pigment composition was produced in the same manner as in Examples 51 to 59. (Evaluation of Pigment Composition) In order to evaluate the properties of the pigment composition of the present invention, the viscosity of the obtained composition was measured by a β-type viscometer (25 ° C 'rotation speed of 1 rpm) in terms of haze ( The light transmittance was measured by 20%. The haze was measured, and the performance of the dispersion was evaluated by the initial viscosity and the haze (the viscosity is as low as possible, and the haze is as small as possible). The initial viscosity and the haze were dispersed and allowed to stand at room temperature for one day, and the time-dependent viscosity was measured at 4 (the time after rc was placed for a week). The results are shown in Table 7. [Table 7]

The above evaluation results show that the use of the present invention, 51, 59, "Pigment Composition 16, initial viscosity (6), and almost no increase in viscosity over time: shows good stability. Further, the haze is also low. The pigment composition of Examples 6 and 7 was higher in viscosity and haze than the above, and it was found that the dispersibility was problematic. (Example 60) 9 parts of pigment blue as a pigment 15 : 3, i parts of the pigment derivative (γ 〇, containing the test group 312XP / invention specification (supplement) / 97 · 〇 1 / 96 ΐ 25528 69 200829618 Dispersing agent 3 (solid), 29 parts of alkyd resin ("Phthalkyd 133-6" manufactured by Hitachi Chemical Co., Ltd.), and 6 parts of cyclohexanone in a cannabis bottle, placed in a diameter of 25 parts A 5 mm cerium oxide bead was used as a dispersing medium and was officially dispersed by a paint shaker to obtain a pigment dispersion. &amp; The viscosity of the obtained pigment dispersion was measured by a B-type viscometer to have a viscosity of $ TI (6 rpm). The viscosity of the time/viscosity at 6 rpm) was evaluated for the performance of the dispersion. The viscosity at 6 rpm was 11 〇mpa.s, the viscosity at 6 rpm was 100 mPa.s, and the TI value was lu. The obtained pigment was divided into 5 (TC thermostats for storage of the week, and after the time-dependent promotion, the viscosity change of the pigment dispersion before and after the aging was measured. The viscosity at 6 o'clock was 105 mPa.s, the rate of change 5%. After the pigment dispersion is coated on the glass, the solvent is removed, and the weight is 20 (rc heating) The % loss was 8.5%. (Examples 61 to 11 9) Ο In the same manner as in Example 60, according to the blending ratios (_weight i ratio) shown in Tables 8 and 9, respectively, only pigment dispersion was obtained. Further, it was evaluated in the same manner as in Example 6 (the lower the viscosity, the more excellent the TI value is, and the better the TI value is.) (Evaluation of the pigment dispersion) ^ For the viscosity stability, if it is 5 (TC preservation) The viscosity change rate around 1 week is recorded as 〇 within ±1〇%, and as X when it exceeds ±10%. For the coating film, the weight is lost. If the film is coated on the glass and the solvent is removed, it is heated in 2001. If the weight loss after the small day 4 is less than 1, it is recorded as 〇, if it exceeds 1 〇% 312XP / invention manual (supplement V97-01/96125528 70 200829618 is recorded as X. The results are shown in Tables 10 and 11. 71 312ΧΡ/Invention Manual (Supplement)/97-01/96125528 200829618 [Table 8] Pigment Pigment Derivative (Y) Dispersant Alkyd Resin Cyclohexanone CI No. wt% Species wt% Species wt% wt% wt% Example 60 Pigment Blue 15 : 3 9 Y1 1 Dispersant 3 1 29 60 Example 61 Pigment Blue 15 : 3 9 Y1 1 Dispersant 7 1.5 28.5 60 Example 62 Pigment 15 : 3 9 Y1 1 Dispersant 8 1 29 60 Example 63 Pigment Blue 15 : 3 9 Y1 1 Dispersant 10 1 29 60 Example 64 Pigment Blue 15 : 3 9 Y1 1 Dispersant 13 1 29 60 Example 65 Pigment Blue 15 : 3 9 Y1 1 Dispersant 14 1 29 60 Example 66 Pigment Blue 15 : 3 9 Y1 1 Dispersant 15 1 29 60 Example 67 Pigment Blue 15 : 3 9 Y1 1 Dispersant 16 1 29 60 Example 68 Pigment Blue 15 : 3 9 Y1 1 Dispersant 17 1 29 60 Example 69 Pigment Blue 15 : 3 9 Y1 1 Dispersant 21 1 29 60 Example 70 Pigment Blue 15 : 3 9 Y1 1 Dispersant 23 1 29 60 Example 71 Pigment Red 122 9 Y7 1 Dispersant 11 2 28 60 Example 72 Pigment Red 122 9 Y7 1 Dispersant 12 2 28 60 Example 73 Pigment Red 122 9 Y7 1 Dispersant 22 2 28 60 Example 74 Pigment Green 36 8 Y2 2 Dispersant 4 2 28 60 Example 75 Pigment Green 36 8 Y2 2 Dispersant 18 2 28 60 Example 76 Pigment Green 36 8 Y2 2 Dispersant 19 2 28 60 Example 77 Pigment Green 36 8 Y2 2 Dispersant 20 2 28 60 Example 78 Pigment Violet 23 8 Y6 2 Dispersant 3 2 28 60 Example 79 Pigment Violet 23 8 Y6 2 Dispersant 5 2 28 60 Example 80 Pigment Yellow 12 9 Y8 1 Dispersant 2 2 28 60 Example 81 Pigment Yellow 12 9 Y8 1 Dispersant β 2 28 60 Example 82 Pigment Black 7 9 Y1 1 Dispersant 1 1 29 60 Example 83 Pigment Black 7 9 Y1 1 Dispersant 8 1 29 60 Example 84 Pigment Black 7 9 Y1 1 Dispersant 9 1 29 60 Example 85 Pigment Red 122 9 Y3 1 Dispersant 7 2 28 60 Example 86 Pigment Red 254 9 Y4 1' Dispersant 14 2 28 60 Example 87 Pigment Blue 6 8 Y5 2 Dispersant 20 2 28 60 Example 88 Pigment Violet 23 8 Y6 2 Dispersant β 2 28 60 Example 89 Pigment Red 57 · 1 9 Y9 1 Dispersant 21 2 28 60 72 312XP / Invention Specification (supplement) / 97- 01/96125528 200829618

[Table 9] Pigment pigment derivative (Y) Dispersant alkyd resin cyclohexanone CI. No. wt% Species wt% Species wt% wt% wt% Example 90 Pigment Red 57 : 1 9 Y10 1 Dispersant 23 2 28 60 Example 91 Pigment Red 57 : 1 9 Y10 1 Dispersant 24 2 28 60 Example 92 Pigment Red 57 : 1 9 Y10 1 Dispersant 25 2 28 60 Example 93 Pigment Red 57 : 1 9 Y10 1 Dispersant 26 2 28 60 Example 94 Pigment Red 57 : 1 9 Y10 1 Dispersant 27 2 28 60 Example 95 Pigment Red 57 : 1 9 Y10 1 Dispersant 28 2 28 60 Example 96 Pigment Red 57 : 1 9 Y10 1 Dispersant 29 2 28 60 Example 97 Pigment Red 57 : 1 9 Y10 1 Dispersant 30 2 28 60 Example 98 Pigment Red 57 : 1 9 Y10 1 Dispersant 31 2 28 60 Example 99 Pigment Green 36 8 Y2 2 Dispersant 36 2 28 60 Example 100 Pigment Green 36 8 Y2 2 Dispersant 37 2 28 60 Example 101 Pigment Green 36 8 Y2 2 Dispersant 38 2 28 60 Example 102 Pigment Green 36 8 Y2 2 Dispersant 39 2 28 60 Example 103 Pigment Green 36 8 Y2 2 Dispersant 40 2 28 60 Example 104 Pigment Green 36 8 Y2 2 Dispersant 41 2 28 60 Example 105 Pigment Green 36 8 Y2 2 Dispersant 42 2 28 60 Real Example 106 Pigment Green 36 8 Y2 2 Dispersant 43 2 28 60 Example 107 Pigment Green 36 8 Y2 2 Dispersant 44 2 28 60 Example 108 Pigment Green 36 8 Y 2 2 Dispersant 45 2 28 60 Example 109 Pigment Green 36 8 Y2 2 dispersant 46 2 28 60 Example 110 Pigment Green 36 8 Y2 2 Dispersant 47 2 28 60 Example 111 Pigment Green 36 8 Y2 2 Dispersant 48 2 28 60 Example 112 Pigment Green 36 8 Y2 2 Dispersant 49 2 28 60 Example 113 Pigment Green 36 8 Y2 2 Dispersant 50 2 28 60 Example 114 Pigment Blue 15 : 3 9 Y1 1 Dispersant 30 1 29 60 Example 115 Pigment Blue 15 : 3 9 Y1 1 Dispersant 32 1 29 60 Example 116 Pigment Blue 15 : 3 9 Y1 1 Dispersant 33 1 29 60 Example 117 Pigment Blue 15 : 3 9 Y1 1 Dispersant 34 1 29 60 Example 118 Pigment Blue 15 : 3 9 Y1 1 Dispersant 35 1 29 60 Example 119 Pigment Red 57 : 1 9 Y10 1 Dispersant 35 2 28 60 312XP / Invention Manual (supplement) / 97-01/96125528 73 200829618 [Table ί ] Viscosity (mPa-s) ΤΙ Value Viscosity Stability coating film weight loss 6 rpm 60 rpm Example 60 110 100 1.10 〇〇 Example 61 100 100 1.00 〇〇 Example 62 100 95 1.05 〇 Example 63 95 90 1.06 〇〇Example 64 85 85 1.00 〇〇Example 65 130 125 1.04 〇〇Example 66 120 115 1.04 〇〇Example 67 180 150 1.20 〇〇Example 68 200 150 1.33 〇〇Example 69 150 130 1.15 〇〇Example 70 160 145 1.10 〇〇Example 71 200 180 1.11 〇〇Example 72 220 210 1.05 〇〇Example 73 160 150 1.07 〇〇Example 74 300 260 1.15 〇〇Example 75 400 320 1.25 〇〇Example 76 350 330 1.06 〇〇Example 77 310 300 1.03 〇〇Example 78 140 140 1.00 〇〇Example 79 160 150 1.07 〇〇Example 80 400 320 1.25 〇〇Example 81 500 350 1.43 〇〇Example 82 80 75 1.07 〇〇Example 83 50 50 1.00 〇〇Example 84 65 60 1.08 〇〇Example 85 200 205 0.98 〇〇Example 8 6 240 230 1.04 〇〇Example 87 400 380 1.05 〇 〇Example 88 180 160 1.13 〇〇Example 89 350 300 1.17 〇〇74 312XP/Invention Manual (supplement)/97-01/96125528 200829618 [Table 11] Viscosity (mPa*s) Viscosity Stability coating weight loss 6 rpm 60 rpm _ 实施 Example 90 300 270 1.11 〇〇 Example 91 310 300 1.03 〇〇 Example 92 340 290 1.17 〇〇 Example 93 390 380 1.03 〇〇 Example 94 500 400 1.25 〇〇Example 95 500 450 1.11 〇〇Example 96 450 410 1.10 〇〇Example 97 330 310 1.06 〇〇Example 98 340 330 1.03 〇〇Example 99 370 310 1.19 〇〇Example 100 330 300 1.10 〇 〇Example 101 350 340 1.03 〇〇Example 102 300 250 1.20 〇〇Example 103 250 210 1.19 〇〇Example 104 320 320 1.00 〇〇Example 105 380 350 1.09 〇〇Example 106 280 270 1.04 〇〇Implementation Example 107 280 280 1.00 〇〇 Example 108 310 280 1.11 〇〇 Example 109 280 270 1.04 〇〇 Example 110 350 350 1.00 〇〇 Embodiment 111 360 320 1.13 〇〇 Example 112 300 300 1.00 〇〇 Example 113 280 280 1.00 〇〇Example 114 80 75 1.07 〇〇Example 115 75 75 1.00 〇〇Example 116 100 90 1.11 〇〇Example 117 12 0 100 1.20 〇〇Example 118 150 130 1.15 〇〇Example 119 300 290 1.03 〇〇75 312XP/Invention Manual (Supplement)/97-01/96125528 200829618 (Comparative Examples 8 to 24) The same as Example 60 In the manner, according to the blending ratio (weight f ratio) shown in Table 12, a pigment dispersion was obtained, respectively. Further, it was evaluated in the same manner as in Example 6 (the more the viscosity is, the more excellent the viscosity is, and the more the τ 丨 value is closer to 1, the more excellent). If the viscosity change rate before and after storage at 50 °C for one week is within ±1〇%, it is recorded as 〇' if it exceeds ±1 〇%, it is denoted as x. For the weight loss of the coating film, if the coating film is on the glass and the solvent is removed, it is recorded as 〇 at 20 (the weight loss before and after rc heating for 1 hour is 10% or less, and if it exceeds 1% by weight, it is recorded as X. Table 13 is shown. [Table 12] Pigment pigment derivative (Y) Dispersant alkyd resin cyclohexanone CI No. wt% Species wt% Species wt% wt% wt% Comparative Example 8 1 member blue 1 5 : 3 9 Y1 1 - a 30 60 Comparative Example 9 Pigment Blue 15 : 3 9 Y1 1 Comparative Dispersant 1 1.5 28. 5 60 Comparative Example 1 0 Comparative Example 11 Pigment Blue 15 : 3 9 Y1 1 Comparative Dispersant 2 1.5 28. 5 60 j shell material blue 1 5 : 3 9 Y1 1 comparative dispersant 2 4. 5 25. 5 60 Comparative example 1 2 Pigment blue 1 fi : 3 9 Y1 1 Comparative dispersant 2 9 21 60 Comparative example 13 Pigment red 1 9 Y7 1 Comparative Dispersant 2 2 28 60 Comparative Example 14 Pigment Red 1 ?? 9 Y7 1 Comparative Dispersant 2 4. 5 25. 5 60 Comparative Example 1 5 - Pigment Green 36 8 Y2 2 Comparative Dispersant 1 2 28 60 Comparison Example 1 6 - Pigment Green 36 8 Y2 2 Comparative Dispersant 2 2 28 60 Comparative Example 1 7 Pigment Violet 23 8 Y6 2 Comparative Dispersant 2 4 26 60 Comparative Example 18 One Pigment Yellow 12 9 Y8 1 Comparative Dispersant 1 4. 5 25. 5 60 comparison Example 1 9 12 9 Y8 1 Comparative Dispersant 2 4. 5 25. 5 60 Comparative Example 2 0 —JULit 7 9 Y1 2 Comparative Dispersant 2 4. 5 24. 5 60 Comparative Example 21 36 8 Y2 2 Comparative Dispersant 3 3 27 60 Comparative Example 2 2 36 8 Y2 2 Comparative Dispersant 4 3 27 60 Comparative Example 2 3 -JUtA Strip 36 8 Y2 2 Comparative Dispersant 5 3 27 60 Comparative Example 24 36 8 Y2 2 Comparative Dispersant 5 6 24 60 76 312XP/Invention 5 Upstream (Replenishment and Collection) 200829618 [Table 13]

Comparative Example 8 Comparative Example 9 Comparative Example 1 0 Comparative Example 11 Undispersible Dispersible Undispersible 500 200 50 Comparative Example 1 2 200 200 1. 00 Comparative Example 1 3 Undispersible 〇

Comparative Example 1 4 Comparative Example 1 5 Comparative Example 1 6 Unable to measure 40 0 Undispersible Undispersible X

------- II I U_ X

Rn&quot;^Evaluation result f shows that the use of the polydispersant of the present invention is an embodiment in which the initial viscosity is low and the viscosity over time is almost increased. Moreover, the tolerance of the coating film is also high. In contrast, the pigment dispersions of Comparative Examples 8 to 24 have a high viscosity and must be used in an amount of the dispersant. Further, since a low molecular weight dispersant is used in a large amount, even if the viscosity is not problematic, the resistance of the coating film is problematic. (Industrial Applicability) The polyester dispersant of the present invention can be preferably used in the fields of coatings and coloring resin compositions, and more specifically, it can be preferably used for lithographic inks, gravure inks, and color filters. Sheet photoresist, inkjet ink, etc. Using the polyester dispersant of the present invention, it is possible to produce a dispersion which is excellent in non-assembly, fluidity, and storage stability, 312XP/invention specification (supplement)/97-01/96125528 77 200829618. The present invention has been described above on the basis of specific aspects, and modifications or improvements are also apparent to those skilled in the art. 312XP/Invention Manual (supplement)/97-01 /96125528 78

Claims (1)

200829618 X. Patent application scope: 1. A polyester dispersant which is a vinyl group in a single terminal region containing two hydroxyl groups (vinyl p〇lymer) (a) and tetracarboxylic anhydride (b) The above-mentioned ethylene type polymer (a) is an ethylene-unsaturated monomer in the presence of a compound (al) having two hydroxyl groups and a thiol group in the molecule. It is produced by radical polymerization. A polyester dispersant comprising a hydroxyl group in a single terminal region (a hydroxyl group in the ethylene type polymer (a), and a polyol compound (c) other than the above ethylene type polymer (a) The meridine group is formed by reacting with an acid anhydride group in the tetracarboxylic anhydride (b); the above ethylene type polymer (a) is in the presence of a compound (al) having two hydroxyl groups and a thiol group in the molecule. The ethylenically unsaturated monomer is subjected to radical polymerization to form a polyester dispersant, which is a permeation group in the ethylene-based polymer (a) having two hydroxyl groups in a single terminal region, and four The acid anhydride group in the slow acid anhydride (b) and the acid anhydride group in the tricarboxylic acid anhydride (d) are reacted, and the ethylene type polymer (a) is a compound containing two base groups and one thiol group in the molecule ( In the presence of a), an ethylenically unsaturated monomer is subjected to radical polymerization to form a polyester dispersant, which is a hydroxyl group in the ethylene polymer (a) having two hydroxyl groups in a single terminal region. And a meridine in the polyol compound (c) other than the above vinyl type polymer, 312XP/Invention Manual (Supplement)/97-01/96125528 79 200829618 The anhydride group of the tetracarboxylic anhydride (b) and the anhydride group in the tricarboxylic anhydride (d) are reacted to form; 'The above ethylene type polymer (a) It is produced by radical polymerization of a hydrazine-ethylenically unsaturated monomer in the presence of a compound (al) containing two thiol groups in the molecule, and is formed by a polyester dispersant. The ethylenically unsaturated monomer is subjected to radical polymerization in the presence of a compound (a2) formed by reacting a hydroxyl group in a compound (al) having two hydroxyl groups and i subunits with an acid anhydride clay in a tetracarboxylic anhydride. And produced. 6 · A t-flavor dispersing agent' is a hydroxyl group in a compound (al) containing two radicals and one thiol group in the molecule and a polyol compound (c,) containing no thiol group In the presence of a compound (a3) formed by reacting an acid anhydride group in a tetracarboxylic anhydride (b), an ethylenically unsaturated monomer is subjected to radical polymerization to form. 7 · A t-flavor dispersant is attached to a molecule a hydroxyl group in the compound (al) containing two thiol groups In the presence of the compound (a4) formed by reacting an acid anhydride group in the carboxylic anhydride (b) and an acid anhydride group in the dicarboxylic anhydride (d), an ethylenically unsaturated monomer is radically polymerized to form. a polyester dispersant which is prepared by a compound (al) having two hydroxyl groups and one thiol group in the molecule and a thiol group-free polyol compound (c,) and a tetracarboxylic anhydride (b) In the presence of the compound (a5) formed by reacting an acid anhydride group in the acid anhydride group and the tricarboxylic acid anhydride (d), an ethylenically unsaturated monomer is subjected to radical polymerization to form a product. The polyester dispersant of any one of the above items, 312XP/invention specification (supplement)/97-01/96125528 80 200829618 has an average molecular weight of 2 to 25_1 and an acid value of 5 to. 10. If the polyester is dispersed in any one of the beans, the formula is expressed by the following formula (1) or (2): (1) [Chemical Formula 1] (!) [in the general formula (1), k is 1 or 2] Formula (2) [Chemical 2] [In the general formula (2), Qi -COOCH2CH2OCO- λ -S〇2-[3] is a direct bond, -Ο-, , C(CF3)2-, with the formula: a CO-312XP/invention specification ( Supplement)/97-01/96125528 81 200829618 The base expressed, or the formula: [Chemical 4] The base expressed]. 11 The polyester dispersion of the polyester dispersion obtained by radical polymerization of the ethylenically unsaturated monomer in the polyester dispersion of any of the items i to 8 of the patent application range is 1000. ~10_. 12, as in the polyester vinegar dispersible sheet 1 to any one of the above-mentioned patents, wherein the ethylene-polymer portion obtained by radical polymerization of the ethylenically unsaturated monomer has a glass transition temperature of - 50~7rc. The (meth) acetoacetate vinegar contained in the ethylenically unsaturated monomer is from 20% by weight to 70% by weight based on the total body of the early body. . 312XP/Invention Manual (Supplement)/97-01/96125528 82 200829618 14. As in the patent application range j to 8: single: medium, the ethylenically unsaturated monomer contains the following general formula (3) [Chemical 5] (3) Linear or branched burning [In the formula (3), R is a carbon atom group]. A pigment composition comprising a polyester dispersant according to any one of claims 8 to 8, and a pigment. The pigment composition of claim 15, wherein the pigment composition further comprises a pigment derivative containing an organic compound, a green onion derivative containing a test group, a derivative containing a core group, and At least one of the test derivatives selected from the group consisting of three derivatives of the hard base. π. - A pigment dispersion which is obtained by dispersing a pigment composition of the scope of the patent application in a varnish. 18. A method for producing a dispersing agent, comprising the steps of: Step A1 'a compound having two hydroxyl groups and one thiol group in the molecule (al) = presenting an 'ethylenically unsaturated single The body is subjected to radical polymerization to produce an ethylene type polymer (4) having two hydroxyl groups in a single terminal region; and a step B1 for reacting the above ethylene type polymer (a) with a tetracarboxylic acid anhydride (b). 312XP/Invention Manual (Supplement)/97-01/96125528 83 200829618 19. A method for producing a polyester dispersant, comprising the steps of: Step A2' containing two base groups and a thiol group in the molecule In the presence of the compound (al), the ethylenically unsaturated monomer is subjected to radical polymerization to produce an ethylene type polymer having two hydroxyl groups in a single terminal region; and in the step B2, the above ethylene type polymer (4), tetracarboxylic acid Xuan (seven)', and the polyol compound k) other than the above ethylene type polymer (a) reacted. 20. A method for producing a polyester dispersant, comprising the steps of: Step A3 'in the presence of a compound (al) having 2 thiol groups and i thiol groups in the molecule, making an ethylenically unsaturated single The body is subjected to radical polymerization to produce an ethylene type polymer containing two hydroxyl groups in a single terminal region; and in step B3, the above ethylene type polymer (a) is reacted with a tetracarboxylic anhydride and a tricarboxylic anhydride (d). A method for producing a polyester dispersant, comprising the steps of: Step A4, in the presence of a compound (al) having two hydroxyl groups and one thiol group in the molecule, making an ethylenically unsaturated single Free radical polymerization to produce an ethylene type polymer (a) having two hydroxyl groups in a single terminal region; and step B4' to polymerize the above ethylene type polymer (a), tetraphthalic anhydride (匕), and the above ethylene type The polyol compound (c) other than the substance (a) and the tri-hectoric anhydride (d) are reacted. A method for producing a polyester dispersant, comprising the steps of: Step B5, wherein a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in the molecule and a tetracarboxylic acid anhydride (b) The acid anhydride group is reacted to produce the compound (a2); and the step A5 is carried out in the presence of the above compound (a2) to make the ethylenic unsaturated 312XP/invention specification (supplement)/97-01/96125528 84 200829618 and the monomer Radical Polymerization. A method for producing a polyester dispersant, comprising the steps of: Step B6, a hydroxyl group in a person (al) having two hydroxyl groups and one thiol group in a molecule, and a thiol group-free group The base group in the polyol compound (c,) is reacted with an acid anhydride group in the tetracarboxylic anhydride (b) to produce a compound (&amp;3) and, in step A6, in the presence of the above compound (a3), to make an ethyl group The unsaturated monomer undergoes radical polymerization. A method for producing a polyester dispersant, comprising the steps of: Step B7 'make a hydroxyl group in a compound (al) having two hydroxyl groups and one thiol group in a molecule, and a tetracarboxylic anhydride (b) The compound (&amp;4) is reacted with an acid anhydride group in the acid anhydride group and the tricarboxylic anhydride (d); and the step A7, the ethylenically unsaturated monomer is subjected to radical polymerization in the presence of the above compound (a4) . A method for producing a polyester dispersant, comprising the steps of: Step B8, wherein a hydroxyl group in a compound (al) having two hydroxyl groups and a thiol group in a molecule, and a tetracarboxylic anhydride (b) An acid anhydride group-containing, thiol group-free polyol compound (hydroxyl group in hydrazine, and acid field reaction in ferulic acid needle (4) to produce compound (a5); and Y騄A8 in the above compound (a5) In the presence of the above, the ethylenically unsaturated monomer is subjected to radical polymerization. 26. The method for producing a polyacetal dispersant according to any one of the claims 帛18纟25, wherein the four (four) liver (b) is as follows Expressed by the general formula (1) or the general formula (2), 312XP/invention specification (supplement)/9101/% 125528 85 200829618 general formula (1) [Chemical 6] ([In the general formula (1), k is 1 or 2], and the general formula (2) [Chemical 7] [In the general formula (2), Q! is a direct bond, -0-, -CO-, -COOCH2CH2OCO-, -S〇2-, -C(CF3)2-, with the formula: [Chemical 8] 312XP / invention manual (supplement) /97-01/96125528 86 0, 200829618 The basis, or formula: [Chemistry 9] Γ The basis of the statement]. The method for producing a polyester dispersant according to any one of claims to 25, wherein the ethyl methacrylate contained in the ethylenically unsaturated monomer is 20% by weight of the total monomer. ~7〇% by weight. $28·Dispersion of polyester as claimed in any of claims 18 to 25 The method for producing an agent, wherein the ethylenically unsaturated monomer contains a monomer represented by the following formula (3), and the formula (3) [Chemical Formula 10] 0) 2 'R is a linear or branched burning of carbon number 卜4 312XP / invention manual (supplement) /97-01/96125528 87 200829618 VII. Designated representative figure: (1) Representative of the case Pictured: None (2) Simple description of the symbol of the representative figure: No C 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No 312XP/Invention Manual (Supplement)/97-01/ 96125528 4