JP2002526614A - Graft copolymers containing urea or imide functions as pigment dispersants - Google Patents

Abstract

  (57) [Summary] A polymer dispersant for pigments based on an acrylic graft copolymer, wherein the graft copolymer has a weight average molecular weight of at least 1500 and 2 to 97% by weight of a polymer backbone and 97 to 2% by weight attached to the backbone. % Of the macromonomer side chains and the graft copolymer has at least about 1% by weight of imide or urea functional dispersing substituents attached to the backbone, macromonomer, or both backbone and macromonomer. .

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION The present invention relates to pigment dispersions comprising graft copolymers having urea functionality, imide functionality, or both.

[0002] Coating compositions typically include a carrier liquid, a film-forming polymer, a curing (crosslinking) agent, and various additives such as pigments, extenders, UV stabilizers, dispersants, and the like. . Pigments are insoluble particles that are dispersed in a carrier liquid to provide color, hiding power, hardness, durability, and corrosion resistance. Typically,
Pigments are finely ground natural or synthetic, inorganic or organic particles, often in the form of a fine powder. Extender pigments are inexpensive fillers, lowering costs, achieving durability, modifying appearance, controlling rheology, and affecting other desired properties. In this specification, the terms pigment and pigment dispersant should be interpreted to include extenders as well.

[0003] Covering the pigment particle surface with a carrier liquid is referred to as wetting or dispersing the pigment, and the resulting mixture is referred to as a pigment dispersion. If the pigment dispersion is not appropriate,
There will be clusters of dry pigment particles bound by surface forces, a condition known as agglomeration. This dry pigment particle cluster applies mechanical force,
Alternatively, pulverization can be carried out by adding a pigment dispersant acting on the interface between the carrier liquid and the pigment particles. Pigment dispersants, also known as dispersants, improve the suspension stability of the pigment in a liquid medium. Also, the pigment dispersant acts on the interface between the carrier liquid and the pigment particles, thereby reducing the flocculation that forms pigment particle clusters after wetting the particles.

[0004] It is an object of the present invention to provide a novel pigment dispersant comprising a graft copolymer having a macromonomer grafted to the polymer backbone. The graft copolymer contains urea functionality, imide functionality, or both, located on the backbone, macromonomer, or both. Preferred macromonomers are those polymerized from acrylic monomers. It is a further object of the present invention to provide a method for making a graft copolymer comprising polymerizing a monomer mixture in the presence of a macromonomer formed with a Co ²⁺ and / or Co ³⁺ chelating chain transfer agent. It has been found that such graft copolymers are useful in the production of stable non-agglomerated pigment dispersions and provide excellent pigment wetting action.

SUMMARY OF THE INVENTION [0005] The pigment dispersants of the present invention include a graft copolymer having urea functionality, imide functionality, or both. The graft copolymer is formed by grafting a macromonomer onto a polymer backbone having an ethylenically unsaturated monomer. The macromonomer has one terminal ethylenically unsaturated group that reacts with the backbone monomer to attach the macromonomer to the backbone. The macromonomer may contain a urea function, an imide function, or both.

[0006] The polymer backbone comprises about 2 to 97% by weight of the graft copolymer and the macromonomer contains about 97 to 2% by weight of the graft copolymer. Further, the graft copolymer comprises at least about 1% by weight of dispersing substituents selected from the group consisting of imide-functional compounds, urea-functional compounds, or both. The dispersing substituent is also known as a fixing group for fixing the polymer to the pigment surface, and the dispersing substituent is formed by copolymerizing with the main chain, the macromonomer, or both. Attached to the graft copolymer. Also, the dispersible substituent can bind to the graft copolymer by reacting with the functional groups of the backbone, macromonomer, or both. In short, the dispersing substituent is an imide-functional compound, a urea-functional compound, or both, and may be located on the backbone, macromonomer, or both.

The urea-functional compound has the formula

[0008]

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Is represented by

Wherein each R is hydrogen, substituted or unsubstituted saturated and unsaturated aliphatic and alicyclic, substituted and unsubstituted aromatic and heterocyclic, and -NH-
Independently selected from the group consisting of divalent radicals containing oxygen and sulfur, and wherein at least one R group is an unsaturated polymerizable monomer that reacts with monomers contained in the backbone, macromonomer, or both. Containing at least one R
The groups include functional groups that react with reactive functional species of the backbone, macromonomer, or both.

The imide-functional compound has the formula

[0012]

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Is represented by

Wherein each R ′ is hydrogen, substituted or unsubstituted saturated and unsaturated aliphatic and cycloaliphatic compounds, substituted and unsubstituted aromatic and heterocyclic compounds, and —NH
-Independently selected from the group consisting of divalent radicals containing oxygen and sulfur, and wherein at least one R 'group is an unsaturated monomer which reacts with monomers contained in said main chain, macromonomer, or both. The polymerizable group, or at least one R 'group, includes a functional group that reacts with a reactive functional species of the backbone, macromonomer, or both.

The pigment dispersant of the present invention is formed by grafting a macromonomer to a polymer main chain. The macromonomer is polymerized in the presence of the cobalt chain transfer agent to form a macromonomer having one terminal ethylenically unsaturated group. The macromonomer is then reacted with an ethylenically unsaturated main chain monomer and polymerized to form a main chain with grafted macromonomer side chains. A dispersing substituent can be added during the polymerization of the macromonomer, the copolymerization of the macromonomer and the main chain monomer, or both.

[0016] The pigment dispersion is readily formed by combining the pigment dispersant of the present invention with a number of commercially available pigments and a suitable liquid vehicle.

DETAILED DESCRIPTION OF THE INVENTION The pigment dispersant of the present invention comprises a graft copolymer formed by copolymerizing an ethylenically unsaturated main chain monomer in the presence of a macromonomer. Macromonomers polymerized from acrylic monomers, especially methacrylate monomers, are preferred. The macromonomer has a weight average molecular weight of about 300 to 30,000, preferably about 1,000 to 10,000, and has a hydroxyl value of about 20 to 180.

To ensure that the resulting macromonomer has only one terminal ethylenically unsaturated group, which polymerizes with the backbone monomer to form a graft copolymer,
The polymerization of the macromonomer is carried out in the presence of a cobalt chain transfer agent containing Co ²⁺ groups, Co ³⁺ groups or both. Usually, formation of the macromonomer is performed by polymerizing a methacrylate-based monomer mixture in the presence of a cobalt chain transfer agent. The polymerization of the macromonomer is carried out in an organic solvent or solvent mixture using a conventional polymerization catalyst. Preferred cobalt chain transfer agents or catalysts are Janowi
cz in U.S. Patent Nos. 4,680,352 and 4,722,984. The most preferred cobalt chain transfer agent is pentacyanocobalt (II)
Acid salt, diaquabis (borondifluorodimethylglyoximato) cobalt (I
I) and diaquabis (borondifluorophenylglyoximato) cobaltate (II). Usually, these chain transfer agents are used at a concentration of about 2 to 5000 ppm based on the particular monomer being polymerized.

[0019] Typical polymerization catalysts are peroxy and azo derivatives. Azo type such as 2,2-azobis (2-methylbutanenitrile), 2,2-azobis (2,4-dimethylpentanenitrile), 2,2-azobis (2,4-dimethyl-4-methoxyvaleronitrile) Polymerization catalysts are most preferred. Examples of peroxy-based catalysts include di-t-butyl peroxide, di-cumyl peroxide, t-amyl peroxide, cumene hydroperoxide, di (n-propyl) peroxydicarbonate,
and t-amyl peracetate.

Representative solvents that can be used to form the macromonomer include ketones such as methyl ethyl ketone, isobutyl ketone, ethyl amyl ketone and acetone, alcohols such as methanol, ethanol, isopropanol and butanol, ethyl acetate and butyl acetate. Esters, such as ethylene glycol and propylene glycol, ethers such as tetrahydrofuran, ethylene glycol monobutyl ether and propylene glycol methyl ether, and mixed ether acetates such as propylene glycol methyl ether acetate and diethylene glycol monobutyl ether acetate.

The macromonomer contains a single terminal ethylenically unsaturated group and mainly comprises polymerized monomers of methacrylic acid, its esters, amides, nitriles, or monomer mixtures thereof. Preferred monomers include alkyl methacrylates, cycloaliphatic methacrylates, aryl methacrylates, and hydroxy-functional methacrylates.

Representative alkyl methacrylates that can be used are those having from 1 to 18 carbon atoms as the alkyl group and include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, -Ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate and the like.

Cycloaliphatic methacrylates that can be used include trimethylcyclohexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, t-butylcyclohexyl methacrylate, and the like.

Aryl methacrylates that can be used include phenyl methacrylate, benzyl methacrylate and the like. Hydroxy-functional methacrylates that can be used include:
Examples include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

Examples of amide and nitrile monomers include methacrylamide, methacrylonitrile, n-butoxymethyl methacrylamide, methoxymethyl methacrylamide, methoxy methacrylamide, and the like. Examples of acid-functional monomers include methacrylic acid, methacryloxyethyl phosphate, sulfoethyl methacrylate, and the like. Also, epoxy-functional monomers such as glycidyl methacrylate can be copolymerized.

Other ethylenically unsaturated derivatives such as alkyl acrylates, alicyclic acrylates, hydroxy acrylates, aryl acrylates and vinyl aromatic compounds can be used to form the macromonomer. Preferred alkyl acrylates are those having from 1 to 18 carbon atoms as the alkyl group and include methyl acrylate, ethyl acrylate, n-butyl acrylate, i
-Butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and the like.

Cycloaliphatic acrylates that can be used include t-butylcyclohexyl acrylate, cyclohexyl acrylate, and the like. Hydroxyl acrylates that can be used include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and the like. Aryl acrylates such as benzyl acrylate and vinyl aromatic compounds such as styrene, t-butyl styrene and vinyl toluene can also be copolymerized.

Other ethylenically unsaturated derivatives that can be used to form the macromonomer include sulfonic, sulfinic, phosphonic and ester derivatives, isocyanates, anhydrides, nitriles, amides, amines, and silanes. is there. Examples include, but are not limited to, maleic anhydride, itaconic anhydride, isocyanate ethyl methacrylate, acrylonitrile, acrylamide, dimethylaminoethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid, trimethoxysilylpropyl methacrylate, and the like. is not.

The macromonomer can be chemically modified via a reaction of its functional group. The acid or amine functional macromonomer can be modified with an epoxy functional derivative. The hydroxy-functional macromonomer can be further reacted with an isocyanate-functional derivative. E-caprolactone is present in the graft copolymers OH and N
Reacts with H-functional species.

The functional groups that can be incorporated into the graft copolymer structure include acids such as hydroxyl group, carboxylic acid, sulfonic acid, and phosphoric acid, amide, alkoxymethylamide, isocyanate, silane, alkoxysilane, amine, epoxy, and acetoacetoxy. and so on. This functional group can be located on the backbone, macromonomer, or both, by copolymerization of a suitable functional ethylenically unsaturated monomer.

The backbone contains polymerized monomers, and any of the monomers described above for the macromonomer may be used in the backbone. This main chain monomer is copolymerized with the macromonomer using the above-mentioned conventional azo or peroxide type catalyst and an organic solvent. The graft copolymer thus formed has at least 150
It has a weight average molecular weight of 0 and has a urea or imide functional group on the backbone, macromonomer or both.

A dispersing substituent having a urea functional species, an imide functional species, or both urea and imide functional groups, is added to the graft copolymer to provide a functional group of the backbone, macromonomer, or both, and urea and imide. And / or an imide-functional derivative. The urea and / or imide functional species can also cause the ethylenically unsaturated imide and / or
Alternatively, it is obtained by adding a urea-functional monomer. The graft copolymer has a hydroxyl value of about 20-180. Table I summarizes the various functional group combinations and positions for the graft copolymer.

[0033]

[Table 1]

[0034] Cases 4 and 5 are preferred embodiments and are represented in Examples 7 and 13, respectively. The most preferred embodiment is Case 4. Cases 7-9 require an excess of either the urea or imide functional species, either in the backbone or macromonomer, with the location of the excess dispersing substituent being the primary anchor point for the pigment particles.

The imide-functional compound useful in the present invention has the formula

[0036]

Embedded image

Wherein the urea-functional compound is represented by the formula

[0038]

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Is represented by Wherein each R and each R ′ are hydrogen, saturated substituted aliphatic and alicyclic, saturated unsubstituted aliphatic and alicyclic, unsaturated substituted aliphatic and alicyclic, unsaturated unsubstituted aliphatic Independently selected from the group consisting of aromatic and alicyclic compounds, substituted aromatic and heterocyclic compounds, unsubstituted aromatic and heterocyclic compounds, and divalent radicals containing -NH-, oxygen and sulfur .

Examples of R and R ′ aliphatic compounds include methyl, ethyl, propyl, n-butyl and the like. Examples of R and R 'cycloaliphatic compounds include cyclohexyl, methylcyclohexyl, and the like. Examples of R and R 'aromatics include phenyl, benzyl, p-toluyl and the like. Examples of R and R 'heterocyclic compounds include morpholine, benzimidazole, triazole, imidazole, piperazine, pyridine, pyrimidine and the like. Specifically, 1- (2-aminoethyl) piperazine,
2-aminoethylmorpholine, 4- (2-aminoethyl) pyridine, or 3-
Reaction of the amino-1,2,4-triazole with the isocyanate-functional monomer produces a urea-substituted heterocyclic pigment interacting group.

Examples of ethylenically unsaturated urea monomers are described in US Pat. Nos. 5,030,726 and 5,045,616. Preferred monomers are acrylate derivatives of 2-hydroxyethylethylene urea (HEEU), methacrylate derivatives of HEEU, acrylamide derivatives of 2-aminoethylethylene urea (AEEU), and methacrylamide derivatives of AEEU.

[0042]

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[0043]

Embedded image

The most preferred monomer commercially available is methacryloxyethyl ethylene urea.

[0045]

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In a preferred embodiment, the graft copolymer comprises about 5% by weight methacryloxyethyl ethylene urea, about 5 to 50% by weight polymeric backbone monomer, and about 50 to 95% by weight macromonomer. I have.

Examples of imide-functional monomers include maleic anhydride derivatives such as phenylmaleimide, methylmaleimide, ethylmaleimide, benzylmaleimide.

Examples of imide functional species resulting from functional group chemistry include the reaction of epoxy functional macromonomers or backbones with imides such as succinimide, phthalimide. In a preferred embodiment, the graft copolymer comprises about 5% by weight of the reaction product of glycidyl methacrylate and phthalimide, about 5 to 50% by weight of the polymeric backbone monomer, and about 50 to 95% by weight of the macromonomer. Contains.

Examples of urea functional species obtained by chemical reaction of functional groups include the reaction of dimethyl m-isopropenylbenzyl isocyanate (MTMI) or isocyanatoethyl methacrylate (IEMA) with HEEU or AEEU, and urethane (H
EEU) or an unsaturated polymerizable monomer to which urea binds via a urea group.
Equation 1 shows the reaction between MTMI and AEEU, and Equation 2 shows the reaction between IEMA and HEEU. The reaction between MTMI and HEEU and the reaction between IEMA and AEEU are not particularly exemplified, but are within the scope of the present invention.

[0050]

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[0051]

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[0052] The graft copolymer should preferably contain at least 1% by weight, calculated from the total composition of the graft copolymer, of urea functions, imide functions, or both. Calculations can be made from the chemical composition of the urea and / or imide functional groups present in the binder.

% By weight is present in the binder

[0054]

Embedded image

Expressed as a percentage of

Such a graft copolymer can be used to form a pigment dispersion or a millbase. The pigment is added to the graft copolymer in a solvent or mixture and dispersed using conventional techniques such as high speed mixing, ball milling, sand grinding, attritor guiding, or two or three milling. The weight ratio of the pigment to the dispersant binder in the obtained pigment dispersion is about 0.1 / 100.
From 2000/100.

The pigment dispersion can be formed using any of the conventional pigments used in paints. Examples of suitable pigments include titanium dioxide, metal oxides such as iron oxides and zinc oxides of various colors, filled pigments such as carbon black, talc, clay, barite, carbonates and silicates, quinacridone, phthalocyanine , Perylene, azo pigments, indanthrone, carbazole such as carbazole violet, isoindolinone,
There is a wide range of organic pigments, such as isoindrone, thioindigo red and benzimidazolinone, and metal flakes, such as aluminum flakes, pearl flakes and the like.

It is desirable to add other optional ingredients to the pigment dispersion, such as antioxidants, flow modifiers, UV stabilizers, light quenchers and absorbers, rheology control agents such as fumed silica and microgels. There will be. Further, other film-forming polymers such as acrylic, acrylourethane, polyester urethane, polyester, alkyd, polyether and the like can be added.

The pigment dispersions of the present invention can be added to various coating compositions such as primers, primer surfacers, topcoats that are also monocoats, or basecoats of clearcoat / basecoat finishes. These compositions may include blocked isocyanates, crosslinked agents such as alkylated melamines, polyisocyanates, epoxy resins, and the like. Preferably, the glassy copolymer contains a functional group that becomes part of the final network structure by reacting with the crosslinking agent.

The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise noted. Molecular weights were determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as carrier solvent. All viscosity measurements were reported using the Gardner Holdt scale. MN represents the number average molecular weight, and MW represents the weight average molecular weight. The acid value was measured by a titration method using an alcoholic KOH solution and phenolphthalein as an indicator. The solid content was measured after holding at 105 ° C. for 1 hour.

Examples Example 1: Macromonomer This example illustrates the preparation of a macromonomer according to the present invention. The reactor is equipped with a stirrer, thermocouple and condenser. The reactor was maintained at a positive pressure under nitrogen and the following components were employed. Part 1 parts by weight butyl acetate 19 2-ethylhexyl methacrylate 30 2-hydroxyethyl methacrylate 7 part 2 ® 88 initiator ^* 0.03 part 3 butyl acetate 0.25 part 4 2-ethylhexyl methacrylate 22 2-hydroethyl methacrylate 6 VAZO ® 88 initiator 0.10 butyl acetate 5.9 part 5 butyl acetate 0.5 Part 6 VAZO® 88 initiator 0.03 Butyl acetate 1.97 Part 7 Butyl acetate 0.25 Part 8 t-Butylperoxy 2-ethylhexanoate 0.02 Butyl acetate 1.98 Over preparative 9 butyl acetate 1 Total 100 ^* VAZO (TM) 88 is a 1,1-azobis (cyclohexane carbonitrile) free-radical polymerization initiator, E. I. DuPont de Ne
available from Mours and Company, Wilmington, DE.

Part 1 was charged to the reactor and heated at a reflux temperature of about 150 ° C. Part 2 was added to the reactor in a one-shot feed, followed by Part 3 as a rinse step. Subsequently, Part 4 was fed to the reactor over 4 hours. The reactor contents were rinsed with part 5 and then held at reflux for 30 minutes. Part 6 was fed to the reactor over 1 hour. The reactor contents were rinsed with part 7 and subsequently held at reflux for 1 hour. Following Part 8, Part 9 was added to the reaction vessel and the contents were cooled to room temperature.

Test Results Solid Content 62.5% Viscosity T Acid Value 0.5 MN 5400 MW 10000

Example 2: Macromonomer The following changes were made and the recipe of Example 1 was repeated. Part 1 30% by weight of 2-ethylhexyl methacrylate, 11.25% by weight of 2-ethylhexyl methacrylate and 18.75% by weight of isobornyl methacrylate
Replaced with Part 4 22% by weight of 2-ethylhexyl methacrylate was replaced by 8.25% by weight of 2-ethylhexyl methacrylate and 13.75% by weight of isobornyl methacrylate.

Test Results Solid Content 63.5% Viscosity Z2 Acid Value 1.8 MN 5000 MW 9000

Example 3 Macromonomer Replace 2-ethylhexyl methacrylate with methyl methacrylate,
The formulation of Example 1 was repeated, substituting 2-hydroxypropyl methacrylate for hydroxyethyl methacrylate.

Test Results Solid Content 61.9% Viscosity Z + ／ Acid Value 0.3 MN 1100 MW 2200

Example 4 Macromonomer The recipe of Example 1 was repeated with the following changes. Part 1 parts by weight butyl acetate 19 2-ethylhexyl methacrylate 8.125 2-hydroxyethyl methacrylate 8.125 isobornyl methacrylate 16.25 part 2 catalyst 0.0052 methyl ethyl ketone 1.9958 butyl acetate 1.97 VAZO® 88 Initiator 0.03 Part 4 2-Ethylhexyl methacrylate 8.125 2-Hydroxyethyl methacrylate 8.125 VAZO® 88 Initiator 0.10 Butyl acetate 5.9 Isobornyl methacrylate 16.25 All other parts This is the same as in the first embodiment.

Test Results Solid Content 62.2% Viscosity U + ／ Acid Value 2.1 MN 2300 MW 4000

Comparative Example 5: Macromonomer This example illustrates the synthesis of a polyester-based macromonomer by ring opening polycondensation. Part 1 parts by weight 2-hydroxyethyl methacrylate 130 butyl acetate 370.35 methoxyhydroquinone 0.65 part 2 methylhexahydrophthalic anhydride 672 part 3 butyl acetate 30 part 4 Cardura E10 ^* 1130 part 5 butyl acetate 50 part 6 dimethylbenzylamine 1 .8 Butyl Acetate 8.2 Part 7 Butyl Acetate 7 Total 2400 ^* Cardura E10 is a trademark of versatic acid glycidyl ester, available from Shell Chemical Company.

Part 1 was heated to reflux at about 130 ° C. Part 3 was added following Part 2 and the reactor contents were held at reflux for 10 minutes. Add Part 5 after Part 4 and acid value is 5
The reactor contents were held at reflux until they fell below. Part 7 was added.

Test Results Solids 79.9% Viscosity K Acid Value 0.3 MN 1370 MW 1780

Comparative Example 6: Macromonomer part 1 was replaced by 185 parts of t-butylaminoethyl methacrylate, 400.07
The procedure of Comparative Example 5 was repeated, substituting 5 parts of butyl acetate and 0.925 parts of methoxyhydroquinone.

Test Results Solids 76.4% Viscosity K Acid Value 3.4 MN 1420 MW 2130

Example 7: Graft copolymer with urea functionality The following components were charged to a 2 liter flask equipped with the equipment of Example 1 to form a graft copolymer solution. Part 1 Parts by weight Macromonomer Example 1 100 Part 2 Styrene 19.5 butyl acrylate 6.5 2-hydroxyethyl methacrylate 13 Plex6844-0 ^* 26 Trigonox42S ^** 1.3 butyl acetate 8.7 part 3 butyl acetate 2 part 4 Trigonox 42S 0.15 butyl acetate 4.85 part 5 butyl acetate 1 part 6 butyl acetate 17 total 200 ^* 25% ethylene urea ethyl methacrylate solution in methyl methacrylate, available from Huls Chemical Company, Germany. ^** t-butylperoxy 3,3,5-isononanoate, AKZO Corp., Netherlands. Available from

Part 1 was refluxed (± 135 ° C.) and part 2 was fed over 3 hours, followed by performing part 3 as a rinsing step. Hold at reflux for 20 minutes and apply Part 4 for 30 minutes.
Added over minutes and performed Part 5 as a rinse step. Further, the contents of the flask were kept at reflux for 1 hour and Part 6 was added.

Test Results Solid Content 65.8% Viscosity Z6 or More Acid Value 1.4 MN 6820 MW 20800

Example 8: Graft copolymer with urea functionality The formulation of Example 7 was repeated. Part 1 Parts by weight Macromonomer Example 1 70 Part 2 Styrene 11.7 2-Hydroxyethyl methacrylate 3.25 Nouricl MA123M50 ^* 16.25 Trigonox 42S ^** 0.8 Butyl acetate 3.7 Part 3 Butyl acetate 1 Part 4 Trigonox 42S 0.0. 1 butyl acetate 1.9 part 5 butyl acetate 1 part 6 butyl acetate 2 total 100 ^* 50% ethylene urea ethyl methacrylate solution in methyl methacrylate, AKZO Corp., Netherlands. Available from ^** t-butylperoxy-2-ethylhexanoate, Netherlands,
AKZO Corp. Available from

Test Results Solid Content 66.6% Viscosity Z5 + ／ Acid Value 1.8 MN 2400 MW 5300

Comparative Example 9: Linear copolymer having the same composition as in Example 7 The formulation of Example 7 was repeated. Part 1 parts by weight butyl acetate 35 part 2 styrene 19.5 butyl acrylate 6.5 2-hydroxyethyl methacrylate 26 Plex 6844-0 26 2-ethylhexyl methacrylate 52 Trigonox 42S 2.6 butyl acetate 7.4 part 3 butyl acetate 2 part 4 Trigonox 42S 0.15 butyl acetate 4.85 part 5 butyl acetate 1 part 6 butyl acetate 33 total 216

Test Results Solids 59.4% Viscosity Z4 Acid Value 1.4 MN 9000 MW 34500

Comparative Example 10: Graft copolymer with acid functionality Plex 6844-0 is a 25% solution of acrylic acid in methyl methacrylate 26
And the formulation of Example 7 was repeated.

Test Results Solid Content 64.8% Viscosity Z6 or More Acid Value 39 MN 6500 MW 19300

Comparative Example 11: Graft Copolymer with Amine Functionality The procedure of Example 7 was repeated, except that Plex 6844-0 was replaced with 26 parts of a 25% solution of diethylaminoethyl methacrylate in methyl methacrylate. Tr
igonox42S was replaced with VAZO® 88 initiator.

Test Results Solid Content 64.8% Viscosity Z + ／ Acid Value 0.6 MN 4800 MW 9600

Comparative Example 12: Graft copolymer based on the polyester macromonomer of Example 5 Part 1 parts by weight Solvesso 100 ^* 20 Part 2 Polyester macromonomer Example 5 36 2-Hydroxypropyl methacrylate 8.4 Plex 6844-00 24 Acrylic acid 6 Trigonox B ^** 0.6 Solvesso 100 3/4 Part 3 Solvesso 100 1 Part 4 Butyl acetate 6 Total 100 ^* Aromatic solvent mixture available from Exxon Chemical, USA. ^** Di-t-butyl peroxide, AKZO Corp., Netherlands. Available from

Part 1 was heated to reflux (± 168 ° C.) and Part 2 was added over 3 hours, followed by Part 3 as a rinse step. The reactor contents were refluxed for 2 hours and Part 4 was added.

Test Results Solid Content 59.2% Viscosity Z4 Acid Value 5.8 MN 3000 MW 10000

Example 13 Graft Copolymer Having Imide Functionality The formulation of Example 1 was followed up to the addition of Part 6. Part 1 Parts by weight Macromonomer Example 1 100 Part 2 Styrene 26 Methyl methacrylate 15.6 2-Hydroxyethyl methacrylate 13 Glycidyl methacrylate 5.2 Trigonox 42S 1.3 Butyl acetate 8.7 Part 3 Butyl acetate 2 Part 4 Trigonox 42S 0.15 After butyl acetate 4.85 part 5 butyl acetate 1 part 6 butyl acetate 8.3 part 6, the following components were added to the reactor.

Phthalimide 5.2 Butyl acetate 1 40% Benzyltrimethylammonium hydroxide in methanol 1.04 Butyl acetate 6.66 Total 200 Hold reactor contents at 100 ° C. until acid number drops to 2 or less did.

Test Results Solid Content 65.6% Viscosity Z3 + 1/2 Acid Value 1.5 MN 5800 MW 13400

Comparative Example 14: The formulation of Comparative Example 9 was followed up to the addition of the linear copolymer having the overall composition of Example 13 Part 4. Part 1 Parts by weight Solvesso 100 12 Part 2 Styrene 12 2-Hydroxyethyl methacrylate 12 2-Ethylhexyl methacrylate 22.8 Glycidyl methacrylate 6.6 Part 3 Solvesso 100 1 Part 4 Butyl acetate 15.3 After the addition of Part 4, the contents of the reactor The product was heated to 100 ° C., and the following components were sequentially added.

Phthalimide 6.6 butyl acetate 1 40% benzyltrimethylammonium hydroxide in methanol 1.32 butyl acetate 2.38 total 100 Keep the contents of the reactor at 100 ° C. until the acid number drops below 2 did.

Test Results Solid Content 59.8% Viscosity J-1 / 3 Acid Value 1 MN 1600 MW 4000

Dispersions were formed using several pigments to compare various acrylic-based graft copolymers with polyester macromonomer linear and graft copolymers. In this test, 30 g of a certain weight of polymer (see table)
Of sand, 40 g of xylene and 4.5 g of pigment. Red this mixture
30 using a Devil Tools Red Devil paint shaker.
Let go for a minute. Thereafter, the pigment dispersion was evaluated as follows. 0 No flocculation 1 Light flocculation 2 Medium flocculation 3 Heavy flocculation

The following pigments were tested: Pigment 1: Special black 4 from Degussa, Germany Pigment 2: Perrindo maroon 6436 from Bayer, Germany Pigment 3: Monastral green L from Zeneca, Netherlands
og C Pigment 4: Irgazin blue X3627 from Ciba, Switzerland

[0097]

[Table 2]

The test results show that grafted acrylic copolymers with urea and / or imide functionality are superior pigment dispersants compared to linear polymers with or without the same functionality. . This example also demonstrates that graft copolymers based on acrylic macromonomers having urea and / or imide functionality were compared to graft copolymers based on polyester macromonomers having urea and / or imide functionality. It is an excellent pigment dispersant.

Various modifications, changes, additions or substitutions of the components used in the compositions of the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the present invention. The present invention is not limited to the exemplary embodiments disclosed herein, but is limited by the appended claims.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] August 24, 2000 (2000.8.24)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image An imide-functional compound represented by the formula: ii)

Embedded image And iii) the dispersible substituent selected from the group consisting of a mixture of i) and ii); wherein each R and R ′ is hydrogen, a saturated substituted fatty Aliphatic and alicyclic compounds, saturated unsubstituted aliphatic and alicyclic compounds, unsaturated substituted aliphatic and alicyclic compounds, unsaturated unsubstituted aliphatic and alicyclic compounds, substituted aromatic and heterocyclic compounds, A solvent containing independently selected from the group consisting of unsubstituted aromatic and heterocyclic compounds, and divalent radicals containing -NH-, oxygen and sulfur, and having a weight average molecular weight of at least about 1500 Pigment dispersant for paints.

Embedded image An imide-functional compound represented by the formula: ii)

Embedded image And iii) a mixture of i) and ii), wherein each R and R 'are hydrogen, saturated substituted aliphatic and alicyclic Formula compounds, saturated unsubstituted aliphatic and alicyclic compounds, unsaturated substituted aliphatic and alicyclic compounds, unsaturated unsubstituted aliphatic and alicyclic compounds, substituted aromatic and heterocyclic compounds, unsubstituted aromatic And a pigment dispersant, independently selected from the group consisting of -NH-, oxygen and sulfur-containing divalent radicals, and the produced pigment dispersant has a weight average molecular weight of at least 1500. how to.

──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J027 AA02 AJ05 BA05 BA07 BA08 BA09 BA13 CA34 CB03 CC02 CD08 4J037 AA00 CC11 CC29 DD24 EE28 EE43 FF15

Claims (17)

[Claims] 1. A polymer backbone comprising from about 2 to 97% by weight of an ethylenically unsaturated monomer; and (b) having one terminal ethylenically unsaturated group, wherein said terminal group allows said main chain to be formed. From about 97 to 2% by weight of a macromonomer grafted onto the backbone; and (c) at least about 1 weight% attached to a position selected from the group consisting of said backbone, macromonomer, and both backbone and macromonomer. % Dispersing substituents, i) having the formula: Ii) an imide-functional compound represented by the formula: And iii) said dispersible substituent selected from the group consisting of a mixture of i) and ii), wherein each R and R 'is hydrogen, saturated Substituted aliphatic and alicyclic, saturated unsubstituted aliphatic and alicyclic, unsaturated substituted aliphatic and alicyclic, unsaturated unsubstituted aliphatic and alicyclic, substituted aromatic and heterocyclic A pigment dispersant selected independently from the group consisting of compounds, unsubstituted aromatic and heterocyclic compounds, and divalent radicals containing -NH-, oxygen and sulfur. 2. at least one R group and at least one R ′ group comprising: a) a functional group which reacts with a reactive functional group located on said main chain, macromonomer or both main chain and macromonomer; b) a reactive group selected from the group consisting of: an unsaturated polymerizable group that reacts with a monomer contained in the main chain, the macromonomer, or both the main chain and the macromonomer. The dispersant according to any one of the above. 3. The method of claim 1, wherein the urea-functional compound is an acrylamide derivative of 2-aminoethylethylene urea, a methacrylamide derivative of 2-aminoethylethylene urea, an acrylate of 2-hydroxyethyl ethylene urea, and 2-hydroxyethyl ethylene. The dispersant of claim 1, wherein the dispersant is selected from the group consisting of methacrylates of urea. 4. The urea-functional compound is selected from the group consisting of methacryloxyethyl ethylene urea, methacrylamidoethyl ethylene urea, acrylamidoethyl ethylene urea, ethylene urea ethyl methacrylate, and ethylene urea ethyl acrylate. The dispersant according to claim 3, wherein 5. The dispersant according to claim 1, wherein said imide-functional compound is selected from the group consisting of succinimide, phthalimide and maleic anhydride derivatives. 6. The dispersant according to claim 5, wherein the maleic acid derivative is selected from the group consisting of phenylmaleimide, methylmaleimide, ethylmaleimide and benzylmaleimide. 7. The macromonomer has a weight average molecular weight of about 500 to 200.
The dispersant according to claim 1, wherein the dispersant is 00. 8. The dispersant according to claim 1, wherein the macromonomer has a hydroxyl value of about 20 to 180. 9. The dispersant of claim 1, wherein the weight average molecular weight of the dispersant is at least about 1500. 10. The method according to claim 1, further comprising a functional monomer selected from the group consisting of alkoxysilane, amine, carboxylic acid, sulfonic acid, phosphoric acid, epoxy, acetoacetoxy, amide, and alkoxymethylamide. The dispersant according to any one of the above. 11. The macromonomer further comprises a polymerized methacrylate monomer, wherein the macromonomer has a weight average molecular weight of about 500 to 20,000,
The dispersant according to claim 1, wherein the hydroxyl value is from 20 to 180. 12. The polymer backbone further comprises a monomer selected from the group consisting of acrylates, methacrylates, vinyl aromatic compounds, and mixtures thereof, wherein the weight average molecular weight of the dispersant is at least 1500, The dispersant according to claim 1, wherein the dispersant has a value of 20 to 180. 13. The urea-functional compound is selected from the group consisting of methacryloxyethyl ethylene urea, methacrylamidoethyl ethylene urea, acrylamidoethyl ethylene urea, ethylene urea ethyl methacrylate, and ethylene urea ethyl acrylate, wherein the dispersant is 2. The composition according to claim 1, comprising from 5 to 50% by weight of said polymer backbone and from 50 to 95% by weight of said macromonomer.
2. The dispersant according to 1. 14. The imide-functional compound is a reaction product of glycidyl methacrylate and phthalimide, and the dispersant comprises 5 to 50% by weight of the polymer main chain and 50 to 95% by weight of the macromonomer. The dispersant according to claim 11, characterized in that: 15. A method for producing a pigment dispersant, comprising: a) polymerizing the macromonomer in the presence of a cobalt chain transfer agent such that the macromonomer contains one terminal ethylenically unsaturated group. B) grafting the macromonomer onto a polymer backbone comprising ethylenically unsaturated monomers; c) attaching dispersible substituents to the macromonomer, backbone, or both macromonomer and backbone. Thus, the step of adding said dispersible substituent in step a), b) or in both steps a) and b), wherein said dispersible substituent has the formula: i) Ii) an imide-functional compound represented by the formula: And iii) a mixture of i) and ii), wherein each R and R 'is hydrogen,
Saturated substituted aliphatic and alicyclic, saturated unsubstituted aliphatic and alicyclic, unsaturated substituted aliphatic and alicyclic, unsaturated unsubstituted aliphatic and alicyclic,
A method characterized in that it is independently selected from the group consisting of substituted aromatic and heterocyclic compounds, unsubstituted aromatic and heterocyclic compounds, and divalent radicals containing -NH-, oxygen and sulfur. 16. The method according to claim 15, wherein the polymerization reaction is performed in an organic solvent. 17. A pigment dispersion comprising a pigment and the pigment dispersant according to claim 1. Description: