Pigment dispersing agent - EP 0358358 A2

®

Europaisches Patentamt

European Patent Office

Office europeen des brevets

© Publication number: 0 3 5 8 3 5 8

A 2

© E U R O P E A N PATENT A P P L I C A T I O N

© Application number. 89308356.8 © Int. CI.5: C08F 8/32 , C09D 1 3 3 / 1 4

® Date of filing: 17.08.89

® Priority: 26.08.88 JP 210789/88 © Applicant: NIPPON OIL AND FATS COMPANY, 1 2.05.89 JP 1 1 9666/89 LIMITED 12.05.89 JP 119667/89 10-1, Yuraku-cho 1-chome 20.06.89 JP 155649/89 Chiyoda-ku Tokyo(JP) 20.06.89 JP 155650/89 19.07.89 JP 184497/89 © Inventor: Yamamoto, Toshio

473 Shimokurata-Cho Totsuka-Ku @ Date of publication of application: Yokohama City Kanagawa Pref.(JP)

14.03.90 Bulletin 90/11 Inventor: Matsukura, Yoshiaki 1113 Shimokurata-Cho Totsuka-Ku

© Designated Contracting States: Yokohama City Kanagawa Pref.(JP) DE ES FR GB Inventor: Ohe, Osamu

17-3, Ebara 7-Chome Shinagawa-Ku Tokyo(JP) Inventor: Ogawa, Hisao 19-69 Ikego 2-Chome Zushi City Kanagawa Pref.(JP) Inventor: Ishidoya, Masahiro 26-6-305, Kajiwara 2-Chome Kamakura City Kanagawa Pref.(JP) Inventor: Matsubara, Yoshiro 910-4, Kasama-Cho Sakae-Ku Yokohama City Kanagawa Pref.(JP)

© Representative: Sheader, Brian N. et al ERIC POTTER & CLARKSON 27 South Street Reading Berkshire, RG1 4QU(GB)

© Pigment dispersing agent.

{ ^ ® A pigment dispersing agent for paints is a combination of particular amine compound and particular acrylic ^copolymer or a combination of particular amine compound, particular acrylic copolymer and particular polyester

M resin. This pigment dispersing agent is applicable to both acrylic resin series paints and polyester resin series m paints. CO 00 i n co

©

CL LU

Xerox Copy Centre

EP 0 358 358 A2

PIGMENT DISPERSING AGENT

This invention relates to a pigment dispersing agent used when a pigment is mixed with a coating composition in the manufacture of paints.

In the manufacture of paints, it is important to mix the pigment with the coating composition. In this case, the pigment to be usually used in the paint is dispersed into only a part of a vehicle constituting the

5 paint together with a proper solvent, diluent or other additive by means of a mill used in the paint industry to obtain a dispersion paste. Then, this paste is mixed with the remaining amount of the vehicle and another necessary additives to obtain a pigment dispersing composition as a paint. However, a greatest problem of such a pigment dispersing composition lies in that the pigment particles are apt to be agglomerated. As a result, it is known to cause unfavorable phenomena such as decrease of paint stability, occurrence of

io troubles in the painting, reductions of color strength, gloss and distinctness of image of the finally obtained paint film, flooding, floating, color change with time and the like. Such a phenomenon that the pigment particles are apt to be agglomerated is explained by London - van der Waals force attracting the particles each other. In order to overcome this attracting force, it is necessary to provide an adsorption layer onto the surface of the particle, and consequently various methods are attempted. For instance, there are known (1)

75 a method of dispersing the pigment by using non-ionic, anionic or cationic surfactant, or a wetting agent such as aliphatic polyvalent carboxylic acid or the like as an assistant; (2) a method of mixing the pigment with a certain substituted derivative of the pigment as disclosed in Japanese Patent laid open No. 51- 18,736; (3) a method of dispersing the pigment by using a high molecular weight dispersing agent obtained the bonding of a basic substance and a polyester compound as disclosed in Japanese Patent laid open No.

20 60-166,318 and No. 61-174,939; (4) a method of dispersing the pigment by using a high molecular weight dispersing agent obtained through the bonding of a basic substance and an acrylic polymer as disclosed in Japanese Patent laid open No. 46-7,294; and the like. In the dispersion assistant used in the method (1), however, the adsorption layer adsorbed on the particle surface is thin and does not develop the satisfactory stabilizing effect and hence the pigment dispersing performances are not observed. The pigment derivative

25 used in the method (2) is naturally colored, so that it can not generally be used for various pigments. The basic thought of the dispersing agent used in the methods (3) and (4) is a technical idea of making a block structure from a polymer portion capable of solvating with a solvent and an anchor portion adsorbed on the pigment as described by A. Topham in Progress in Organic Coatings, vol. 5, (1977) pp 237-243. In this technique, it is important that the polymer portion capable of solvating with the solvent is excellent in the

30 compatibility with a resin added as a film forming component of the paint film and the adsorption state of the dispersing agent to the pigment is tail-like. If the polymer portion capable of solvating with the solvent is poor in the compatibility with the resin added as the film forming component of the paint film, the solvated polymer portion agglomerates to cause the degradation of pigment dispersing performances.

In the dispersing agent used in the method (3), therefore, when the compatibility between the 35 dispersing agent and the dispersion vehicle is good, the remarkable improvement of the pigment dispersing

performances is observed, but when using the dispersion vehicle having a poor compatibility, the protective layer for the dispersing agent adsorbed on the particle surface agglomerates to undesirably degrade the pigment dispersing performances. Especially, since the dispersing agent consists mainly of polyester compound, it is poor in the compatibility with an acrylic resin or the like important as a painting resin, so

40 that it is difficult to obtain good pigment dispersing performances in case of acrylic resin series paints. Furthermore, the polyester portion of this dispersing agent has not a functional group reacting with a curing agent in the paint such as melamine resin, urea resin, polyisocyanate resin or the like, it acts as a plasticizer in the paint film to cause degradation of weather resistance, humidity resistance and the like in the paint film and the local floating of the pigment dispersing agent onto the surface of the paint film after

45 the curing of the paint or so-called bleeding phenomenon, whereby the gloss and hardness are lowered. Moreover, when the dispersing agent is used for multilayer coating, it is pointed out to cause adhesion trouble between the paint films due to the presence of the bled component and the like.

On the other hand, the pigment dispersing agent used in the method (4) serves for ordinary acrylic resin series paints because acrylic resin is used as a polymer portion. However, the polymer portion has no

so reaction point such as hydroxyl group, carboxyl group or the like reacting with a crosslinking agent likewise the method (3) and is not chemically fixed in the paint film, so that there is a problem of damaging the quality of paint film due to the plasticizer action as previously mentioned.

Furthermore, in the method (4), all of the polymer portion is comprised of acrylic resin, so that it is difficult to be used for polyester resin series paints.

In both the methods (3) and (4), since the polymer portion has no polar group such as hydroxyl group,

2

EP 0 358 358 A2

carboxyl group or the like, it is poor in the compatibility with a resin having a relatively high polarity, so that it is. difficult to utilize these methods in paints consisting mainly of such a resin and hence the application range thereof is critical.

Under the above circumstances, the inventors have made studies with respect to (1) a pigment 5 dispersing agent capable of widely utilizing in acrylic resin series paints usually used in the art and

simultaneously fixing in the paint film through the curing reaction with an amino resin such as melamine resin, urea resin and also with polyisocyanate resin or the like; and (2) a. pigment dispersing agent capable of utilizing in polyester resin series paints in addition to the acrylic resin series paint and fixing in the paint film through the reaction with a crosslinking agent such as amino resin, polyisocyanate resin or the like, and

10 as a result the invention has been accomplished. That is, the invention provides pigment dispersing agents of the following first and second inventions.

I. A pigment dispersing agent consisting of a product obtained by reacting the following component Ai with the following component B at a mol ratio of component Ai to component B of 1:1 - 1:40.

Component Ai : an amine compound containing one or more amino group and/or imino group in its 75 molecule and having a weight average molecular weight of 60-30,000 and an amine value of 50-2,000 mg

KOH/g; Component B: an acrylic copolymer having a weight average molecular weight of 2,000-100,000

and a hydroxyl value of 5-200 and containing one of glycidyl group

20 ( - C H 2 - C H - C H 2 , c o m p o n e n t B x ) ,

acetoacetoxy group (-O-CO-CH2-CO-CH3, component B2) and cyclocarbonate group

V II 0

( -CH2-CH-CH2, c o m p o n e n t B3)

O O

in a functional group number of 0.7-3.0 on average per molecule as a side chain, provided that 1 mole of glycidyl group is considered to be 1 mol of hydroxyl group in the calculation of hydroxyl value.

II. A pigment dispersing agent consisting of a product obtained by reacting the following component A2 and component B with one of the following six components C at a mol ratio of component A2 to component B to component C of 1:1:1-1:40:40.

Component A2: an amine compound containing one or more amino group or two or more imino group or one or more amino and imino groups in its molecule and having a weight average molecular weight of 60-30,000 and an amine value of 50-2,000 mg KOH/g;

Component B: an acrylic copolymer having a weight average molecular weight of 2,000-100,000 and a hydroxyl value of 5-200 and containing one of glycidyl group

( -CH2-CH-CH2 , c o m p o n e n t Bx ) ,

acetoacetoxy group (-O-CO-CH2-CO-CH3, component B2) and cyclocarbonate group

55

{ -CH2-CH-CH2, c o m p o n e n t B3) ,

0 0 V

II 0

3

EP 0 358 358 A2

in a functional group number of 0.7-3.0 on average per molecule as a side chain, provided that 1 mole of glycidyl group is considered to be 1 mol of hydroxyl group in the calculation of hydroxyl value;

Component C: a polyester resin of the following structures having a weight average molecular weight of 1,000-30,000 and containing isocyanate group or acetoacetoxy group in its terminal

5 R,-0-(CO-R2-0)n-CO-NH-R3-NCO (Ci) Ri -0-(CO-R2-0)n-CO-CH2-CO-CH3 (C2) R, -0-(CO-R4-COO-CHR5-CHR6-0)n-CO-NH-R3-NCO (C3) Ri-0-(CO-R*-COO-CHR5-CHRG-0)n-CO-CH2-CO-CH3 (Ci) R1-CO-(0-CHRs-CHRs-0-COR4-CO)n-0-CHRs-CHRG-OCO-NH-R3-NCO (C5)

70 Ri-CO-(0-CHRs-CHRG-0-COR+-CO)n-0-CHR5-CHR6-OCO-CH2COCH3 (Cs) Ri : aliphatic, alicyclic or aromatic hydrocarbon group having a carbon number of 1-18, R2: alkylene group having a carbon number of 1-7, R3: residual group of aliphatic, alicyclic or aromatic diisocyanate having a carbon number of 6-20, R+: Residual group of aliphatic, alicyclic or aromatic acid anhydride having a carbon number of 2-20,

75 R5, Re: hydrogen atom, aliphatic, alicyclic or aromatic hydrocarbon group having a carbon number of 1-20, -CH2-O-R1 group or -CH2-OCO-R1 group n : an integer of 1 or more.

Moreover, when it is not required to divide components A, B and C into components Ai and A2, components Bi-B3 and components Ci-Cs in the following explanation, these components are abbreviated

20 as components A, B and C. In the first invention, the amine compound of the component A is strongly adsorbed on the surface of

the pigment, and the acrylic resin of the component B is excellent in the compatibility with the acrylic resin as a vehicle and forms a stable and stericaily repulsive layer to prevent the agglomeration of the pigment particles. Furthermore, since the acrylic resin of the component B has a hydroxyl group in its side chain, it

25 is chemically fixed in the paint film at the curing step of the paint film. In the second invention, the polyester resin of the component C is further incorporated in addition to the

components A2 and B, so that the compatibility with the polyester series resin is ensured besides the merits of the first invention, and the resulting pigment dispersing agent acts to both acrylic and polyester resin paints.

30 The pigment dispersing agents according to the invention will be described in detail below. The component Ai used in the first invention is an amine compound containing one or more amino

group and/or imino group in the molecule for providing a bonding point to the component B and having a weight average molecular weight of 60-30,000 and an amine value of 50-2,000 mg KOH/g. The component Ai may include a tertiary amine group. The component A2 used in the second invention is an amine

35 compound containing one or more amino group or two or more imino group or one or more amino and imino groups for providing bonding points to both components B and C and having a weight average molecular weight of 60-30,000 and an amine value of 50-2,000 mg KOH/g. The component A2 may include a tertiary amine group.

When the weight average molecular weight of the component A is less than 60, the adsorption force to 40 the pigment is weak and the pigment dispersing performances "are degraded, while when it exceeds 30,000,

the compatibility with the resin becomes poor and further the adsorption group becomes too long and hence the component A may act as an agglomerating agent to degrade the pigment dispersing performances. When the amine value of the component A is less than 50 mg KOH/g, the adsorbing force is insufficient and the dispersibility is poor, while when it exceeds 2,000 mg KOH/g, the water resistance and

45 weather resistance of the paint film are injured. The amine compound as the component A has any molecular structure such as straight chain,

branched chain, ring and the like. For example, as the component Ai , mention may be made of alkylamines represented by NH2(CH2)nCH3 provided that nS1 such as ethylamine, propylamine, butylamine, pen- tylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine and the like; and alkylimines being

50 isomers of the above alkylamines and containing imino group. As the components Ai, A2, mention may be made of diamines represented by NH2(CH2)nNH2 provided that nS2 such as ethylenediamine, pro- pylenediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine and the like; alkyl polyamines such as 1 ,2,3-triamino propane, tris (2- aminoethyl) amine, tetra (aminomethyl) methane, iminobispropyl amine, methyliminobispropyl amine, N-

55 methylethylene diamine, N-ethylethylene diamine and the like; polyethylene imines represented by NH2- (CH2CH2NH)nCH2CH2NH2 provided that n i such as diethylene triamine, triethylene tetramine, teraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, heptaethylene octamine, octaethylene non- amine, nonaethylene decamine and trade names of Montrec (made by Dow Chemical Co.), Polymine

4

EP 0 358 358 A2

Waterflow (made by BASF AG) and Epomine (made by Nippon Shokubai Kagaku Kogyo K.K.); polyalkyl polyamines obtained by dehydrochlorination reaction of dihalides of chain or ring hydrocarbons having a carbon number of 1-8 with ammonia or organic amines containing chain or ring hydrocarbon group having a carbon number of 1-8; cyclodialkylene diimines such as 1 ,4-diazacyclo heptane, cyclo di(trimethyiene)

5 diimine, cyclo di(heptamethylene) diimine, cyclo di(octamethylene) diimine and the like; aromatic amines such as m-xylenediamine, m-toluylene diamine, dianisidine, p-phenylene diamine, 3,5-dichloro-4,4-diamino diphenylmethane and the like; heterocyclic amines such as N-aminopropyl morpholine, 1-(2-aminoethyl) piperazine, 4-amino-2-methoxy-pyrimidine, 4-(aminoethyl) pyridine, 2-amino-6-methoxy benzothiazole, N,N- diallyl melamine, benzoguanamine, acetoguanamine, 3-amino-1,2,4-triazole, 1-aminoethyl piperazine,

10 meiamine and the like; and dimethyl aminopropyl amine, diethyl aminopropyl amine, morpholine, 1-(2- hydroxyethyl) piperamine, 1-(3-aminopropyl) imidazole, 1 ,2-(hydroxyethyl) imidazole and the like.

The component B used in the invention is an acrylic copolymer having a weight average molecular weight of 2,000-100,000 and a hydroxyl value of 5-200 and containing one of glycidyl group, acetoacetoxy group and cyclocarbonate group as a side chain at a functional group number of 0.7-3.0 per molecule.

15 When the weight average molecular weight is less than 2,000, the sufficient, sterically repulsive layer is not formed and the pigment dispersing performances are degraded, while when it exceeds 100,000, the pigment dispersing agent' is apt to be desorbed from the surface of the pigment and the pigment dispersing performances are degraded. When the hydroxyl value is less than 5, the amount acting as a crosslinking point for the crosslinking agent is insufficient and the pigment dispersing agent derived from the component

20 B is not fixed in the paint film, and consequently the pigment dispersing agent acts as a plasticizer in the paint film, which injuries the film performances such as humidity resistance, water resistance, weather resistance and the like and bleeds out from the surface of the paint film to badly affect the gloss, hardness and adhesion property. Furthermore, the compatibility with the binder resin having a high polarity reduces, so that the pigment dispersing performances are degraded in these systems. On the other hand, when the

25 hydroxyl value of the component B exceeds 200, the polarity becomes excessively high and the water resistance and flexiblity of the paint film are injured, and also the compatibility with the binder resin having a low polarity reduces, so that the application thereof is restricted.

Moreover, in the component B having the glycidyl group, 1 mol of hydroxyl group is produced from 1 mol of glycidyl group through the reaction with the component A, so that it is considered that 1 mol of

30 glycidyl group corresponds to 1 mol of hydroxyl group in the calculation of the hydroxyl value. The component B contains one of glycidyl group, acetoacetoxy group and cyclocarbonate group as a

reaction point to the component A at a functional group number of 0.7-3.0 per molecule, preferably 1.0-2.0 per molecule. The term "molecule" used herein means a molecule having a weight average molecular weight by a gel permeation chromatography based on polystyrene standard. When the functional group

35 number of one of glycidyl group, acetoacetoxy group and cyclocarbonate group is less than 0.7 per molecule, a portion of the component B not reacting with the component A becomes large and the pigment dispersing performances are degraded, while when it exceeds 3.0, there is a possibility of promoting the three-dimensional network structure through the reaction with the component A and hence the increase of viscosity or gellation is undesirably caused.

40 Moreover, as an example, when the amount of the desirable functional group is expressed by the term of equivalent value (epoxy equivalent), it corresponds substantially to a range of 1,000-200,000. Even in the case of the functional group other than glycidyl group, if the desirable amount is expressed by the equivalent value, it is within the above range.

The component B contains one of glycidyl group, acetoacetoxy group and cyclocarbonate group in its 45 side chain portion for the skeleton of acrylic resin. Each of these functional groups in the component B

reacts with the amino or imino group in the component A according to the following reaction formula to form the pigment dispersing agent according to the invention.

so (1) Reaction of glycidyl group

55

5

EP 0 358 358 A2

NH,

o r + a c r y l i c c o p o l y m e r CH-CH,

\ / 2

0 NH-

70 ( C o m p o n e n t A) ( C o m p o n e n t Bx)

75 N H - C H - - C H - 2 I OH

a c r y l i c c o p o l y m e r

20 o r

25

^ N - C E L - C H -

OH


(2) Reaction of acetoacetoxy group 30

35

'NH,

o r + a c r y l i c c o p o l y m e r

0 ii

O ii

OC-CH2-C-CH3

•NH-

40 ( C o m p o n e n t A) ( C o m p o n e n t B2)

45 •NH-C = CH-C-

I » CH, O

a c r y l i c c o p o l y m e r + H20

50 o r

55 N-C = C H - C - 0 "

CHq 11 0


+ H20

6

EP 0 358 358 A2

(3) Reaction of cyclocarbonate group

70

-NH.

o r

•NH-

+ a c r y l i c c o p o l y m e r •CH-CH-

I I 4 O 0 \ /

c

75 ( C o m p o n e n t A) ( C o m p o n e n t B3)

20

OH I

0 CH, II I 2

-NH-C-O-CH - a c r y l i c c o p o l y m e r

25 o r

30

OH I

0 CH- II I 2

N - C - O - C H - a c r y l i c c o p o l y m e r

35

40

45

50

55

The introduction of these functional groups into the component B will be described in detail below. For example, there are two methods, one of which methods being a method of copolymerizing a monomer previously having the functional group with the other copolymerizable monomer and the other of which methods being a method of previously forming a copolymer having no functional group and then introducing the functional group thereinto. In the former method, use may be made of the following monomers.

The monomer containing glycidyl group includes, for example, glycidyl (metha)acrylate, ally Iglycidyl ether and the like. The monomer containing acetoacetoxy group includes, for example, acetoacetoxy ethyl (metha)acrylate, acetoacetoxypropyi (metha)acrylate, allylacetoacetate and the like. The monomer containing cyclocarbonate group includes, for example, 4-(metha)acryloyloxymethyl-1,3-dioxolane-2-on, 4-(metha)- acryloyloxyethyl-1 ,3-dioxolane-2-on, 4-(metha)acryloyloxypropyl-1 ,3-dioxolane-2-on, 4-(metha)- acryloyloxybutyl-1,3-dioxolane-2-on and the like.

As the monomer ingredient usually constituting the acrylic copolymer of the component B, there are mentioned various a, ,8- ethylenically unsaturated monomers always used in the art. For example, mention may be made of alkyl esters of (metha)acrylic acid such as methyl (metha)acrylate, ethyl (metha)acrylate, propyl (metha)acrylate, butyl (metha)acrylate, octyl (metha)acrylate, lauryl (metha)acrylate, stearyl (metha)- acrylate, cyclohexyl (metha)acrylate, phenyl (metha)acrylate, benzyl (metha)acryiate and the like; alkoxyal- kyl esters such as methoxyethyl (metha)acrylate, methoxybutyl (metha)acrylate, ethoxyethyl (metha)- acrylate, ethoxybutyl (metha)acrylate and the like; hydroxyalkyl esters such as 2-hydroxyethyl (metha)- acrylate, 2-hydroxypropyl (metha)acrylate and the like; lactone-modified (metha)acrylates such as Placcel FA-1, FA-2, FM-1, FM-2 and the like (trade name, made by Daicel Chemical Industries Ltd.); di or monoalkyl esters of dibasic acids such as maleic acid, fumaric acid and the like; acrylic acid, methacrylic acid, (metha)acrylonitrile, (metha)acrylamide, N-methylol (metha)acrylamide, N-methoxymethyl (metha)-

7

EP 0 358 358 A2

acrylamide, dimethylaminoethyl (metha)acrylate, diethylaminoethyl (metha)acrylate, dimethylaminopropyl (metha)acrylate, styrene, a-methyl styrene, vinyltoluene, vinyl acetate, vinyl chloride, various vinyl ethers, vinyl esters, allyl ethers, allyl esters and so on.

The component C used in the second invention is a polyester resin having a weight average molecular s weight of 1,000-30,000 and containing isocyanate group or acetoacetoxy group in its terminal and has

anyone of the following Ci-Cs structures. Ri -0-(CO-R2-0)n-CO-NH-R3-NCO (C, ) Ri -0-(CO-R2-0)n-CO-CH2-CO-CH3 (C2) R,-0-(CO-R4-COO-CHR5-CHRs-0)n-CO-NH-R3-NCO (C3)

10 R,-0-(CO-R4-COO-CHR5-CHR6-0)n-CO-CH2-CO-CH3 (C*) Ri-CO-(O-CHR5-CHRs-O-C0R4-CO)n-0-CHR5-CHRs-OC0-NH-R3-NC0 (Cs) Ri -CO-(0-CHRs-CHRs-0-COR4-CO)n-0-CHR5-CHRs-OCO-CH2COCH3 (Cs) Ri: aliphatic, alicyclic or aromatic hydrocarbon group having a carbon number of 1-18, R2: aikylene group having a carbon number of 1-7,

is R3: residual group of aliphatic, alicyclic or aromatic diisocyanate having a carbon number of 6-20, R4: Residual group of aliphatic, alicyclic or aromatic acid anhydride having a carbon number of 2-20, Rs, Rs: hydrogen atom, aliphatic, alicyclic or aromatic hydrocarbon group having a carbon number of 1-20, -CH2-O-R1 group or -CH2-OCO-Ri group n : an integer of 1 or more.

20 The component C is an ingredient necessary when the pigment dispersing agent according to the invention is applied to not only the acrylic resin paints but also the polyester resin paints. The polyester structure in the component C has a compatibility with the polyester resin and exhibits excellent pigment dispersing performances.

When the weight average molecular weight of the component C is less than 1 ,000, it is difficult to form 25 the sufficient, stericaily repulsive layer and the sufficient compatibility with polyester resin in the paint can

not be ensured, and consequently good pigment dispersing performances can not be obtained in the polyester resin paints. While, when the molecular weight of the component C exceeds 30,000, it is difficult to produce the component C with a good reproducibility, resulting in the unsuitable use as an industrial material.

30 The production of the component C will be described in detail below. It is obtained by ring-opening polymerization of lactones with monovalent alcohol as a reaction initiator (corresponding to components C1 and C2), or by successively ring-opening reaction between acid anhydride and epoxy compound with monovalent alcohol or monovalent carboxylic acid as a reaction initiator to obtain an oligomer containing a hydroxyl group in its terminal and then reacting such a hydroxyl group with diisocyanate compound,

35 diketene or acetoacetic acid ester (corresponding to components C3, C*, Cs and Cs). Ri in the components Ci, C2, C3 and C* is an aliphatic, alicyclic or aromatic hydrocarbon group having

a carbon number of 1-18. As a feed material for Ri , mention may be made of monovalent alcohols represented by Ri OH such as

methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, 40 cetyl alcohol, oleyl alcohol, stearyl alcohol and various synthetic alcohols; alicyclic monovalent alcohols

such as cyclopentanol, cyclohexanol and alkyl substituted compounds thereof; phenol, benzyl alcohol, alkyl substituted compounds thereof and the like. Similarly, various glycol ethers, glycol esters and so on may be used.

R2 in the components C1 and C2 is an aikylene group having a carbon number of 1-7. As a feed 45 material for R2l mention may be made of lactones such as s-caprolactone, propiolactone, valerolactone and

so on. Ri in the components Cs and Cs is the same as in the above Ri . In this case, monovalent carboxylic

acids represented by R1COOH and obtained by substituting OH group of the monoalcohol R1OH in the above components C1-C4 are mentioned, for example, as a feed material for this Ri.

50 Ri. in the components C3, C+, Cs and Cs is a residual group of aliphatic, alicyclic or aromatic acid anhydride having a carbon number of 2-20. As a feed material for R+, mention may be made of acid anhydrides represented by

55 o=c c = o

8

EP 0 358 358 A2

such as maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hex- ahydrophthalic anhydride, tetrahalophthalic anhydride, hexahalophthalic anhydride, hymic anhydride, hetic anhydride, various alkyl or alkenylsuccinic anhydrides and the like.

Rs and Rs in the components Ca, Ci, Cs and Cs are a hydrogen atom or an alkyl group having a 5 carbon number of 1-20 or

-CH2-O-R1 or -CH2-O- C -Ri group. II O

As a feed material for CHR5-CHR6, mention may be made of epoxy compounds represented by

10 R c - C H - C H - R , V

such as olefin oxides having a carbon number of 2-20, styrene oxide, alkylglycidyl ethers or glycidyl esters having a carbon number of 1-20, phenylglycidyl ether, alkyl-substituted phenylglycidyl ether and the like.

R3 in the components C1 , C3 and C5 is a residual group of aliphatic, alicyclic or aromatic diisocyanate having a carbon number of 6-20. As a feed material for R3, mention may be made of diisocyanate compounds represented by OCN-R-NCO such as tolylene diisocyanate, isophorone diisocyanate, 4,4 - diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, methylcyclohexane-2,4 (2,6) diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,3-(isocyanatemethyl) cyclohexane, trimethyl- hexamethylene diisocyanate, dimer acid diisocyanate and the like.

The pigment dispersing agent according to the first invention is comprised of the component Ai and the component B and is obtained by reacting the component Ai with the component B at a mol ratio of Ai to B of 1:1-1:40. When the mol ratio is less than 1:1, the sterically repulsive layer is not formed sufficiently and the pigment dispersing performances are degraded, while when it exceeds 1:40, the desorption from the pigment surface is apt to be caused and the dispersibility is degraded.

The pigment dispersing agent according to the second invention is comprised of the component A2, the component B and the component C and is obtained by reacting the component A2 with the components B and C at a mol ratio of A2:B:C of 1:1:1 - 1:40:40. When the mol ratio of A2:B:C is less than 1:1:1, the sterically repulsive layer is not formed sufficiently and the good compatibility with various resins is not obtained, while when it exceeds 1 :40:40, the desorption of the dispersing agent from the pigment surface is undesirably caused. In such a three component system, the components A2 and B are combined with one of components C1-C6 as the component C, but two or more components C may be applied without giving any further merit.

That is, the pigment dispersing agent according to the invention is a combination of the above- mentioned components and is desirable to have an amine value of 10-500 mg KOH/g as the agent itself. When the amine value is less than 10 mg KOH/g, the adsorbing force to the pigment is lacking, while when it exceeds 500 mg KOH/g, the ratio of the sterically repulsive group to the adsorbing group is very small and the sufficient pigment dispersing performances may not be obtained.

Moreover, the measurement of amine value is carried out by using a solution of p-toluene sulfonic acid in acetic acid as a titrating agent in a solvent of acetic acid and calculating from an amount of p-toluene sulfonic acid required for neutralization through nonaqueous potentiometric titration.

The production of the pigment dispersing agent according to the invention will be described below.

(1) Production of component B

The acrylic copolymer of the component B is produced by copolymerizing two or more a, &- ethylenically unsaturated monomers constituting the component B as previously mentioned in the presence of a polymerization initiator. As the copolymerization method, well-known methods such as solution polymerization, block polymerization, suspension polymerization and the like may be applied. Among them, solution polymerization method is preferable.

As the polymerization initiator, use may be made of any substances usually used in the vinyl-type polymerization, which includes, for example, azobisisobutyronitrile, di-t-butyl peroxide, benzoylperoxide, t- butyl peroxybenzoate, t-butyl peroctoate, cumene hydroperoxide, lauroyl peroxide, acetyl peroxide, methylethyl ketone peroxide, dicumyl peroxide and the like.

The organic solvent used in the solution polymerization is not particularly critical. As the solvent, there

9

EP 0 358 358 A2

may be used one or more of aromatic hydrocarbons such as toluene, xylene, ethylbenzene, Solveso #100 and Solveso #150 (registered trade mark, made by Exxon Chemical Co.), turpentine oil, tetraline and the like; aliphatic hydrocarbons such as n-hexane, cyclohexane, methyl cyclohexane, n-heptane, n-octane, n- decane, mineral spirit, isooctane, nonane, trimethylhexane, solvent naphtha, Isopar (registered trade mark,

5 made by Exxon Chemical Co.), Newsol Delax (registered trade mark, made by Nippon Oil Co., Ltd.) and the @ like; esters such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate and the like; ethers such

as ethyl ether, tetrahydrofuran, dioxane, diglyme and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone and the like; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, methylisobutyl carbinol,

10 cyclohexanol, benzyl alcohol and the like; cellosolves and esters thereof such as ethylene glycol mon- omethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol mon- omethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether and so on; chlorinated hydrocarbons such as methylene chloride, trichloroethylene, perchloroethylene, o-dichlorobenzene and the like; dimethylformamide, dimethylsulfoxide and so on.

15

(1 )-a: Production of glycidyl group-containing acrylic copolymer

The glycidyl group-containing monomer such as glycidyl (metha)acrylate, allylglycidyl ether or the like 20 is copoiymerized with the aforementioned usual a, /3-ethylenically unsaturated monomer.

(1 )-b: Production of acetoacetoxy group-containing acrylic copolymer

25 The acetoacetoxy group-containing acrylic copolymers are produced by anyone of the following three methods.

In a first method, a monomer containing an acetoacetic acid ester group such as acetoacetoxyethyl (metha)acrylate, acetoacetoxypropyl (metha)acrylate or the like is copoiymerized with the above usual a, /3- ethylenically unsaturated monomer.

30 In a second method, a hydroxyalkyl ester of (metha)acrylic acid such as 2-hydroxyethyl (metha)- acrylate, 2-hydroxypropyl (metha)acrylate or the like is copoiymerized with the above usual a, /S- ethylenically unsaturated monomer to obtain an acrylic copolymer containing hydroxyl group. Then, the reaction product is held at a temperature of 0-150° C and reacted with diketene for 1-8 hours to acetoacetylate a required amount of the hydroxyl group. In this case, a catalyst is not necessarily used. If

35 necessary, a slight amount of a tertiary amine such as triethylamine or the like, or a carboxylate such as potassium acetate or the like, or an organic metal compound such as dibutyl tin dilaurate or the like is used as a catalyst.

In a third method, the same acrylic copolymer containing hydroxyl group as in the second method is added with an alkyl acetoacetate such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate,

40 butyl acetoacetate, hexyl acetoacetate or the like, which is subjected to a reaction for the removal of alcohol at 100-200° C for 1-8 hours, if necessary, in the presence of an ester exchange catalyst such as calcium acetate, lead oxide or the like.

45 (1 )-c: Production of cyclocarbonate group-containing acrylic copolymer

The cyclocarbonate group-containing acrylic copolymers are produced by either of the following two methods. In a first method, a, ^-ethylenically unsaturated monomer containing cyclocarbonate group such as 4-(metha)acryloyloxymethyl-1 ,3-dioxolane-2-on, 4-(metha)acryloyloxyethyl-1 ,3-dioxolane-2-on, 4-(metha)-

50 acryloyloxypropyl-1,3-dioxolane-2-on, 4-(metha)acryloyloxybutyl-1 ,3-dioxolane-2-on or the like is copoiymerized with the aforementioned usual a, /3-ethylenically unsaturated monomer. Moreover, the cyclocarbonate group-containing monomer can easily be obtained reacting a, /3-ethylenically unsaturated monomer containing oxylane group (epoxy group) such as 2-(metha)acryloyloxymethyl oxylane, 2-(metha)- acryloyloxyethyl oxylane, 2-(metha)acryloyloxypropyl oxylane, 2-(metha)acryloyloxybutyl oxylane or the like

55 with carbon dioxide gas in the presence of potassium iodide or sodium iodide and triphenylphosphine or quartenary ammonium salt as a catalyst at 40-180° C as described in DE-OS 3 529 263.

In a second method, the aforementioned oxylane group-containing monomer is previously copoiymerized with the usual a, /3-ethylenically unsaturated monomer and thereafter reacted with carbon dioxide gas as

10

EP 0 358 358 A2

in the first method to convert the oxylane group into cyclocarbonate group.

(2) Production of component C

(2)-a: Production of components Ci and C2

An alcohol of Ri OH and a lactone of

are reacted in the presence of a tertiary amine such as triethylamine or the like, or an organic metal compound such as tetrabutoxy titanate or the like, or a phosphorus compound such as triphenylphosphine or the like as a catalyst at 1 00-200 'C for 1-10 hours to obtain a polyester oligomer containing hydroxyl group in its terminal. If the viscosity of the resulting product is high, the reaction may be carried out in the co-existence of an organic solvent having no active hydrogen, if necessary.

The component C1 is produced by reacting the above polyester oligomer with a diisocyanate compound of OCN-R3-NCO in the absence or presence of an organic metal compound such as dibutyltin dilaurate, a carboxylate such as potassium benzoate or a tertiary amine such as triethylene diamine or the like as a catalyst in such a manner that a mol ratio of hydroxyl group of the above oligomer to the diisocyanate OCN-R3-NCO is within a range of 1:0.8-1:1.5, preferably 1:1. The reaction conditions are desirably 20-80° C and 1-10 hours.

The component C2 is produced by reacting the above polyester oligomer with diketene at a mol ratio of diketene to hydroxyl group of 0.9-1.1:1, preferably 1:1 under the same reaction conditions as in the above item (1)-b. Alternatively, it may be produced by using acetoacetic acid ester instead of diketene through the reaction for the removal of alcohol.

(2)-b: Production of components C3, C4, C5 and Cs

The components C3 and C4 are produced by reacting monovalent alcohol of Ri OH, acid anhydride of

A

o=c c = o V

and epoxy compound of

RgCH-CH-R,- 5 \ / 6 O

in the absence or presence of a tertiary amine such as triethylene diamine, quaternary ammonium salt such as tetramethyi ammonium chloride, organic carboxylate such as potassium benzoate or inorganic salt such as potassium iodide as a catalyst at 100-180° C for 1-10 hours to obtain a polyester oligomer containing hydroxyl group in its terminal through successive ring-opening of the acid anhydride and epoxy compound. On the other hand, the components Cs and C6 are produced by reacting carboxylic acid of R1COOH instead of R1OH with the acid anhydride and epoxy compound under the same conditions as described above to obtain a polyester oligomer containing hydroxyl group in its terminal through successive ring- opening of the epoxy compound and acid anhydride. Moreover, if the viscosity of the resulting product

11

EP 0 358 358 A2

during these reactions is high, the reaction may be carried out in the co-existence of an organic solvent containing no active hydrogen, if necessary. In the components C3 and C5, the above prepolymer is reacted with diisocyanate compound in the same manner as in the component Ct, while in the components C4 and Cs, the prepolymer is reacted with diketene or acetoacetic acid ester in the same manner as in the

5 component C2, whereby the objective polyester compound containing isocyanate group or acetoacetoxy group in its terminal is obtained.

(3) Production of pigment dispersing agent from components Ai and B 70

The pigment dispersing agent according to the first invention is produced by mixing the components Ai and B and then reacting them in the absence of a catalyst for about 1-10 hours. The reaction temperature is desirable to be 20-1 40 'C in case of glycidyl group as a reaction point of the component B, 20-100° C in case of acetoacetoxy group and 20-120° C in case of cyclocarbonate group. If it is required to use a

15 synthetic solvent, anyone of the solvents described in the production of the component B is used.

(4) Production of pigment dispersing agent from components A2, B and C

20 The pigment dispersing agent according to the second invention is produced by mixing the components A2, B and C and then reacting them in the absence of a catalyst at 20-100° C for 1-10 hours. Alternatively, there are a method wherein the component A2 is reacted with the component B and then the component C is added thereto, and a method wherein the component A2 is reacted with the component C and then the component B is added thereto. When the component A2 is first reacted with the component B,

25 the reaction condition is the same as in the above item (3), and the second reaction stage may only be carried out at 20-100° C. When the component A2 is first reacted with the component C, it is desirable that the reaction is carried out 20-100° C at each stage.

The pigment dispersing agents according to the invention are used for paints, inks, toners and magnetic tape coating materials as well as various colorants. As an objective pigment, mention may be made of

30 inorganic pigments such as titanium dioxide, zinc oxide, cadmium sulfide, iron oxide, calcium carbonate, red lead, zinc sulfide, barium sulfate, barium carbonate, clay, talc, chrome yellow, carbon black and so on; organic pigments such as azo series, diazo series, condensed diazo series, thioindigo series, indanthrone series, anthraquinone series, benzimidazolone series, phthalocyanine series, pyranthrone series, anth- rapyridine series, isoindolinone series, perylene series, quinacridone series, furavanthrone series, dioxazine

35 series, piranthrone series, perinone series and the like. The pigment dispersing agents according to the invention exhibit an effect of enhancing the pigment dispersibility against these pigments.

The pigment dispersing agent according to the invention is used in an amount as a solid content of 1- 200% by weight, preferably 5-100% by weight to the pigment in a so-called pigment dispersion base composition. The pigment dispersion base composition is comprised of the pigment dispersing agent

40 according to the invention, the pigment and the organic solvent, or may further contain a part or whole of a film-forming resin. Such a pigment dispersion base is dispersed by means of a dispersing machine usually used in the art, such as roll mill, ball mill, sand grind mill, attritor, paint shaker, kneader, high speed dispersing machine, ultrasonic dispersing machine, dissolver or the like, which is supplied for use in the colorant.

45 The paints obtained by using the pigment dispersing agent according to the invention are excellent in the dispersibility of pigment and color strength and form a paint film having good gloss, distinctness of image and smoothness. Furthermore, the pigment dispersing agent according to the invention strongly adsorbs on the surface of the pigment to prevent a tendency of agglomerating the pigment particles, resulting in the production of paints having an excellent storage stability and a high solid content.

50 Moreover, the pigment dispersing agent according to the invention has a crosslinking point in the structure, so that it causes a curing reaction with a crosslinking agent, and consequently the pigment dispersing agent is chemically fixed in the paint film likewise the case of the film-forming resin to chemically strengthen the boundary face between the pigment and the resin. Therefore, there is no damage on the water resistance, humidity resistance, weather resistance and the like of the paint film. Furthermore,

55 there is no bleeding of the dispersing agent on the surface of the paint film, so that there is not reduction of gloss, surface hardness and the like and no degradation of adhesion property between paint films. In addition, the invention solves the difficulty using the polymer type pigment dispersing agent. That is, the pigment dispersing agents according to the invention can be applied to both the acrylic resin paint and

12

EP 0 358 358 A2

polyester resin paint greatly used in the art, and also are applicable to paint formulations containing resins of low or high polarity.

The following examples are given in illustration of the invention and are not intended as limitations thereof. In these examples, "part" and "%" are by weight.

Synthesis Examples 1 and 2

10 <Production of polyester resin>

A polyester resin as a main film-forming component for polyester resin series paint was produced as follows.

Into a reaction vessel provided with a reflux condenser, an inlet tube for nitrogen gas, a thermometer 75 and a stirring blade were charged starting materials having a composition (Synthesis Examples 1 and 2) as

shown in the following Table 1, which were heated to an upper limit temperature of 230° C under a stream of nitrogen gas with stirring. Water generated in the progress of the reaction was removed together with xylene through azeotropic distillation and the heating was continued till the acid value was about 10 to complete the reaction. The resulting resin was diluted with xylene so as to render the nonvolatile content

20 into 60%, whereby the objective polyester resins PE-1 and PE-2 were obtained.

Table 1

Synthesis Example

1 2

Polyester resin No. PE-1 PE-2

lauric acid 4.5 tail oil fatty acid - 16.2 castor oil - 3.8 phthalic anhydride 5.8 17.7 isophthalic acid 21 .8 adipic acid 1 .6 5.0 neopentyl glycol 12.8 10.4 trimethylol propane 7.4 pentaerythritol - 8.6 Cardula E-10 11 8.3 xylene 1 .8

xylene (diluting solvent) 36.0 38.3

nonvolatile content (%) 60 60 resin acid value 10 10

1) Cardula E-10: trade name, made by Shell Chemicals Co., Ltd. (glycidylester of versatic acid)

Synthesis Examples 3-11

55 < Production of acrylic resin>

An acrylic resin as a main film-forming component for acrylic resin series paints was produced as follows.

13

EP 0 358 358 A2

Into a reaction vessel provided with a reflux condenser, an inlet tube for nitrogen gas, a thermometer, a stirring blade and a monomer dropping device was charged a solvent shown in the following Table 2 and then the temperature was raised to a reflux temperature under a stream of nitrogen gas. A mixture of each monomer and t-butylperoxy benzoate as a polymerization initiator as shown in Table 2 was added dropwise

5 through the dropping device over 2 hours under reflux state. After the addition, the stirring was further continued for 5 hours under reflux state to complete the polymerization, whereby the objective varnishes AC-1 - AC-9 were obtained.

w Synthesis Examples 12-18

A polyester resin (component C) for the pigment dispersing agent was produced as follows. Into a reaction vessel provided with a reflux condenser, an inlet tube for nitrogen gas, a dropping funnel,

a thermometer and a stirring blade were charged xylene as a solvent, tetrabutoxy titanate and 2-ethyl 15 hexanol or decanol among ingredients shown in the following Table 3 and then the temperature was raised

to 130-140° C under a stream of nitrogen gas. Further, s-caprolactone shown in Table 3 was added dropwise through the dropping funnel over 2 hours under reflux state and thereafter the stirring was continued for about 5 hours.

In Synthesis Example 12, the temperature of the reaction product was lowered to 30 °C and tolylene 20 diisocyanate was added in an amount shown in Table 3 and then the stirring was continued for about 2

hours to obtain a polyester resin Ci having properties shown in Table 3 and containing isocyanate group in its terminal.

In Synthesis Examples 13-18, the temperature of the reaction product was lowered to 70 °C and triethylene diamine shown in Table 3 was added and then diketene shown in Table 3 was added dropwise

25 over about 2 hours with strong stirring to produce polyester resins C2-I -C2-6 containing acetoacetoxy group in their terminal.

Synthesis Examples 19-22 30

In the same synthesis vessel as in Synthesis Example 12, toluene as a solvent, anyone of lauric acid, octylic acid, decanol and cetyl alcohol, phthalic anhydride and tetramethyl ammonium chloride as shown in Table 3 were mixed and then rendered into a reflux state of about 135°C. Next, butylglycidyl ether or a mixture of butylglycidyl ether and phenylglycidyl ether in Table 3 was added dropwise through the dropping

35 funnel over about 1 hour, which was maintained under reflux state for about 5 hours. After the completion of the reaction, xylene in Table 3 was added to conduct dilution.

In Synthesis Examples 19 and 21, the temperature of the reaction product was lowered to 30° C, and dibutyltin dilaurate and tolylene diisocyanate in Table 3 were added and then the stirring was continued for about 2 hours to complete the reaction.

40 In Synthesis Examples 20 and 22, the temperature of the reaction product was lowered to about 50° C, and triethylene diamine in Table 3 was added and further diketene was added dropwise through the dropping funnel over about 30 minutes with strong stirring and the stirring was further continued for 4 hours to produce polyester resins.

45 Synthesis Examples 23-72

A mixture of monomers as shown in the following Table 4 was added dropwise through the dropping funnel in the same vessel according to the same method as described in Synthesis Examples 3-11 over

50 about 2 hours. After the addition, the stirring was further continued for 2 hours to obtain acrylic resins (B1 -1 - Bi-10, B2-I - B2-25, B3-I - B3-15) as a component B for pigment dispersing agent.

Moreover, in Synthesis Examples 51 and 52, the reaction mixture after the completion of the above reaction was cooled to about 50 ° C, and triethylene diamine in Table 4 was added and then diketene in Table 4 was added dropwise over about 30 minutes with strong stirring and the stirring was further

55 continued for about 4 hours to complete the production.

Examples 1-26

14

EP 0 358 358 A2

Pigment dispersing agents of Ai-B type were produced according to a composition ratio as shown in the following Table 5 as follows.

Into the same vessel as in Synthesis Example 1 was charged a component B or a mixture of component B and solvent as shown in Table 5, and then a component Ai was added with strong stirring,

5 which were heated to a temperature shown in the column for reaction conditions of Table 5 and reacted at this temperature for a time shown in the column for reaction conditions of Table 5 to produce the objective pigment dispersing agents.

Moreover, the combination of components Ai and B is represented, for example, as A1-B1 in the column for structure of pigment dispersing agent of Table 5, wherein B1 is component B containing gylcidyl

10 group, B2 is component B containing acetoacetoxy group and B3 is component B containing cyclocarbonate group.

Examples 27-53 rs

Pigment dispersing agents of A2-B-C type were produced according to a composition ratio as shown in the following Table 6 as follows.

Into the same vessel as in Synthesis Example 1 was charged a mixture of component B and solvent as shown in Table 6, and then a component A2 was added at room temperature with strong stirring, which

20 were heated and reacted under synthesis conditions shown in the column for reaction conditions in A2-B reaction of Table 6 likewise Examples 1-26. Then, the temperature of the reaction product was adjusted to a temperature shown in the column of A2-C reaction conditions and a component C was added dropwise over about 30 minutes and stirred for a time described in the same column to produce the objective pigment dispersing agents.

25 Moreover, the combination of components A2, B and C is represented, for example, as A2-B1-C1 in the column for structure of pigment dispersing agent of Table 6, wherein B1-B3 and C1-C6 are the same components as previously mentioned.

30 Application Examples 1-64

Dispersion pastes and paints each having a composition as shown in the following Table 7 were prepared by using the pigment dispersing agents shown in Tables 5 and 6, and then the properties of the paste and film performances of the paint were measured to evaluate the effect of the pigment dispersing

35 agent according to the invention. That is, starting materials were uniformly mixed in accordance with a formulation of dispersion paste

shown in Table 7, and then the mixture was dispersed by means of a paint shaker (made by Red Devil Co.) to obtain a dispersion paste. The viscosity and storage stability of this dispersion paste are shown in the column of paste properties of Table 7.

40 Then, starting materials using the above dispersion paste were mixed in accordance with a formulation for paint shown in Table 7 and thoroughly stirred to prepare a paint. To this paint was added a thinner for dilution (cellosolve acetate/ xylene = 50/50 mixed solvent) so as to adjust a viscosity to 20 seconds (25° C) through Ford Cup No. 4, whereby a finishing paint for spray coating was obtained.

Next, a primer coated plate was provided in order to evaluate the film performances of this paint. That 45 is, an SPCC dull steel sheet (size: 0.8x100x150 mm) subjected to a zinc phosphate treatment was

subjected to an electrodeposition with a general-purpose black cation electropaint (Aqua No. 4200, trade name, made by Nippon Oil and Fats Co., Ltd.) and then baked at 170° C for 30 minutes to obtain a dried paint film of 20 u.m in thickness. Thereafter, an alkyd/melamine series gray intermediate paint for automotive (Epico No. 1500 sealer, trade name, made by Nippon Oil and Fats Co., Ltd.) was diluted with a

50 thinner (Thinner TR 101, trade name, made by Nippon Oil and Fats Co., Ltd.) so as to adjust a viscosity to 30 seconds (25 ° C) through Ford Cup No. 4 and then sprayed onto the above primer coated sheet and baked at 140° C for 30 minutes to obtain a dried paint film of 40 urn in thickness. Then, the aforementioned finishing paint was sprayed onto the thus painted steel sheet and baked at 140° C for 30 minutes to obtain a test film (finished film thickness: 40 u,m). The specular gloss at 30° (Drigon goniophotometer, made by

55 Hunter Laboratories), humidity resistance, weather resistance and presence or absence of bleeding phenomenon of dispersing agent onto film surface were evaluated with respect to the thus obtained test specimen. The result are also shown in Table 7.

As seen from Table 7, all of the dispersion pastes using the pigment dispersing agent according to the

15

EP 0 358 358 A2

invention are excellent in the storage stability. As to the film performances, it has been confirmed that the gloss is excellent in all paint films and the humidity resistance and weather resistance are not damaged. Furthermore, there is observed no bleeding of the pigment dispersing agent on the film surface.

Comparative Examples 1-13

Pigment dispersing agents of Comparative Examples 1-13 were produced in accordance with a composition ratio as shown in the following Table 8 in A-B system in the same manner as in Examples 1-26 and in A-B-C system in the same manner as in Examples 27-53.

Application Comparative Examples 1-16

Dispersion pastes and paints as shown in the following Table 9 were produced by using the pigment dispersing agents of Comparative Examples 1-13 and the pigment dispersing agents of Examples 2 and 22. Either of storage stability of dispersion paste and film performances of paint as shown in Table 9 is poorer than that shown in Table 7.

16

EP 0 358 358 A2

Table 2

Synthesis Example

5 3 4 5 6 7 8 9 10 11

Acrylic resin No. AC-1 AC-2 AC-3 AC-4 AC-5 AC-6 AC-7 AC-8 AC-9

Solvent xylene 40 40 40 10 20 25 20 52 39.8

?o isobutyl acetate - - 30 20 15 20

Monomer methyl 23.4 15.0 30.5 32.0 28.0 2.0 30.0 16.4 24.7 methacrylate

composition ethyl acrylate - 22.0 . . . . . . .

75 butyl acrylate 13.3 - 20.0 - 5.0 5.0 5.0 15.8

butyl - - 5.0 5.0 10.0 4.0 - 16.9 methacrylate

hexyl 10.0 - 20 methacrylate

lauryl 10.0 - - 12.0 6.0 3.0 methacrylate

styrene - 5.0 - 13.0 4.0 30.0 11.0 5.2 5.0 25 2-hydroxyethyl - 7.0 - 8.0 5.0 5.0 5.0

acrylate

2-hydroxyethyl 12.0 - 8.0 - - - - 9.7 11.9 methacrylate

acrylic acid 0.7 0.5 1.0 - - - - 0.3 1.1

t-butyl peroxy 0.6 0.5 0.5 2.0 1.0 2.0 2.0 0.6 0.6 benzoate

Properties nonvolatile 60 60 60 60 60 60 60 50 60 content (%)

weight average 21,000 24,000 25,200 33,800 58,500 28,200 29,300 20,000 21,000 molecular weight

40 hydroxyl value 86 56 58 64 40 40 40 80 86

45

50

17

EP 0 358 358 A2

Table 3

Synthesis Example

12 13 14 15 16 17 18 19 20 21 22

Polyester resin No. Ci C2-1 C2-2 C2-3 C2-4 C2-5 C2-6 C3 C4 C5 Ce

Solvent xylene 40 40 40 40 40 40 40 25 25 25 25

toluene - - 15 15 15 15

Monomer e-caprolactone 55.08 58.44 49.17 53.47 57.11 58.81 41.67

composition lauric acid . . . . . . . . . 2.5 -

octylic acid . . . . . . . . . . 2.9

phthalic - - 27.5 29.4 28.5 26.9 anhydride

2-ethyl hexanol 2.1 0.92 6.5 - -

decanol - - - 4.21 1.85 0.7 11.85 3.6

cetyl alcohol . . . . . . . . 2.4 - -

butylglycidyl - - 21.2 18.2 26.7 13.2 ether

phenylglycidyl 3.5 9.07 - 15.2 ether

tetrabutoxy 0.02 0.02 0.02 0.02 0.02 0.02 0.02 . . . . titanate

tetramethyl - - 0.06 0.06 0.06 0.06 ammonium chloride

triethylene - 0.01 0.01 0.01 0.01 0.01 0.01 - 0.01 - 0.01 diamine

dibutyltin - - 0.04 - 0.04 dilaurate

tolylene 2.8 4.1 2.2 diisocyanate

diketene - 0.61 4.3 2.29 1.01 0.46 6.45 - 0.86 - 1.73

Properties nonvolatile 60 60 60 60 60 60 60 60 60 60 60 content (%)

weight average 3,700 8,500 1,200 2,250 5,120 11,200 800 2,580 6,000 4,670 2,960 molecular weight

50

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24

EP 0 358 358 A2

Table 5(a)

5 Example No. 1 2 3 4 5 6 7 8 9

Structure of pigment dispersing Ai -Bi Ai -B2 agent

Pigment dispersing agent No. 1 2 3 4 5 6 7 8 9

Solvent butanol 17.05 17.32 18.0

ethanol . . . . . . . . .

Component imino bispropyl amine 0.65 . . . . . . . . 15 Ai t9 6T7) (neve Terda/i vt . . . . . . . . .

Epomine SP006 1) - 0.98 0.74

Epomine SP012 11 . . . . . . . . .

20 Epomine SP01 8 11 1.9 4.13

Epomine SP200 1> 4.5 - 4.0

Epomine SP300 1) - - - 2.5 2.0

polypropylene . . . . . . . . . polyamine PA06 2)

Component component B No. Bi-1 Bi-2 B,-3 Bt-4 Bi-5 B1-6 Bi-7 B2-1 B2-2

B formulating amount 82.3 81.7 80.1 95.5 97.5 96.0 98.0 95.87 99.26

30 Properties Ai/B mol ratio 1/2 1/3 1/1.8 1/1.5 1/7.7 1/4.7 1/22 1/1 1/2

amine value 17 21 40 79 44 70 35 109 14

nonvolatile content (%) 50 50 50 60 60 60 60 50 50

hydroxyl value of 40 70 30 77 50 19 27 50 10 component B

molecular weight of 5,000 10,000 25,000 80,000 90,000 30,000 40,000 19,500 21,050 component B

number of reactive 1.2 1.0 1.1 1.7 1.7 1.0 1.0 1.2 1.2 groups in component B 3)

Reaction Ai-B temperature 120 100 120 60 60 60 60 60 60 CC)

conditions reaction time (Hr) 2 4 4 12 12 12 12 2 2

50

25

=P 0 358 358 A2

fable 5(b)

5 Example No. 10 11 12 13 | 14 | 15 | 16 | 17 | 18

Structure of pigment dispersing agent A1-B2

Pigment dispersing agent No. 10 11 12 13 14 15 16 17 18

10 Solvent butanol - - - - - - - 10.0 -

ethanol - - - - 6.7

Component imino bispropyl amine . . . . . . . . .

Ai t6 6T7i ueve TerQaa ve . . . . °t2* . . . .

Epomine SP006 1) - 0.5

Epomine SP01 2 1) . . . . . . . . .

Epomine SP01 8 11 1.74 1.74 1.4 - - - 1.74 20 Epomine SP200 1) - - - 5.12 - - - - 1.74

Epomine SP300 1)

polypropylene polyamine - - - - - - - 1 .05 - PA06 2)

25 - - Component component B No. B2-3 B2-4 B2-5 B2-6 B2-7 B2-8 B2-9 B2-10 B2-11

B formulating amount 98.26 98.26 98.6 94.88 99.76 99.5 98.26 82.25 98.26

Properties A, /B mol ratio 1/2.5 1/2.5 1/2.5 1/2.5 1/3 1/3 1/5 1/2 1/10 30 amine value 46 46 37 134 7 14 37 21 37

nonvolatile content (%) 50 50 50 50 50 50 50 50 50

hydroxyl value of 20 30 30 30 40 40 50 50 62 component B

IS - molecular weight of 19,800 20,100 24,900 35,700 9,820 19,900 9,800 14,000 5,300 component B

number of reactive groups 1.2 1.2 1.2 1.2 1.0 1.0 1.0 1.0 0.8 in component B 3)

40 r Reaction A1-B temperature (° C) 60 60 60 60 60 60 60 60 60

conditions reaction time (Hr) 2 2 2 2 2 2 2 2 2

45

50

26

IP 0 358 358 A2

able 5(c)

5 Example No. 19 | 20 21 | 22 | 23 | 24 | 25 | 26

Structure of pigment dispersing agent Ai-B2 Ai-B3

Pigment dispersing agent No. 19 20 21 22 23 24 25 26

o Solvent butanol 21.37 20.73 - - - - 21.37 20.73

ethanol - - - - - - - -

Component imino bispropyl amine - - - - - - - -

Ai T0 6T7) (iKVi TiTQctjl Vi . . . . . °'T24 5 ^ — — — — — - —

Epomine SP006 1) - - - - - - - -

Epomine SP01 2 1) - 0.77 - - - - - 0.77

Epomine SP0181) 1.33 - 4.13 1.74 1.4 - 1.33 0 Epomine SP200 1) - - - - - - - -

Epomine SP300 1) - - - - - - - -

polypropylene polyamine - - - - - - - - PA06 2)

'5 Component component B No. B2-12 B2-13 B3-1 B3-2 B3-3 B3-4 B3-5 B3-6

B formulating amount 77.3 78.5 95.87 98.26 98.6 99.76 77.3 78.5

Properties A,/B mol ratio 1/2 1/3 1/1 1/2.5 1/2.5 1/3 1/2 1/3

30 amine value 35 20 109 46 37 7 35 20

nonvolatile content (%) 40 40 50 50 50 50 40 40

hydroxyl value of 45 55 50 30 30 40 45 55 component B

35 molecular weight of 26,100 20,500 20,600 19,600 24,300 9,750 25,200 21,000 component B

number of reactive groups 1.0 1.2 1.2 1.2 1.2 1.0 1.0 1.2 in component B 31

40 | Reaction Ai-B temperature f C) 60 60 80 80 80 80 100 90

conditions reaction time (Hr) 2 2 5 5 5 5 4 4

45

50

27

EP 0 358 358 A2

Table 6(a)-1

5 Example No. 27 28 29 30 31 32 33

Structure of pigment A2-B,-Ci Aa-B^Cs A2-B1-C3 A2-Bi-Cm A2-Bi-C5 A2-Bi-C6 A2-B2-C, dispersing agent

jn Pigment dispersing agent No. 27 28 29 30 31 32 33

Solvent xylene 10.7 - 29.1 6.81 10.5 8.7

butanol 7.0 18 5 - 7 9.3 2.2

ethanol - - 10 15 Component imino bispropyl . . . n.59

amine

A2 t8 errj meve . . . . . . .

20 Epomine SP006 1 .7 1)

Epomine SP01 2 - 1.9 - 1.3 1)

25 Epomine SP01 8 - - 1.0 1)

Epomine SP200 . . . . . . . D

30 Epomine SP300 . . . . . . . 1)

polypropylene - - - - - 1.8 1.1 polyamine PA06

35 2>

Component component B B,-2 Bi-3 Bi-6 Bi-1 Bi-3 Bi-2 B2-1 N o . .

B formulating 46.3 64.6 57.5 37.5 46.4 50.5 74.3 40 amount

Component component C Ci C2-2 Cs C* Cs Cs Ci No.

C formulating 34.3 15.5 7.4 45.1 34.8 29.7 22.4 45 amount

so

28

30

35

40

45

50

EP 0 358 358 A2

Table 6(a)-2

Example No. 27 28 29 30 31 32 33

Properties A2/B mol ratio 1/1 1/1 1/2 1/1 1/1 1/1 1/1

A2/C mol ratio 1/2 1/5 1/3 1/1 1/4 1/2 1/2

amine value 36 40 26 15 27 46 28

nonvolatile content (%) 50 50 40 50 50 50 50

hydroxyl value of 70 30 19 40 30 70 50 component B

molecular weight of 10,000 25,000 30,000 5,000 25,000 10,000 19,500 component B

number of reactive groups 1.0 1.1 1.0 1.2 1.1 1.0 1.2 in component B3)

molecular weight of 3,700 1,200 2,580 6,000 4,670 2,960 3,700 component C

Reaction A2-B temperature (° C) 120 120 100 120 120 120 60

conditions reaction time (Hr) 4 4 4 4 4 4 2

Reaction A2-C temperature (' C) 50 50 30 60 30 60 30


10

15

20

25

55

29

EP 0 358 358 A2

Table 6(b)-1

Example No. 34 35 36 37 38 39 40

Structure of pigment dispersing agent A2-B2-C2 A2-B2-C3

Pigment dispersing agent No. 34 35 36 37 38 39 40

Solvent xylene 7.7

butanol 1.05 10 0.57 1.79 1.53 1.3 4.5

ethanol . . . . . .

Component imino bispropyl amine . . . . . .

A2 t9 &ti) <aeve rerBan ve . . °t82 . . . Epomine SP006 " . . . 2.68

Epomine SP012 " 1.71 . . . . . 1.8

Epomine SP01 8 1) - 1.6 - - 2.29 1.95

Epomine SP200 11 . . . . . .

Epomine SP300 1) . . . . . .

polypropylene polyamine PA06 2) . . . . .

Component component B No. B2-14 B2-19 B2-15 B2-16 B2-17 B2-18 B2-5

B formulating amount 77.0 71.0 76.71 62.0 63.61 56.32 74.6

Component component C No. C2-1 C2-3 C2-2 C2-3 C2-4 C2-5 C3

C formulating amount 20.24 9.7 21.9 33.53 32.57 40.43 19.1

30

P 0 358 358

aoie b(D)-2

Example No. 34 35 36 37 38 39 40

Properties A2/B mol ratio 1/1 1/2 1/3.3 1/1.7 1/3.3 1/2.6 1/1

A2/C mol ratio 1/1 1/3 1/2.7 1/1.5 1/5 1/3.4 1/3

amine value 30 34 21 47 40 34 38





molecular weight of 8,500 2,250 1,200 2,250 5,120 11,200 2,580 component C

Reaction A2-B temperature (° C) 60 60 60 60 60 60 60


Reaction A2-C temperature ( C) 60 60 50 60 60 60 30


01

EP 0 358 358 A2

Table 6(c)-1

5 Example No. 41 42 43 44 45 46 47

Structure of pigment dispersing A2-B2-C* A2-B2-C5 A2-B2-Cs A2-B3-C1 A2-B3-C2 agent


Solvent xylene - 12.8 7.1 13.7

butanol 4.5 5 - 6 1.05 0.57 1.79

ethanol - 10.0 . . . . 75 Component imino bispropyl - - 0.6 . . . .

amine

A2 reeriiueve . . . . °t82 TSTQan Vi

20 Epomine SP006 1) - - - . . . 2.68

Epomine SP01 2 1> - - - 1.0 1.71

Epomine SP01 8 1) 1.4 - - . . . .

25 Epomine SP200 1) - - - . . . .

Epomine SP300 " - - - . . . .

polypropylene - 1.7 - . . . . polyamine PA06

30 2>

Component component B No. B2-12 B2-20 B2-16 B3-1 B3-7 B3-8 B3-9

B formulating 79.1 59.2 60.8 69.4 77.0 76.71 62.0 amount

35 Component component C No. C+ C5 C6 Ci C2-I C2-2 C2-3

C formulating 15.0 21.3 21.5 9.9 20.24 21.9 33.53 amount

40

45

50

32

10

!5

to

45

50

able ti(c)-z

Example No. 41 42 43 44 45 46 47

Properties A2/B mol ratio 1/2 1/1 1/1 1/2 1/1 1/3.3 1/1.7

A2/C mol ratio 1/2 1/1 1/1 1/2 1/1 1/2.7 1/1.5

amine value 29 36 15 26 30 21 47





molecular weight of 6,000 4,670 2,960 3,700 8,500 1,200 2,250

component C

Reaction A2-B temperature (' C) 80 70 60 70 80 80 80


Reaction A2-C temperature (* C) 50 30 60 30 50 50 60


5

0

'5

55

30

EP 0 358 358 A2

Table 6(d)-1

Example No. 48 49 50 51 52 53

Structure of pigment dispersing agent A2-B3-C2 A2-B3-C3 A2-B3-C4 A2-B3-C5 A2-B3-C6

Pigment dispersing agent No. 48 49 50 51 52 53

Solvent xylene - 9.4 12.7 - 23.8 8

butanol 1.53 12 5 3.8 5 10

ethanol - - - -

Component imino bispropyl amine

Ai 78 677) oieve Terdccji ce . . . . . .

Epomine SP006 1> - - -

Epomine SP01 2 1) - - 1.6

Epomine SP01 8 1) ' 2.29 1.3 - 1.8

Epomine SP200 1) 6.8

Epomine SP300 1) . . . . . .

polypropylene polyamine PA06 a> - - - 2.0

Component component B No. B3-IO B3-3 B3-10 B3-6 B3-4 B3-9

B formulating amount 63.61 71 .8 64.2 84.4 53.7 46.7

Component component C No. C2-4 C2-3 C3 C+ Cs Cs

C formulating amount 32.57 5.5 16.5 10.0 10.7 33.3

34

EP 0 358 358 A2

able 6(d)-2

Example No. 48 49 50 51 52 53

Properties A2/B mol ratio 1/3.3 1/2 1/2 1/2 1/4 1/1

A2/C mol ratio 1/5 1/2 1/3 1/1 1/2 1/2

amine value 40 34 34 38 179 61

nonvolatile content (%) 60 40 50 50 40 50

hydroxyl value of component 50 30 50 55 40 52 B

molecular weight of 15,200 24,300 15,200 21,000 9,750 8,400 component B

number of reactive groups in 1.2 1.2 1.2 1.2 1.0 1.15 component B3)

molecular weight of 5,120 2,250 2,580 6,000 4,670 2,960 component C

Reaction A2-B temperature (' C) 80 80 100 90 80 70

conditions reaction time (Hr) 5 5 3 4 5 4

Reaction A2-C temperature (* C) 60 50 30 50 30 60

conditions reaction time (Hr) 2 3 3 4 3 3

30

35

40

45

50

35

:P 0 358 358 A2

Note:

1) Epomine: trade name of polyethylene imine having the following molecular weight and amine ralue, made by Nippon Shokubai Kagaku Kogyo K.K.

Trade namer Molecular Amine weight value

Epomine SP006 600 1050 Epomine SP01 2 1,200 1050 Epomine SP01 8 1,800 1050 Epomine SP200 10,000 1050 Epomine SP300 30,000 1050

2) trade name, made by Toso K.K., molecular weight: 600, amine value: 1100 3) Number of reaction group in component B is number of glycidyl, acetoacetoxy or cyclocarbonate

groups per one molecule of component B

36

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m f l l w * ' o > C N l ' J ' ' 1 1 1 ' e o ' 93 CM ^ fl CN ri @q rt CO VO CO 00 « r i f l . l " , " * I I C3 . . . . " i i i i i W i n f l ' w e o ' o i C N ' ' r t ' 1 1 ' c o ' ' ' ' ' En Cm h cn »H ri

ci o o o a a ° c n i . " " i " i i * i . i i i i i i i i i n f l c j ' t o o ' e o 1 1 eo 1 _ ' 1 1 1 1 ' 1 1

rt ... co en o eo e x ^ i 1 . ! " " i i ' i i i i i i i i " i a a 1 W J m cn 1 ' i n ' 1 1 1 1 1 1 ' e o '

CM fl rt ri ri

fl ri JJ fl — — rt — . fl „ vo eo cn CO 2 — . O ri cn ° in U O — O CO eel ^ c o — c N c n r i o o — > m O B r> eo in r* fi "*7 On O l r j o i CO U O 1 1 ri ri a jj c N S r t J e t j p - i J - - •rt t U C U s j c U I O C S OU3 K Eh • ta a > > jj 13 i ri K b o c o j j c o o , o u -rt r t r t c u - n S i r t i o i n j e u f c e q a c u f l t a o o o x e u c u o @-< a - n c o t a t a c a o j s x a u f l f l o f l f l w o j i j o o - h o h d ii n 'H ii gi ?, -n co r i r i t o f l < 4 E m x t t c d > c t : a < « i ^ f l u w rt rt > r t t j 2 , _ p 1 4) t U « r t E j a « U B B B r i B g 4 l 03 rr j j c j j j o o o a a c u e o o o a i w B ' C -ri to cu t o - r t B u c n c n M J J C n c u -rt g1 5 l ) r i 4 l B r i r i O S 0 4 » O O O O O a N 5 ; " - > l > l . > l > l H « J J J J J J - n . H . r ' H O « 'J ' „ C n l j r i r i J 3 J J r i J J In 10 t a r t j O r i r i J O CTi w a c . r t o o ^ j J a e u - r t c a o t c j i a s i c j a o M CUfl'tO a 03 Q< * 4> -O UJJ O h h A O i A A i l H a -rt cu m to u a •rt 41 O 1 41 fl M kl -rt Ll JJ CU JJ 4) to jj o jj ca a « c .rt to rt to a 4) rt 4) a -rt S >i N S fl fi en u rt u o @rt O O O <U -rt Cm rt Cm fa O to

43

eji m cn n U' tn

cn fl N N ° ' Cn 10 jjj

to cn £ o n n 1 « Q , co o co -JJ g " cn in cn p h ° " " en ™ „ -3 P- P« '" ' iflua 1,3 i S

to 2 O r i c n ' o » _ : ' c o o e o - 2 S "* cn in cn h en " „ <-> T3 P" O Ul u _ "3 i n e n o 2 O • , • • . . cn o fl i J m cn S o « , \ o r t 0 e o o e o - g 3 tn cn fl N n ° ' cn _ t3 p- eo en lo a 10 i S

» co o 2 o • , • • . . ri o fl A S r im cn 5 O t o ' i o r i Q - e o o e o - g g a en a cn cn en w SS E 5— , 2 a T) CN CN eo CN "O | 3

° §, , S S « S P" §, <° « |

~J to o ° t , " V o o J, §

ri ai 73 CN CN 03 CN "O , fi a m o JJ, o . . . . ^ . e n o f l i g CN a m CN " O f l f l ' O o O P - o e o - S S

1 m " cn a cn cn ih en n % rg -j "el CN CN CO , CN T3 , g Z. f l o 2 o • • i « . • o o cn ' 2 IT m cn ™ O f l f l ' o - ' o e o o e o - S g P- " cn fl cn cn rH en 03 jj U -i -3 CN "CN CO irt CN "3 , g r-f en o £ o . . . . . . H o m i 2 _Q m cn £ o f l ' f l o ' o c o o eo tj g 7g N cn fl cn cn iH en 10 ^ _ TO CN CN CO CN TJ , g

CN o 2 o . . . « . o o cm I 2 m cn ri O f l ' f l O j - j O e o o e o - g s ; " cn a cn cn i— i cn £

r i o o « ^ « e n 1 w ?J 10 ' 3 £ 5 ' « g ° " * ° « S S

= § 5 "8 "I , "°. « cn 1 eo J, | " - a O O o ' f l o p , e o o e o - § |

en o % 1 ^ , * W. « o cn 1 a < § * " « 2 , , ' S H o f l - o c o - g g

--. n jj >, r- ca in C JJ JJ CD r-t «-t O 41 C -H JJ C ri g cu— . — ri w - h c - u en — > cn enfl in -h c ca c tn -h c a >-t •h edi-t >i o Cm ta u— o u u r - i a u u o O-hw jj.-trj cuto -rt 4)4)01 0>iC C tuen w -h tn — o ori to o jj c a u m jj ea m ca i u c jj u taw cn tn i* -h in -h t-i cu a -h jj cu jj cj c -h C tit} 04ICU ca -H CU « H 01 g r i C tOTjiajSU) B4)*0 o a cu y cujj -i -o jj a >i s-i ca cu c -h-h jj-h oi tn oi 0«-3 tn tn tn o tn tn v j H r i > - h o E tn cata tncuo) E -H T3 .-4 -rt <a JJ W « 'ri u O CU 4) St O 34) 414) H HH e« no id > - 3 a | t a 0 0 i ' 0 | e a a 6 ri JJ cn J3 u 3 u to aJ3

4) 1 JJ jj to tu a id n ri o to ri 1 0) a) 3 jj 1 01 ca tv-< a e c c Qi-h oi e O JJ H O-ri O JJ rl M MU O-Htt) UUM-I-H CM 0) O Dm JJ a CM 01 O MJ

44

EP 0 358 358 A2

Note:

5 1) pigment dispersing agent of Examples (Tables 5 and 6) 2) acrylic resin for film formation in Table 2 3) polyester resin for film formation in Table 1 4) titanium dioxide JR-602 (made by Teikoku Kako K.K., trade name) 5) carbon black FR-200 (made by Degussa AG, trade name)

w 6) Fosterparm Yellow H3Q (benzimidazolone series organic pigment, made by Hoechst, trade name) 7) Fastogen Blue RGA (copperphthalocyanine series organic pigment, made by Dainippon Ink &

Chemicals, Inc., trade name) 8) Paliogen Maroon L3820 (perylene series organic pigment, made by BASF Ag, trade name) 9) Rubicron Red 500RG (quinacridone series organic pigment, made by Toso K.K., trade name)

75 10) Paliotol Red L3670 (perylene series organic pigment, made by BASF AG, trade name) 11) Paliogen Violet L-5080 (thioindigo series organic pigment, made by BASF AG, trade name) 12) Noboperm Red F3RK-70 (azo series organic pigment, made by Hoechst, trade name) 13) Irgazine Red BPT (perylene series organic pigment, made by Ciba Geigy, trade name) 14) amount of pigment dispersing agent added as solid content on pigment (%)

20 15) paste viscosity: measured by means of B-type viscometer at 20° C (unit: CP) 16) After the dispersion paste was left to stand at 50 *C for 5 days, the viscosity was measured at

20 °C by means of B-type viscometer (trade name, made Tokyo Keiki K.K.). When the ratio of initial viscosity to viscosity after 5 days is within a range of 0.9-1.4, the storage stability is good, while when it exceeds 2.0, the property is poor.

25 17) melamine resin: Uban 220 (made by Mitsui Toatsu Chemicals, Inc., trade name, nonvolatile content: 60%)

18) leveling agent: Modaflow (made by Monsanto Co., trade name, 10% xylene solution) 19) thinner for dilution; cellosolve acetate/xylene = 50/50% 20) Humidity test

30 After the test sheet was held at 50±1 " C in a moisture atmosphere of not less than 95%RH for 120 hours, it was taken out from the above atmosphere and left to stand for 24 hours. The good or bad humidity resistance was evaluated by the size and density of resulting blister.

21) The 60° specular gloss was measured by means of a sunshine carbon weathermeter after the sheet was exposed for 1000 hours according to a method for weather acceleration test of JIS D0205-7.6.

35 The property was represented by the gloss retention (%). 22) Test for judgment of bleeding

After the cured film was rubbed with a methanol impregnated cloth several times, the film gloss or glossy feeling was judged by the presence or absence of bleeding, no change: no bleeding

40 enhancement of gloss: presence of bleeding

45

, 4 - i T f r i " i @ i co 1 1 1 n * oi t - o d c o co V c r i « i o t- ,_: cm n r- o t- 03

co @ in 1 ' ' jn r ,7 P o c o , * -- cn u io T- cm r~~ i- CQ

^ i t - i i i ' c n j ' 1 1 @ m r- 1 1 - ^ ^ Si

CD

i en i > @ -J- in cfl 1 1 - co 03 cri °? V fN : o n CJ3 CO h»

O ' LO 1 1 1 1 1 ' 1 1 •* CO > ' s. co r»- Is-, T • CO O m CO

CM CD Is"

O) ' ~4" 1 1 ' 1 1 CO 1 1 ' O i— ' 1 co m ip ^ T gj ° o £ cn

CO @ LO ' 1 1 1 l N ' ' 1 CM ffl ffl -- » M ~ 5 5 3 <s 3 J-s CD CO CO CO 0 N O O I O 1 ' ' .a •* i° --- cri en ' S ca t- t- « i° !_. cd

CO ' O ' ' 1 ' 1 C5 ' 1 ' C 3 T - ' 1 co in cd --' - o £ CQ CO

in i w ' @ • 1 @ -4- 1 1 @ -- to -4- cn o j I O c m co V « « ffl CO U ~ CD

rf < Q < 1 < 1 ' C i ' 1 ' CO t- ' ' t- in cd --' - o CD CO

CO

CL 0 c

'1 c >> C c f I t P C M C 0 O o I | p | p >, 2 O T- -r- O O <n @5- £ ^ £

o i c i 0 W ^ w < w w i i c ? l c ?

2 - O T § i S # c s o o o o o ^ E E £ E « x ia E .5 S lu uj lu lu lu a. o £ o £ UJ ijj ! 1 1 1 1 1 1 1 ' 1 '

> t£ € = ••= T3 iS 0 CO ca — c c c 1 § I a a a E £ § 5 E E o .2> o o o o O ex co G < O C Q O O

46

CM —

1 CO CO O O 1 ' O 1 1 O CM "D CM CO CD CM CO O i- C o

@r- m" °>

CMCMOJOO O CM O O LO O CM -g ~ ^ fl CO O ' CM CO CO o ZL "~ co o a" lo" °> cm

CMCMOJOO O O O O CM O CM r- 1 — — cm in o ' o co co o ° ^ ^ K o o

in co" °> CM

C M ' U O O O O O ' CO CM ' ' T3 ^ CM If) O ' CO O c N 2, m" 05

CM

N ' t O O O — ' O lO ' ' "O 1 CM fl O • CO O co ^ in o cm" 05

c o ' o o o o cm ' o in 1 1 -g ^ CM fl O ^ CO O ^ s, CM

c o ' o j o o o i- ' g fl 1 ' -g @ fl CO O ' CM O

£ £ s £ § S 8 2 § § ^ 8 ^ "8 c o L " - ^ , _ LO CO o co 05 o @9 c o ' o o f l o o 1 g a- @ 1 -o u S f l ^ C M l O L O C M ^ CM g r— ^ C fl m t- o ri _r OJ

c o ' o o n o fl ' g co 1 • "55 • fl LO CO O ,* CM CO ri O ri ri m" CM

r-- O 03 O CM O CM O O L 0 O C M T 3 • in co m o o cm co co g CM CM m O ,_ O ri ri cm" lo" 05 CM

c o ' o o o o m 1 o f l ' ' " o ^ fl LO CO O d CM O

to" . °> CM

§ CD CD vO 2 1 - 1 - ct = 3 ^ fi O CD O 2 t = 2 t £ »- > ri cd i- cd ct

d 5 o 0 8 | 2 | 5 £ § ' | 0 ! I I I Z CO CO .3 <D >C ^ . C r i C C 1 1 m To •= — ® u » ° ° ca®

UJ < < co c .c o c o c .5 c o < w < ir >, CD 1 1 1 1 1 1 1 ' 5 — CO CO Q. § I I I I

£ I ^ 1 1 O 0_ O LL.

47

o cm -a rr\\ ft ° ^ ^ N. O O m" co" =» CM

C M ' L O O O O O ' O N ' 1 -d ^ cm in o ' co o

1* 03 N s, CM

C M ' f l O O O ri • O LO ' ' "O ^ CM fl o • CO g CO ri LO o

20 C O ' O O O O CM ' 0 IX) ' ' "g ^ cm fl o ^ co g

CM

c o ' O j o o o ri ' g fl 1 ' -g @ fl co o @ cm g 25 CO S cl 85

^ ? 5 | § § s 8 2 § § ^ 8 ^ 1 C O " 5 - ^ ' ' - LO CO 0

30 •£ @9 c o ' o o f l 0 0 ' g @ 1 -a u S - t - ' C M L O L O C M ^ cm g r— ^ C fl LO ri 0 ri OJ

c o ' o o n 0 fl ' g co 1 • 15 • f l L O C O O ^ * : CM CO ^ 0 ri 35 »

r - - 0 0 5 0 C M O CM O O L 0 O C M T 3 • - i i n c o m 0 0 cm co co g CM CM m O - 0 ri ri cm" lo" 05 CM

40 C 0 ' O O O O i n ' O f l , , T 3 ^ ^ f l L O C O O d CM O

10' a CM

ct = ^ 3 ^ fi 0 cd 0 2 - r 2 - r S »- > *- CO it. CD C±> I S 0 I 0 3 " ^ p 5 1= 2

d 5 0 , 8 | n § | | 0 I I I I Z c 8 C 0 ^ < D > C ^ C r i C 1 _ C 1 1

S £ £ g O O Q . y Q . ^ g ^ Q . = = c B m o - l c - o £ - 5 £ £ o - o £ c q ca U J < < co c £ o c o c.5 c o < w < ii >, CD 1 1 1 1 i 1 1 1 5 ~ ( 0 CO Q. t I .1 1 1

£ 1 ^ 1 1 O 0_ lT 0 ll.

47

EP 0 358 358 A2

Table 9(a)- 1

Comparative Application Example

1 2 3 4 5 6 7 8


Acrylic resin No. AC-3 AC-8 AC-3 - AC-3 AC-8 AC-8 AC-8

Polyester resin N o . . . . pe-i . . . .

Formulation pigment dispersing agent 15 5.8 15 5.8 18.8 22.5 22.5

of acrylic resin 29.2 49.1 29.2 - 29.2 24.7 24.7 62.7

dispersion polyester resin - - - 49.1 . . . .

paste xylene 20.8 22.3 20.8 22.3 17.0 20.0 20.0 9.2

ethyl cellosolve . - - - - - - - 9.3

cellosolve acetate 20.0 4.0 20.0 4.0 20.0 17.8 7.8

titanium dioxide JR 602 . . . . . . . .

carbon black FW-200 . . . . . . . .

Fosterperm Yellow-H3G . . . . . . . .

Fastogen Blue-RGA . . . . . . . .

Paliogen Maroon L3820 15.0 15.0 15.0

Rubicron Red 500RG . . . . . . . .

Paliotol Red L3670 - - 18.8 - - - 18.8

Noboperm Red F3RK-70 - 18.8 - - - 15.0 15.0

Paliogen Violet L-5080 . . . . . . . . 35

40

45

50

55

48

P 0 358 358 A2

able V(a)-z

3 Comparative Application Example

1 2 3 4 5 6 7 8

Properties amount of 50 20 50 20 50 60 60 0

pigment 0 dispersing agent added

of viscosity 12,400 8,750 9,700 10,300 14,300 2,200 4,600 gel s of

dispersion paste (CP)

paste storage poor poor poor poor poor good good poor 0 stability of

dispersion paste

Formulation dispersion 52.0 44.2 52.0 44.2 52.0 52.0 52.0 44.2

>5 paste

of acrylic 23.8 24.2 23.8 - 23.8 23.8 23.8 29.0 resin

paint polyester - - - 24.2 - . . . jo resin

melamine 19.5 20.8 19.5 20.8 19.5 19.5 19.5 20.8 resin

leveling 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6

35 agent

thinner 4.1 10.2 4.1 10.2 4.1 4.1 4.1 5.4

Properties 30° 32 64 30 51 21 82 80 56 specular

40 gloss

of humidity good good good good good occurrence occurance good resistance of blister of blister

paint weather 80 85 78 81 80 58 58 85

45 resistance

film absence absence absence absence absence absence presence presence absence or presence of

50 bleeding

49

EP 0 358 358 A2

Table 9(b)-1

Comparative Application Example

9 10 11 12 13 14 15 16


Acrylic resin No. AC-8 AC-9 AC-9 AC-9 AC-8

Polyester resin N o . . . . . . pf£.2 pe-1 PE-2

Formulation pigment dispersing agent 12.0 21.0 11.6 5.8 7.5 6.0 9.0

of acrylic resin 31.7 24.2 43.3 49.1 34.2

dispersion polyester resin . . . . . 35 7 34 2 41 .7

paste xylene 21.3 19.8 22.3 22.3 23.3 22.3 21.8 23.3

ethyl cellosolve . . . . . . . .

cellosolve acetate 20.0 20.0 4.0 4.0 20.0 20.0 20.0 20.0

titanium dioxide JR 602 . . . . . . . .

carbon black FW-200 . . . . . . . .

Fosterperm Yellow-H3G - - - - 15.0

Fastogen Blue-RGA . . . . . . . .

Paliogen Maroon L3820 - 15.0

Rubicron Red 500RG 15.0

Paliotol Red L3670 . . . . . . . .

Noboperm Red F3RK-70 - - 18.8 - 15.0 - 15.0

Paliogen Violet L-5080 - - - 18.8 - - 15.0 35

40

45

50

50

h L -a L s

so " cd i-i a W m e w S rtj _ cu «

^ 2 cn J o ri « «n 0 „ * g - - O ri Q, -h cn

0 2 ° ri O @ . fN CN CO ,_ CN _T C

20 ri _ CO U CN CN CO _ ^ ^ ^ | a °

J s : ; ' s = s " i ° : "ri, ft

> cu u -H U 0) 0) 4J c J u CO irt CN CN 00 .rt CN 1)10 C 25 U . _ O q • • . • • CO Li *H ID <D

10 d 2 0(1 o «r 1 o ' o r - u r i o w CN « o i f l C N CN ° ri 3 J3 ffl 1 K CJ 1 o u uj a

CT> O CJJ 0) 30 <U 0 o

° "S ^ ^ , * ». * « 2 3 co I

o _r cn lo cn r i ° ^ 3 Jj « ri o n ro o tw a Eh o o CD U U 0) CD

J0 ° T o a c o L n . _ , cu in c cn ° o o C N c o ' c n o ' c o v t r i t o m * Ol LO CN H ° 3 J2 J> ri u l-l

U U ft o o

40 C ^ @a o o @a in tw „, @a i4 o cu a)

jj £, >, 0 J G O C iii jj ii ii o c a c a j

fl) -H -rt 4J JJ C r H J J C C j W EtU'C ri in in -rt C JJ cn in JJ CD

4c Cn cn -rt co cd a to -rt c -h v> u D , o cd in w a cn cd cd w

cn — . j j c s c t i ) u t o ri u tu w tw a >iPj w o o n w 3 u ° * o - r t J J t j -rt-H c u a j c n u > i cn

U l - H w d J W W U J J C i C H C U JJ U O J C JJ U W 0"l Wt W4 -H tfl -rt -H 0) 0* "rt CD U -H CCD OflJ CdCD 11 H «) g H fi u T3 J3 CTJ 3 0 i U J J n D i a > i > i f a a ) c ! -h t J m 9 !

50 O M M W O M W V 4 r i r i > - r t o g f d W ft w t3 TO cd a, g ,h jj cn xt 3 co jo

c w o w CD 'H CD •H0> *> J-1 ri JJ jj jj to a c lj tn ri -rt Vt -rt 55 cu rd 3(0 2 5 ^ . Q.0, Eft f t f t E O H O ri

O t*-4 W «" ri 1 pj O o Pj o1"

51

EP 0 358 358 A2

Claims 5

1. A pigment dispersing agent consisting of a product obtained by reacting the following component Ai with the following component B at a mol ratio of component Ai to component B of 1:1 - 1:40.

Component A,: an amine compound containing one or more amino group and/or imino group in its molecule and having a weight average molecular weight of 60-30,000 and an amine value of 50-2,000 mg

m KOH/g; Component B: an acrylic copolymer having a weight average molecular weight of 2,000 - 100,000

and a hydroxyl value of 5 - 200 and containing one of glycidyl group (component Bi ), acetoacetoxy group (component B2) and cyclocarbonate group (component B3) in a functional group number of 0.7 - 3.0 on average per molecule as a side chain, provided that 1 mol of glycidyl group is considered to be 1 mol of

15 hydroxyl group in the calculation of hydroxyl value. 2. A pigment dispersing agent consisting of a product obtained by reacting the following component A2

and component B with one of the following six components C at a mol ratio of component A2 to component B to component C of 1 :1 :1 - 1 :40:40.

Component A2: an amine compound containing one or more amino group or two or more imino group 20 or one or more amino and imino groups in its molecule and having a weight average molecular weight of

60-30,000 and an amine value of 50-2,000 mg KOH/g; Component B: an acrylic copolymer having a weight average molecular weight of 2,000-100,000 and

a hydroxyl value of 5-200 and containing one of glycidyl group (component B1), acetoacetoxy group (component B2) and cyclocarbonate group (component B3) in a functional group number of 0.7-3.0 on

25 average per molecule as a side chain, provided that 1 mole of glycidyl group is considered to be 1 mol of hydroxyl group in the calculation of hydroxyl value;

Component C: a polyester resin of the following structures having a weight average molecular weight of .1 ,000-30,000 and containing isocyanate group or acetoacetoxy group in its terminal Ri -0-(CO-R2-0)n-CO-NH-R3-NCO (Ci )

30 Ri-0-(CO-R2-0)n-CO-CH2-CO-CH3 (C2) Ri-0-(CO-R4-COO-CHR5-CHRs-0)n-CO-NH-R3-NCO (C3) Ri-0-(CO-R+-COOH-CHR5-CHRs-0)n-CO-CH2-CO-CH3 (Ct) Ri-CO-(0-CHR5-CHRs-0-COR4.-CO)n-0-CHR5-CHRs-OCO-NH-R3-NCO (C5) Ri-CO-(0-CHR5-CHRs-0-COR4-CO)n-0-CHR5-CHRs-OCO-CH2COCH3 (C6)

35 Ri: aliphatic, alicyclic or aromatic hydrocarbon group having a carbon number of 1-18, R2: aikylene group having a carbon number of 1-7, R3: residual group of aliphatic, alicyclic or aromatic diisocyanate having a carbon number of 6-20, R*: Residual group of aliphatic, alicyclic or aromatic acid anhydride having a carbon number of 2-20, Rs, Rs: hydrogen atom, aliphatic, alicyclic or aromatic hydrocarbon group having a carbon number of 1-20,

40 -CH2-O-R1 group or -CH2-OCO-R1 group n : an integer of 1 or more.

52

Pigment dispersing agent - EP 0358358 A2

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