CA1304852C - Dispersants resistant to color change - Google Patents
Dispersants resistant to color changeInfo
- Publication number
- CA1304852C CA1304852C CA000586053A CA586053A CA1304852C CA 1304852 C CA1304852 C CA 1304852C CA 000586053 A CA000586053 A CA 000586053A CA 586053 A CA586053 A CA 586053A CA 1304852 C CA1304852 C CA 1304852C
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- Prior art keywords
- segment
- acid
- block copolymer
- aromatic
- derived
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Acrylic AB block copolymers that are useful as pigment dispersants and which are resistant to yellowing and other color changes, characterized by aromatic substituents bonded to the A segment of the block copolymer.
Acrylic AB block copolymers that are useful as pigment dispersants and which are resistant to yellowing and other color changes, characterized by aromatic substituents bonded to the A segment of the block copolymer.
Description
~L3~852 DISPERSANTS RESISTANT TO COLOR CHANGE
~CKGROUND OF THE INVENTION
Previously, AB block copolymers have been developed which show good action as dispersants, which use aromatic carboxylic acids incorporated in the A
segment to provide binding to a pigment surface. Such copolymers are described, for example, in Hutchins et al., U.S. Patent 4,656,226, issued April 7, 1987.
Hutchins et al. note that many carboxylic acids, when incorporated onto the A segment of the block copolymer, can provide improved dispersant characteristics.
Preferred acids which can be so used include benzoic acid, 2-,3-,4-nitrobenzoic acid, 3,5-dinitrobenzoic acid, l-napthoic acid, and 3-chlorobenzoic acid.
While the Hutchins et al. compositions provide excellent dispersant characteristics, many of these compounds exhibit color changes upon extended exposure to light and aging. Because dispersants are often used in mixtures designed to produce a specific color, changes in the color over time are undesirable.
SUMMARY OF THE_INVENTION
The present inventlon is based on the discov-ery of a specific class of phenyl aromatic AB block copolymers which exhibit excellent performance as dispersants and which resist color changes due to exposure to light or aging.
Specifically, the instant invention provides a block copolymer having at least one A segment and at least one B segment, each segment having a molecular weight of at least about 500 and the backbones of which consist essentially of at least one polymerized ~3~L852 methacrylate or acrylate ester, at least about 20% of the acrylic moieties of the A segment having bonded thereto a moiety derived from an acid, amide or sulfonamide which is a substituent of a phenyl aromatic; the phenyl aromatic having another substituent which is a con~ugating group; the phenyl aromatic having no nitrogen, thiol, or OH group directly bonded to an aromatic ring, and wherein the B
segment contains less than about 20% of the acid, amide or sulfonamide moieties present in the A segment.
Preferably, the block copolymer is made by Group Transfer Polymerization techniques (GTP). A
preferred monomer for the A segment is 2,3-epoxypropyl methacrylate which is later reacted using a basic catalyst with the phenyl aromatic.
pETAILED DESCRIPTION OF_THE INVENTION
The instant invention is based on the discov-ery that, in block copolymers of the general type described in Hutchins et al., U.S. Patent 4,656,~26, the presence of certain aromatic substituents on the A
segment will provide excellent performance of the block coolymers as dispersants, and, at the same time, do no~
exhibit yellowing or other co:Lor change when exposed to light and aqing. Accordingly, the present compounds are exceptionally well suited for use as dispersants for pigments and in other applications where color change would not be desirable.
The block copolymers of the present invention have at least one A segment and at least one B segment.
While the block size is not critical to the present invention, each segment generally has a molecular weight of at least about S00. The bacXbones of the segments consist essentially of at least one polymerized methacrylate or acrylate ester. In the , ~L304852 context of the present invention, both methacrylate and acrylate units are designated as acrylic moieties. At least about 20~ of the acrylic moieties of the A
segment have bonded thereto a ~ragment derived from an acid, amide, or sulfonamide which is a substituent of a phenyl aromatic. The term fragment is used in the usual sense of meaning that portion of the moiety remaining after bonding to the A segment. Thus, for example, it will be understood that a phenyl aromatic having an acid group would bond to the A segment through that group, after which the acidic hydrogen would no longer be present.
The phenyl aromatic also has another substi-tuent which i5 a conjugating group. The term conjugating group will be understood to mean one having an atom attached to an aromatic ring and having a double or triple bond. Examples of such conjugating groups include ester, nitrile aromatic or substituted aromatic, or sulfonamide groups.
Another important characteristic of the phenyl aromatics bonded to the A segments of the present block copolymers is that they have no nitrogen, thiol, or OH group directly bonded to an aromatic ring, regardless of whether the aromatic ring is the primary component of the phenyl aromatic or a substituent.
Specific examples of such esters or amides include 4-sulfamido benzoic acid, n-phthaloyl~lycine, saccharin, and 4-biphenyl carboxylic acid.
4-sulfamido benzoic acid has the structural formula As can be seen from the formula, this compound, as required by the present invention, is a phenyl aromatic, has both a carboxylic acid group and a sulfonamide group, and has no nitrogen, thiol, or hydroxy groups directly bonded to the aromatic ring.
4-biphenyl carboxylic acid has the structural formula ~/~ C02H
This compound, as required by the present invention, is a phenyl aromatic having a carboxylic acid group. As a conjugating group, this compound has an aromatic substituent, a second aromatic ring. In addition, there are no nitrogen, sulfur, or hydroxy groups directly bonded to the aromatic ring.
Similarly, it can be seen that n-phthaloyl-glycine, o ~ ~ / CO2H
~ C H 2 and saccharin O
~S~
/
O O
satisfy the structural requirements of the present claims.
The B segment of the present copolymers contains less than about 20% of the acid, amide, or sulfonamide moieties present in the A segment, and :'' . .
~304852 preferably none of these moieties. The B segment is preferably prepared from an alkyl methacrylate or blend of alkyl methacrylates such as methyl methacrylate (MMA), MMA
and butyl methacrylate (BMA), BMA alone, or 2-ethylhexyl methacrylate (2-EHMA).
The block copolymers of the present invention can be prepared using the general techniques described in Hutchins et al., U.S. Patent 4,656,226. Using the techni~ues described therein, it has been found to be convenient to form the basic AB block copolymer, and then attach the reguired phenyl aromatic derivative by bringing the amide or ester into contact with the basic block copolymer under reaction conditions, reacting the ester or amide with the lS epoxy group in the block copolymer structure. In the alternative, monomers compatible with a block copolymerization processr such as GTP, which introduce appropriate pendant groups can be used directly. One such monomer, for example, is 2-(4-phenylbenzoyloxy) ethyl methacrylate.
The compounds of the present invention, by reason of the different polar characteristics of the A and B
segments, demonstrate outstanding performance as pigment dispersants. The presence of two conjugating groups confers excellent dispersion properties, particulary for pigments which are difficult to disperse. Moreover, these compositions are remarkably resistant to color change on aging or exposure to light. While this advantage is not fully understood, it is believed to be a result o* the polar groups having no nitrogen, thiol or hydroxy groups directly attached to an aromatic ring. It is believed that these groups allow formation of highly conjugated or quinone type structures upon exposure to light or aging.
In addition, the present compositions avoid the A
., ~ll3~3S2 .
more complex napthyl ~tructure seen in ~ome of the compound~ disclosed by Hutchins et alr In addition to th~ir complexity, these naphthyl material~ do not appear to be uniformly resistant to color changes upon S exposure to light and aging.
In the following Examples and Comparative Examples, the dispersants were evaluated according to established techniques ~or dispersing performance and yellowing. The Dispersion Rating refers to the sum of 4 ratings in MI~K, as explained in the Hutchins et al.
patent at Column 6, line 67 to Column 7, line 18.
According to that evaluation procedure, 4 represents a - perfect dispersant, while 16 indicates poor dispersant performance.
lS The increase in yellowne~s was evaluated by exposure to light and aging on a QW instrument, fo~lowed by color measurement on the LAB scale.
According to this test, the resulting number represents the change in yellow~ess of a white paint. The least change is therefore the most desirable. According to this test, for example, lor greater is unacceptable.
In the Examples and Control Examples, all monomers and solvents were purified of residual alco~
hols and water by distillation, use of 4 Angstr~m molecular ~$ev~s, or by passing throug~ a column of activity 1 alumina, as appropriate, and were stored under nitroqen.
In the followin~ Examples 1-4 and Comparative Examples B-D, the basic AB block copolymer, to which was added the various substituent group~, was prepared according to ths following procedur~.
A 5-liter fla~k was purged with nitrogen and charged with 1580 g of 60/40w/w propylene carbonate/~etrahydrofuran, 403.6 9 glycidyl meth-35 ~crylate, 41.3 g 1-methoxy-1-trimethylsiloxy-2-~L3101~L~3Si2 methylpropene (hereafter termed "initiator~), 4.2 g xylenes, and 0.4 g toluene. The glycidyl methacrylate was the primary component of the A block. After cooling to 5 C, reaction was initiated by the addition of 10.4 mL 0.34 M tetrabutylammonium-3-chlorobenzoate in tetrahydro~uran (hereafter termed ~catalyst~). The temperature rose, without cooling, to 45.8 C in 23 minutes. A feed of 1145g of 41.3/58.7 w/w methyl methacrylate/butyl methacrylate over 30 minutes was begun 28 minutes after first addition of catalyst. The methyl methacrylate/butyl methacrylate monomers were the primary components of the B block of the copolymer.
Beginning at the same time, 5.22 mL of catalyst was added over 30 minutes. At the end of the same time, 5.22 mL of catalyst was added over 30 minutes. At the end of the monomer feed, the reaction temperature was ca. 65 C. After a further 7 minutes, the temperature had risen to 85 C; an ice bath was used for 45 minutes to lower the temperature. After the ice bath was removed, 7.6 g methanol was added. Actual solids of the resin was measured as 48.77 wt %,theoretical solids was 49.15 % (obtained 99O2 % of theory). The actual epoxy content of the resin was 0.869 meq epoxy per gram of resin. The theoretical content was 0.888 meq/gram resin (obtained 97.9 ~ of theory)~
This compound was designated as Block Precur-sor 1.
In Control Example A, Block Precursor 2 was used. This Block Precursor is prepared by the same general procedures as Block Precursor 1. However, it was prepared in dimethoxyethane, at 55 ~ solids, as a block copolymer of methyl methacrylate and glycidyl methacrylate with nominal degrees of polymerization of 40//8. The epoxy number of the resin was 0.7 meq/gram.
~3~ 52 Block Precursor 2 was also used in Control Examples E, F, G, and H.
Example 1 - Esterification with 4-sulfamidobenzoic acid ~lock Precursor 1 (102.7 g) was combined with 17.1 g 4-sulfamidobenzoic acid and 1.1 mL 40 wt %
benzyl trimethylammonium hydroxide in methanol; the mixture was brought to 95 C (start of reflux) and a 5 mL sample was removed. The translucent white mixture was refluxed for about 45 minutes before the taking of a 5 mL sample an~ the addition of 35.7 g tetrahydro-furan. Samples of 5 mL were taken each hour for two hours, and 30 minutes later. After 2 further hours a fifth sample was removed, and after a final 1/2 hour at reflux, the reaction was judged sufficiently complete.
The product was a translucent white resin, 48 % solids.
The epoxy values of the samples were as follows:
Sample Epoxy value (meq epoxy/gram resin) 1 0.705
~CKGROUND OF THE INVENTION
Previously, AB block copolymers have been developed which show good action as dispersants, which use aromatic carboxylic acids incorporated in the A
segment to provide binding to a pigment surface. Such copolymers are described, for example, in Hutchins et al., U.S. Patent 4,656,226, issued April 7, 1987.
Hutchins et al. note that many carboxylic acids, when incorporated onto the A segment of the block copolymer, can provide improved dispersant characteristics.
Preferred acids which can be so used include benzoic acid, 2-,3-,4-nitrobenzoic acid, 3,5-dinitrobenzoic acid, l-napthoic acid, and 3-chlorobenzoic acid.
While the Hutchins et al. compositions provide excellent dispersant characteristics, many of these compounds exhibit color changes upon extended exposure to light and aging. Because dispersants are often used in mixtures designed to produce a specific color, changes in the color over time are undesirable.
SUMMARY OF THE_INVENTION
The present inventlon is based on the discov-ery of a specific class of phenyl aromatic AB block copolymers which exhibit excellent performance as dispersants and which resist color changes due to exposure to light or aging.
Specifically, the instant invention provides a block copolymer having at least one A segment and at least one B segment, each segment having a molecular weight of at least about 500 and the backbones of which consist essentially of at least one polymerized ~3~L852 methacrylate or acrylate ester, at least about 20% of the acrylic moieties of the A segment having bonded thereto a moiety derived from an acid, amide or sulfonamide which is a substituent of a phenyl aromatic; the phenyl aromatic having another substituent which is a con~ugating group; the phenyl aromatic having no nitrogen, thiol, or OH group directly bonded to an aromatic ring, and wherein the B
segment contains less than about 20% of the acid, amide or sulfonamide moieties present in the A segment.
Preferably, the block copolymer is made by Group Transfer Polymerization techniques (GTP). A
preferred monomer for the A segment is 2,3-epoxypropyl methacrylate which is later reacted using a basic catalyst with the phenyl aromatic.
pETAILED DESCRIPTION OF_THE INVENTION
The instant invention is based on the discov-ery that, in block copolymers of the general type described in Hutchins et al., U.S. Patent 4,656,~26, the presence of certain aromatic substituents on the A
segment will provide excellent performance of the block coolymers as dispersants, and, at the same time, do no~
exhibit yellowing or other co:Lor change when exposed to light and aqing. Accordingly, the present compounds are exceptionally well suited for use as dispersants for pigments and in other applications where color change would not be desirable.
The block copolymers of the present invention have at least one A segment and at least one B segment.
While the block size is not critical to the present invention, each segment generally has a molecular weight of at least about S00. The bacXbones of the segments consist essentially of at least one polymerized methacrylate or acrylate ester. In the , ~L304852 context of the present invention, both methacrylate and acrylate units are designated as acrylic moieties. At least about 20~ of the acrylic moieties of the A
segment have bonded thereto a ~ragment derived from an acid, amide, or sulfonamide which is a substituent of a phenyl aromatic. The term fragment is used in the usual sense of meaning that portion of the moiety remaining after bonding to the A segment. Thus, for example, it will be understood that a phenyl aromatic having an acid group would bond to the A segment through that group, after which the acidic hydrogen would no longer be present.
The phenyl aromatic also has another substi-tuent which i5 a conjugating group. The term conjugating group will be understood to mean one having an atom attached to an aromatic ring and having a double or triple bond. Examples of such conjugating groups include ester, nitrile aromatic or substituted aromatic, or sulfonamide groups.
Another important characteristic of the phenyl aromatics bonded to the A segments of the present block copolymers is that they have no nitrogen, thiol, or OH group directly bonded to an aromatic ring, regardless of whether the aromatic ring is the primary component of the phenyl aromatic or a substituent.
Specific examples of such esters or amides include 4-sulfamido benzoic acid, n-phthaloyl~lycine, saccharin, and 4-biphenyl carboxylic acid.
4-sulfamido benzoic acid has the structural formula As can be seen from the formula, this compound, as required by the present invention, is a phenyl aromatic, has both a carboxylic acid group and a sulfonamide group, and has no nitrogen, thiol, or hydroxy groups directly bonded to the aromatic ring.
4-biphenyl carboxylic acid has the structural formula ~/~ C02H
This compound, as required by the present invention, is a phenyl aromatic having a carboxylic acid group. As a conjugating group, this compound has an aromatic substituent, a second aromatic ring. In addition, there are no nitrogen, sulfur, or hydroxy groups directly bonded to the aromatic ring.
Similarly, it can be seen that n-phthaloyl-glycine, o ~ ~ / CO2H
~ C H 2 and saccharin O
~S~
/
O O
satisfy the structural requirements of the present claims.
The B segment of the present copolymers contains less than about 20% of the acid, amide, or sulfonamide moieties present in the A segment, and :'' . .
~304852 preferably none of these moieties. The B segment is preferably prepared from an alkyl methacrylate or blend of alkyl methacrylates such as methyl methacrylate (MMA), MMA
and butyl methacrylate (BMA), BMA alone, or 2-ethylhexyl methacrylate (2-EHMA).
The block copolymers of the present invention can be prepared using the general techniques described in Hutchins et al., U.S. Patent 4,656,226. Using the techni~ues described therein, it has been found to be convenient to form the basic AB block copolymer, and then attach the reguired phenyl aromatic derivative by bringing the amide or ester into contact with the basic block copolymer under reaction conditions, reacting the ester or amide with the lS epoxy group in the block copolymer structure. In the alternative, monomers compatible with a block copolymerization processr such as GTP, which introduce appropriate pendant groups can be used directly. One such monomer, for example, is 2-(4-phenylbenzoyloxy) ethyl methacrylate.
The compounds of the present invention, by reason of the different polar characteristics of the A and B
segments, demonstrate outstanding performance as pigment dispersants. The presence of two conjugating groups confers excellent dispersion properties, particulary for pigments which are difficult to disperse. Moreover, these compositions are remarkably resistant to color change on aging or exposure to light. While this advantage is not fully understood, it is believed to be a result o* the polar groups having no nitrogen, thiol or hydroxy groups directly attached to an aromatic ring. It is believed that these groups allow formation of highly conjugated or quinone type structures upon exposure to light or aging.
In addition, the present compositions avoid the A
., ~ll3~3S2 .
more complex napthyl ~tructure seen in ~ome of the compound~ disclosed by Hutchins et alr In addition to th~ir complexity, these naphthyl material~ do not appear to be uniformly resistant to color changes upon S exposure to light and aging.
In the following Examples and Comparative Examples, the dispersants were evaluated according to established techniques ~or dispersing performance and yellowing. The Dispersion Rating refers to the sum of 4 ratings in MI~K, as explained in the Hutchins et al.
patent at Column 6, line 67 to Column 7, line 18.
According to that evaluation procedure, 4 represents a - perfect dispersant, while 16 indicates poor dispersant performance.
lS The increase in yellowne~s was evaluated by exposure to light and aging on a QW instrument, fo~lowed by color measurement on the LAB scale.
According to this test, the resulting number represents the change in yellow~ess of a white paint. The least change is therefore the most desirable. According to this test, for example, lor greater is unacceptable.
In the Examples and Control Examples, all monomers and solvents were purified of residual alco~
hols and water by distillation, use of 4 Angstr~m molecular ~$ev~s, or by passing throug~ a column of activity 1 alumina, as appropriate, and were stored under nitroqen.
In the followin~ Examples 1-4 and Comparative Examples B-D, the basic AB block copolymer, to which was added the various substituent group~, was prepared according to ths following procedur~.
A 5-liter fla~k was purged with nitrogen and charged with 1580 g of 60/40w/w propylene carbonate/~etrahydrofuran, 403.6 9 glycidyl meth-35 ~crylate, 41.3 g 1-methoxy-1-trimethylsiloxy-2-~L3101~L~3Si2 methylpropene (hereafter termed "initiator~), 4.2 g xylenes, and 0.4 g toluene. The glycidyl methacrylate was the primary component of the A block. After cooling to 5 C, reaction was initiated by the addition of 10.4 mL 0.34 M tetrabutylammonium-3-chlorobenzoate in tetrahydro~uran (hereafter termed ~catalyst~). The temperature rose, without cooling, to 45.8 C in 23 minutes. A feed of 1145g of 41.3/58.7 w/w methyl methacrylate/butyl methacrylate over 30 minutes was begun 28 minutes after first addition of catalyst. The methyl methacrylate/butyl methacrylate monomers were the primary components of the B block of the copolymer.
Beginning at the same time, 5.22 mL of catalyst was added over 30 minutes. At the end of the same time, 5.22 mL of catalyst was added over 30 minutes. At the end of the monomer feed, the reaction temperature was ca. 65 C. After a further 7 minutes, the temperature had risen to 85 C; an ice bath was used for 45 minutes to lower the temperature. After the ice bath was removed, 7.6 g methanol was added. Actual solids of the resin was measured as 48.77 wt %,theoretical solids was 49.15 % (obtained 99O2 % of theory). The actual epoxy content of the resin was 0.869 meq epoxy per gram of resin. The theoretical content was 0.888 meq/gram resin (obtained 97.9 ~ of theory)~
This compound was designated as Block Precur-sor 1.
In Control Example A, Block Precursor 2 was used. This Block Precursor is prepared by the same general procedures as Block Precursor 1. However, it was prepared in dimethoxyethane, at 55 ~ solids, as a block copolymer of methyl methacrylate and glycidyl methacrylate with nominal degrees of polymerization of 40//8. The epoxy number of the resin was 0.7 meq/gram.
~3~ 52 Block Precursor 2 was also used in Control Examples E, F, G, and H.
Example 1 - Esterification with 4-sulfamidobenzoic acid ~lock Precursor 1 (102.7 g) was combined with 17.1 g 4-sulfamidobenzoic acid and 1.1 mL 40 wt %
benzyl trimethylammonium hydroxide in methanol; the mixture was brought to 95 C (start of reflux) and a 5 mL sample was removed. The translucent white mixture was refluxed for about 45 minutes before the taking of a 5 mL sample an~ the addition of 35.7 g tetrahydro-furan. Samples of 5 mL were taken each hour for two hours, and 30 minutes later. After 2 further hours a fifth sample was removed, and after a final 1/2 hour at reflux, the reaction was judged sufficiently complete.
The product was a translucent white resin, 48 % solids.
The epoxy values of the samples were as follows:
Sample Epoxy value (meq epoxy/gram resin) 1 0.705
2 0.332
3 0.295
4 0.242 0.173 Final 0.141 Dispersion Rating in methyl isobutylketone After 29 days of Q W exposure, the b (yellowness) measurement increased by only 0.36 units.
- ~ 3~ 52 Example 2 - _Esterification with N-phthaloYlqlYcine Block Presursor 1 (101.8 g) was combined with 17.2 g N-phthaloyl glycine and 1.1 mL 40 wt % benzyl trimethylammonium hydroxide in methanol. When the mixture came to reflux, a 5 mL sample was taken.
Samples of 5 mL were taken at 30 minute intervals for two samples, after which 7.5 and 10.2 g THF wers adcled.
An hour later, another 5 mL sample was taken, and after a further 2 hours another sample was taken. After 0.5 further hours the reaction was sufficiently complete.
The product was a thick, translucent resin, 50.4 %
solids after thinning with 5.1 g THF. The epoxy values of the samples were as follows:
15Sample Epoxy value (meq epoxy/gram resin) 1 0.622 2 0.340 3 0.279 4 0.185 0.132 Final O.oss Dispersion Rating in m~thyl isobutylketone After 29 days of Q W exposure, the b (yellowness) measurement increased by only 0.37 units.
~l~30~ 2 Example 3 - Esterification with saccharin Block Precursor 1 (282.3 g) was combined with 42.6 g of saccharin, or o-benzoic sulfimide, 53 g diacetone alcohol, and 2.33 g 40 wt % benzyl trimethylammonium hydroxide in methanol. When the mixture was at reflux 45 minutes, a sample was taken (epoxy content 0.35~ me~/gram). Solvent was removed by distillation to bring the reflux temperature to 125C, then after a total of 1.5 hrs at reflux, T}~F (20 mL) was added, and a final sample was analyzed for epoxy content (0.02 meq/gram).
Dispersion Rating in methyl isobutylketone After 29 days of Q W exposure, the b (yellowness) measurement increased by only 0.5 units.
Example 4 - Esterification with 4-biphenylcarboxylic acid Block Precursor 1 (105.1 g) was combined with 17.2 g 4-biphenylcarboxyylic acid, and 1.1 ml 40 wt %
benzyl trimethylammonium hydroxide in methanol, using the same general reaction techniques as in Control Example A. Dispersion Rating in methyl isobutylketone After 22 day~ ~f Q W exposure, the b (yellowness) measurement decreased by 0.14 units.
~31~852 Control Example A - Esterification with 4-nitrobenzoic acid Block Precursor 2 t150.3 g) was combined with 17.5 g 4-nitroben~oic acid, and 250. g of a 60:40 (w:w) mixture of toluene and methyl is~butyl ketone. The mixture was brought to reflux, and, over an hour, 250 g of dis~illate was removed, until the distillate temp-erature was 107C. The resulting mixture was refluxed 4.5 hours. The final resin had an epoxy content of 0~05 meq/gram of resin.
Dispersion Rating in methyl isobutylketone After 3 days of Q W exposure, the b (yellowness) measurement increased by 3.2 units.
Control Example B - Esterification with l-napthyl acetic acid Block Precursor 1 ~100.7 g) was combined with 14.7 g l-napthylacetic acid and 1.1 mL 40 wt % benzyl trimethylammonium hydroxide in methanol. The mixture was brought to 69C and a 5 mL sample was removed. The clear yellow mixture was refluxed for abou~ 45 minutes before the taking of a 5 mL sample and the addition of 9.3 g tetrahydrofuran. Samples of 5 mL were taken each hour for two hours, and 30 minutes later, when 9.5 grams tetrahydrofuran was added. After 2 further hours a fifth sample was removed, and after a final 1/2 hour at reflux, the reaction was sufficiently complete. The product was a clear yellow resin which was diluted with 14.6 g THF to 47.25 % solids.
~L304~52 52 % solids. The epoxy values of the samples were as follows:
Sam~le Epoxy value (meq epoxy/gram resin) ~ 0.596 2 0.344 3 0.232 ~ 0.127 Final 0.070 Dispersion Rating in methyl isobutylketone After 4 days of QW exposure, the b (yellowness) measurement increased by 4.2 units.
Control Example D - Esterification with N-(4-carboxyphenvl~pthalimide.
Block Precursor 1 llO0.9 g) was combined with 21.1 g N-(4-carboxyphenyl)phthalimide and 1.1 mL 40 w~
% benzyl trim~thylammonium hydroxide in methanol. When the mixture came to reflux, a 5 mL sample was taken.
Samples of 5 mL were taken at 30 minute intervals for two samples, after which 7.5 and 10.2 g THF were added.
Then,an hour later, another 5 mL sample was taken, and after a ~urther 2 hours another sample was taken.
After 0.5 further hours the reaction was sufficiently complete. The product was a thick, translucent resin, 50.4 % solids after thinning with 5.1 g THF. The epoxy values of the samples were as follows:
~3~ 52 The epoxy values of the samples were as follows:
Sample Epoxy value (meq epoxy/gram resin) 1 0.734 2 0.50~
3 0.354 4 0.193 0.077 10Final 0O074 Dispersion Rating in methyl isobutylketone lSW811 After 22 days of Q W exposure, the b (yellowness) measurement increased by 1.34 units.
Control Example C - Esterification with 3-hydroxy-2-napthoic acid Block Precursor 1 (104.1 g) was combined with 16~2 g 3-hydroxy-2-napthoic acid and 1.1 mL 40 wt %
benzyl trimethylammonium hydroxide in methanol and 8.5 g THF. The mixture was brought to 78 C and it was observed that the mixture was tranparent but very dark brown. When the mixture came to refluxj a 5 mL sample was taken. Samples of 5 mL were taken at 30 minute intervals for two samples, then an hour later,and 30 minutes later 9.9 grams tetrahydrofuran was added.
After 1.5 further hours the reaction was sufficiently complete. The product was a clear, thick, brown resin, ~31048S2 Sample EpoxY value (meq epoxy/gram r~sin) 1 0.622 2 0.340 3 0.279 4 0.185 0.132 Final 0.099 Dispersion Rating in methyl isobutylketone After 29 days of OW exposure, the b (yellowness) measurement increased by 2.6 units.
The dispersion characteristics and increase in yellowness for the block copolymers of Examples 1-4 and Control Examples A-D are summarized in Table I.
TABLE I
DISPERSON YELLOWNESS
EXAMPLE ESTER FROM RATING _ INCREASE
1 4-SULFAMIDO BENZOIC 4 G 0.36 G
2 N-PHTHALOYLGLYCINE 4 G 0.37 G
3 SACCHARIN 7 G 0.5 G
4 4-BIPHENYL CARBOXYLIC 7 G 0.14 G
A 4-NITROBENZOIC 4 G 3.0 B
B 1-NAPTHYL ACETIC 6 G 1.3 B
ACID 4 G 4.2 B
PHTHALIMIDE 5 G 2.6 B
~3~14~S2 Control Example E - Esterification with 3-chlorobenzoic acid Block Precursor 2 t149.6 g) was combined with 15.6 g 3-chlorobenzoic acid, and 276.3 g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone.
The mixture was brought to reflux, and over 1.3 hours, 253.7 g of distillate was removed, until the pot temperature was 118C. The resulting solution was refluxed overnite (20 hours) further. Final solids was 60.4%, ~inal epoxy number was 0.05 meq/gram.
Dispersion Rating in methyl isobutylketone After 29 days of Q W exposure, the b (yellowness) measurement was essentially unchanged (~/- 0.05).
Control Example F - Esterification with l-napthoic acid Block Precursor 2 (146.3g) was combined with 18.0 g l~napthoic acid, and 2~0.7 g of a 60040 (w:w) mixture of toluene and methyl isobutyl ketone. The mixture was brought to reflux, and over 1.3 hours, at least 266 g of distillate was removed, until the distillate temperature was 108.2C. The sol ids (80.77%) was unusually high, probably due to loss of solvent. More toluene:methyl isobutylketone (82.4 g) was added, and the fluid, homogeneous mixture was refluxed 2.5 hours.
~L3~ 52 Dispersion Rating in methyl isobutylketone ~805 After 29 days of Q W exposure, the b (yellowness) measurement increased by only 0.2 units.
Control Exam~le G - Esterification with 2-nitrobenzoic acid.
Block Precursor 2 (148.3 g) was combined with 17.5 g 2-nitrobenzoic acid, and 280.6 g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone.
The mixture was brought to reflux, and over an hour, 2-50 y of distillate was removed, until the distillate temperature was 105C. The resulting mixture was refluxed 2 hours. The final resin had an acid and epoxy content of 0.05 meq/gram of resin, and the resin was 63.6 % solids.
Dispersion Rating in methyl isobutylketone After 7 days of Q W exposure, the b (yellowness) me-asurement increased by 2.0 units.
Control Example H - Esterification with 3-nitrobenzoic acid Block Precursor 2 was combined with 17.5 g 4-nitrobenzoic ~cid, and 250. g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone. The 13~352 mixture was brought to reflux, and over an hour, 250 g of distillate was removed, until the distillate temper-ature was 107C. The resulting mixture was refluxecl 4.5 hours. The final resin had an epoxy content of 0.051 meq/gram of resin.
Dispersion Rating in methyl isobutylketone W~11 3 After 7 days of Q W exposure, the b (yellowness) measurement increased by 2.0 units.
The dispersion characteristics and increase in yellowness for the block copolymers of Control Examples E-H are summarized in Table II.
TABLE II
DISPERSION YELLOWNESS
EXAMPLE ESTER FROM RATINGINCREASE
E 3-CHLORO 11 B -0.03 G
F l-NAPTHOIC 8 B/G 0.2 G
G 2-NITRO 11 B 2.0 s H 3-NITRO 10 B 2.0 B
Control Exam~le I - Esterification with 3.4.5~trimethoxybenzoic acid.
Block Precursor 2 (149.3 g) was combined with 21.6 g 3,4,5-trimethoxybenzoic acid, and 276.8 g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone. The mixture was brought to reflux, and, over 1.3 hours, 253.7 g of distillate was removed, until the boiling temperature was 108.2 C. The resulting ,~
.
1304~52 , solution was further refluxed overnite (14 hours). The final solids was 54.0 ~, and the final epoxy number was O.07 meq~gram.
Dispersion Rating in methyl isobutylketone Control Example J - Esterification with 4-nitrobenzoic acid For this preparation, Block Precursor 3 was used, which was prepared according to the same general procedures as Block Precursor 1, but which had an epoxy content of 0.993 meq/gram of resin, and solids of 61.5 %, versus a theoretical of 1.07 meq/g and 59.6 %
solids.
Block Precursor 3 (99.4 g) was heated to 70 C. 4-Nitrobenzoic acid~l4.8 g) was added, followed immediately by 4.9 mL lM tetrabutylammonium3-chloro-benzoate in acetonitrile. The mixture was stirred and refluxed for 3 hours, and diluted with 30 g of toluene, to yield a resin of 48.2 % solids, and epoxy content of 0.022 megjgram.
Dispersion Rating in methyl isobutylketone After 14 days of Q W exposure, the b (yellowness) measurement increased by 3.0 units.
~04852 ~ -- 19 --Control Example K - Esterification with 2.4-dihydroxybenzophenone Block Precursor 2 (146.7 g) was combined with 20.9 g 2,4-dihydroxybenzophenone, and 279.6 g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone. The mixture was brought to reflux, and, over 1.5 hours, at least 254.2 g of distillate was removed, until the distillate temperature was 111.2 C. The mixture was refluxed for 20 hours, to give a final resin of 53.6 % solids and epoxy number of 0.05 meq/gram.
Dispersion Rating in methyl isobutylketone W~53 3
- ~ 3~ 52 Example 2 - _Esterification with N-phthaloYlqlYcine Block Presursor 1 (101.8 g) was combined with 17.2 g N-phthaloyl glycine and 1.1 mL 40 wt % benzyl trimethylammonium hydroxide in methanol. When the mixture came to reflux, a 5 mL sample was taken.
Samples of 5 mL were taken at 30 minute intervals for two samples, after which 7.5 and 10.2 g THF wers adcled.
An hour later, another 5 mL sample was taken, and after a further 2 hours another sample was taken. After 0.5 further hours the reaction was sufficiently complete.
The product was a thick, translucent resin, 50.4 %
solids after thinning with 5.1 g THF. The epoxy values of the samples were as follows:
15Sample Epoxy value (meq epoxy/gram resin) 1 0.622 2 0.340 3 0.279 4 0.185 0.132 Final O.oss Dispersion Rating in m~thyl isobutylketone After 29 days of Q W exposure, the b (yellowness) measurement increased by only 0.37 units.
~l~30~ 2 Example 3 - Esterification with saccharin Block Precursor 1 (282.3 g) was combined with 42.6 g of saccharin, or o-benzoic sulfimide, 53 g diacetone alcohol, and 2.33 g 40 wt % benzyl trimethylammonium hydroxide in methanol. When the mixture was at reflux 45 minutes, a sample was taken (epoxy content 0.35~ me~/gram). Solvent was removed by distillation to bring the reflux temperature to 125C, then after a total of 1.5 hrs at reflux, T}~F (20 mL) was added, and a final sample was analyzed for epoxy content (0.02 meq/gram).
Dispersion Rating in methyl isobutylketone After 29 days of Q W exposure, the b (yellowness) measurement increased by only 0.5 units.
Example 4 - Esterification with 4-biphenylcarboxylic acid Block Precursor 1 (105.1 g) was combined with 17.2 g 4-biphenylcarboxyylic acid, and 1.1 ml 40 wt %
benzyl trimethylammonium hydroxide in methanol, using the same general reaction techniques as in Control Example A. Dispersion Rating in methyl isobutylketone After 22 day~ ~f Q W exposure, the b (yellowness) measurement decreased by 0.14 units.
~31~852 Control Example A - Esterification with 4-nitrobenzoic acid Block Precursor 2 t150.3 g) was combined with 17.5 g 4-nitroben~oic acid, and 250. g of a 60:40 (w:w) mixture of toluene and methyl is~butyl ketone. The mixture was brought to reflux, and, over an hour, 250 g of dis~illate was removed, until the distillate temp-erature was 107C. The resulting mixture was refluxed 4.5 hours. The final resin had an epoxy content of 0~05 meq/gram of resin.
Dispersion Rating in methyl isobutylketone After 3 days of Q W exposure, the b (yellowness) measurement increased by 3.2 units.
Control Example B - Esterification with l-napthyl acetic acid Block Precursor 1 ~100.7 g) was combined with 14.7 g l-napthylacetic acid and 1.1 mL 40 wt % benzyl trimethylammonium hydroxide in methanol. The mixture was brought to 69C and a 5 mL sample was removed. The clear yellow mixture was refluxed for abou~ 45 minutes before the taking of a 5 mL sample and the addition of 9.3 g tetrahydrofuran. Samples of 5 mL were taken each hour for two hours, and 30 minutes later, when 9.5 grams tetrahydrofuran was added. After 2 further hours a fifth sample was removed, and after a final 1/2 hour at reflux, the reaction was sufficiently complete. The product was a clear yellow resin which was diluted with 14.6 g THF to 47.25 % solids.
~L304~52 52 % solids. The epoxy values of the samples were as follows:
Sam~le Epoxy value (meq epoxy/gram resin) ~ 0.596 2 0.344 3 0.232 ~ 0.127 Final 0.070 Dispersion Rating in methyl isobutylketone After 4 days of QW exposure, the b (yellowness) measurement increased by 4.2 units.
Control Example D - Esterification with N-(4-carboxyphenvl~pthalimide.
Block Precursor 1 llO0.9 g) was combined with 21.1 g N-(4-carboxyphenyl)phthalimide and 1.1 mL 40 w~
% benzyl trim~thylammonium hydroxide in methanol. When the mixture came to reflux, a 5 mL sample was taken.
Samples of 5 mL were taken at 30 minute intervals for two samples, after which 7.5 and 10.2 g THF were added.
Then,an hour later, another 5 mL sample was taken, and after a ~urther 2 hours another sample was taken.
After 0.5 further hours the reaction was sufficiently complete. The product was a thick, translucent resin, 50.4 % solids after thinning with 5.1 g THF. The epoxy values of the samples were as follows:
~3~ 52 The epoxy values of the samples were as follows:
Sample Epoxy value (meq epoxy/gram resin) 1 0.734 2 0.50~
3 0.354 4 0.193 0.077 10Final 0O074 Dispersion Rating in methyl isobutylketone lSW811 After 22 days of Q W exposure, the b (yellowness) measurement increased by 1.34 units.
Control Example C - Esterification with 3-hydroxy-2-napthoic acid Block Precursor 1 (104.1 g) was combined with 16~2 g 3-hydroxy-2-napthoic acid and 1.1 mL 40 wt %
benzyl trimethylammonium hydroxide in methanol and 8.5 g THF. The mixture was brought to 78 C and it was observed that the mixture was tranparent but very dark brown. When the mixture came to refluxj a 5 mL sample was taken. Samples of 5 mL were taken at 30 minute intervals for two samples, then an hour later,and 30 minutes later 9.9 grams tetrahydrofuran was added.
After 1.5 further hours the reaction was sufficiently complete. The product was a clear, thick, brown resin, ~31048S2 Sample EpoxY value (meq epoxy/gram r~sin) 1 0.622 2 0.340 3 0.279 4 0.185 0.132 Final 0.099 Dispersion Rating in methyl isobutylketone After 29 days of OW exposure, the b (yellowness) measurement increased by 2.6 units.
The dispersion characteristics and increase in yellowness for the block copolymers of Examples 1-4 and Control Examples A-D are summarized in Table I.
TABLE I
DISPERSON YELLOWNESS
EXAMPLE ESTER FROM RATING _ INCREASE
1 4-SULFAMIDO BENZOIC 4 G 0.36 G
2 N-PHTHALOYLGLYCINE 4 G 0.37 G
3 SACCHARIN 7 G 0.5 G
4 4-BIPHENYL CARBOXYLIC 7 G 0.14 G
A 4-NITROBENZOIC 4 G 3.0 B
B 1-NAPTHYL ACETIC 6 G 1.3 B
ACID 4 G 4.2 B
PHTHALIMIDE 5 G 2.6 B
~3~14~S2 Control Example E - Esterification with 3-chlorobenzoic acid Block Precursor 2 t149.6 g) was combined with 15.6 g 3-chlorobenzoic acid, and 276.3 g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone.
The mixture was brought to reflux, and over 1.3 hours, 253.7 g of distillate was removed, until the pot temperature was 118C. The resulting solution was refluxed overnite (20 hours) further. Final solids was 60.4%, ~inal epoxy number was 0.05 meq/gram.
Dispersion Rating in methyl isobutylketone After 29 days of Q W exposure, the b (yellowness) measurement was essentially unchanged (~/- 0.05).
Control Example F - Esterification with l-napthoic acid Block Precursor 2 (146.3g) was combined with 18.0 g l~napthoic acid, and 2~0.7 g of a 60040 (w:w) mixture of toluene and methyl isobutyl ketone. The mixture was brought to reflux, and over 1.3 hours, at least 266 g of distillate was removed, until the distillate temperature was 108.2C. The sol ids (80.77%) was unusually high, probably due to loss of solvent. More toluene:methyl isobutylketone (82.4 g) was added, and the fluid, homogeneous mixture was refluxed 2.5 hours.
~L3~ 52 Dispersion Rating in methyl isobutylketone ~805 After 29 days of Q W exposure, the b (yellowness) measurement increased by only 0.2 units.
Control Exam~le G - Esterification with 2-nitrobenzoic acid.
Block Precursor 2 (148.3 g) was combined with 17.5 g 2-nitrobenzoic acid, and 280.6 g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone.
The mixture was brought to reflux, and over an hour, 2-50 y of distillate was removed, until the distillate temperature was 105C. The resulting mixture was refluxed 2 hours. The final resin had an acid and epoxy content of 0.05 meq/gram of resin, and the resin was 63.6 % solids.
Dispersion Rating in methyl isobutylketone After 7 days of Q W exposure, the b (yellowness) me-asurement increased by 2.0 units.
Control Example H - Esterification with 3-nitrobenzoic acid Block Precursor 2 was combined with 17.5 g 4-nitrobenzoic ~cid, and 250. g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone. The 13~352 mixture was brought to reflux, and over an hour, 250 g of distillate was removed, until the distillate temper-ature was 107C. The resulting mixture was refluxecl 4.5 hours. The final resin had an epoxy content of 0.051 meq/gram of resin.
Dispersion Rating in methyl isobutylketone W~11 3 After 7 days of Q W exposure, the b (yellowness) measurement increased by 2.0 units.
The dispersion characteristics and increase in yellowness for the block copolymers of Control Examples E-H are summarized in Table II.
TABLE II
DISPERSION YELLOWNESS
EXAMPLE ESTER FROM RATINGINCREASE
E 3-CHLORO 11 B -0.03 G
F l-NAPTHOIC 8 B/G 0.2 G
G 2-NITRO 11 B 2.0 s H 3-NITRO 10 B 2.0 B
Control Exam~le I - Esterification with 3.4.5~trimethoxybenzoic acid.
Block Precursor 2 (149.3 g) was combined with 21.6 g 3,4,5-trimethoxybenzoic acid, and 276.8 g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone. The mixture was brought to reflux, and, over 1.3 hours, 253.7 g of distillate was removed, until the boiling temperature was 108.2 C. The resulting ,~
.
1304~52 , solution was further refluxed overnite (14 hours). The final solids was 54.0 ~, and the final epoxy number was O.07 meq~gram.
Dispersion Rating in methyl isobutylketone Control Example J - Esterification with 4-nitrobenzoic acid For this preparation, Block Precursor 3 was used, which was prepared according to the same general procedures as Block Precursor 1, but which had an epoxy content of 0.993 meq/gram of resin, and solids of 61.5 %, versus a theoretical of 1.07 meq/g and 59.6 %
solids.
Block Precursor 3 (99.4 g) was heated to 70 C. 4-Nitrobenzoic acid~l4.8 g) was added, followed immediately by 4.9 mL lM tetrabutylammonium3-chloro-benzoate in acetonitrile. The mixture was stirred and refluxed for 3 hours, and diluted with 30 g of toluene, to yield a resin of 48.2 % solids, and epoxy content of 0.022 megjgram.
Dispersion Rating in methyl isobutylketone After 14 days of Q W exposure, the b (yellowness) measurement increased by 3.0 units.
~04852 ~ -- 19 --Control Example K - Esterification with 2.4-dihydroxybenzophenone Block Precursor 2 (146.7 g) was combined with 20.9 g 2,4-dihydroxybenzophenone, and 279.6 g of a 60:40 (w:w) mixture of toluene and methyl isobutyl ketone. The mixture was brought to reflux, and, over 1.5 hours, at least 254.2 g of distillate was removed, until the distillate temperature was 111.2 C. The mixture was refluxed for 20 hours, to give a final resin of 53.6 % solids and epoxy number of 0.05 meq/gram.
Dispersion Rating in methyl isobutylketone W~53 3
Claims (11)
1. A block copolymer having at least one A segment and at least one B segment, each segment having a molecular weight of at least about 500 and the backbones of which consist essentially of at least one polymerized methacrylate or acrylate ester, at least about 20% of the acrylic moieties of the A segment having bonded thereto a moiety derived from an acid, amide or sulfonamide which is a substituent of a phenyl aromatic; the phenyl aromatic having another substituent which is a conjugating group;
the phenyl aromatic having no nitrogen, thiol, or OH group directly bonded to an aromatic ring, and wherein the B
segment contains less than about 20% of the acid, amide or sulfonamide moieties present in the A segment.
the phenyl aromatic having no nitrogen, thiol, or OH group directly bonded to an aromatic ring, and wherein the B
segment contains less than about 20% of the acid, amide or sulfonamide moieties present in the A segment.
2. A block copolymer of Claim 1 wherein the fragment which is a substituent of the phenyl aromatic is selected from carboxylic acid or sulfonamide.
3. A block copolymer of Claim 1 wherein the B segment contains substantially no acid, amide or sulfonamide moieties derived from phenyl aromatics.
4. A block copolymer of Claim 1 wherein the conjugating group on the phenyl aromatic is selected from ester, nitrile, aromatic and sulfonamide groups.
5. A block copolymer of Claim 1 wherein the moiety bonded to the A segment is derived from 4-sulfamidobenzoic acid.
16. A block copolymer of Claim 1 wherein the moiety bonded to the A segment is derived from n-phthaloyl glycine.
7. A block copolymer of Claim 1 wherein the moiety bonded to the A segment is derived from saccharine.
8. A block copolymer of Claim 1 wherein the moiety bonded to the A segment is derived from 4-biphenylcarboxylic acid.
9. A pigment dispersion in organic solvent dispersed by means of a composition of Claim 1.
10. A coating composition comprising a pigment dispersion of Claim 9, a film former and a liquid medium.
11. A molding composition comprising a pigment dispersion of Claim 9 and a resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/138,039 US4812517A (en) | 1987-12-28 | 1987-12-28 | Dispersants resistant to color change |
| US138,039 | 1987-12-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1304852C true CA1304852C (en) | 1992-07-07 |
Family
ID=22480164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000586053A Expired - Lifetime CA1304852C (en) | 1987-12-28 | 1988-12-15 | Dispersants resistant to color change |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4812517A (en) |
| EP (1) | EP0323181A3 (en) |
| JP (1) | JPH01204914A (en) |
| CA (1) | CA1304852C (en) |
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| US6462125B1 (en) | 1999-12-16 | 2002-10-08 | Ppg Industries Ohio, Inc. | Pigment dispersions containing dispersants prepared by controlled radical polymerization having hydrophilic and hydrophobic segments |
| US6441066B1 (en) | 1999-12-16 | 2002-08-27 | Ppg Industries Ohio, Inc. | Pigment dispersions containing dispersants prepared by controlled radical polymerization and having pendent hydrophobic polymeric segments |
| US6336966B1 (en) | 1999-12-16 | 2002-01-08 | Ppg Industries Ohio, Inc. | Pigment dispersions containing dispersants having core and arm star architecture prepared by controlled radical polymerization |
| US6294014B1 (en) | 1999-12-16 | 2001-09-25 | Ppg Industries Ohio, Inc. | Pigment dispersions containing dispersants prepared by controlled radical polymerization and having pendent hydrophilic polymeric segments |
| US6326420B1 (en) | 1999-12-16 | 2001-12-04 | Ppg Industries Ohio, Inc. | Pigment dispersions containing dispersants prepared by controlled radical polymerization |
| US6306209B1 (en) | 1999-12-16 | 2001-10-23 | Ppg Industries Ohio, Inc. | Pigment dispersions containing dispersants having pendent hydrophobic polymeric segments prepared by controlled radical polymerization |
| US6472463B1 (en) | 1999-12-17 | 2002-10-29 | E. I. Du Pont De Nemours And Company | Graft copolymer pigment dispersant |
| US6495618B1 (en) | 1999-12-17 | 2002-12-17 | E. I. Du Pont De Nemours And Company | Graft copolymer with an amide functional group as a pigment dispersant |
| US6576722B2 (en) * | 2000-12-13 | 2003-06-10 | Ppg Industries Ohio, Inc. | Acrylic-halogenated polyolefin copolymer adhesion promoters |
| US6849679B2 (en) * | 2001-05-21 | 2005-02-01 | Ciba Specialty Chemicals Corporation | Pigment compositions with modified block copolymer dispersants |
| US7186770B2 (en) * | 2002-02-25 | 2007-03-06 | E. I. Du Pont De Nemours And Company | Unfinished rutile titanium dioxide slurry for paints and paper coatings |
| CN101205418B (en) * | 2007-11-29 | 2010-06-09 | 东华大学 | Polyether primary amine derivative disperser for paint, preparation and use thereof |
| EP2889880A4 (en) | 2012-08-23 | 2015-07-15 | Bando Chemical Ind | Conductive paste |
| JP7090399B2 (en) | 2017-02-21 | 2022-06-24 | 日本ペイント・オートモーティブコーティングス株式会社 | Water-based paint composition and multi-layer coating |
| WO2019092036A1 (en) | 2017-11-07 | 2019-05-16 | Clariant Plastics & Coatings Ltd | Dispersion agent for pigments in non-aqueous colourant preparations |
| WO2022177010A1 (en) | 2021-02-22 | 2022-08-25 | 日本ペイント・オートモーティブコーティングス株式会社 | Multi-layer coating film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1108261A (en) * | 1963-08-01 | 1968-04-03 | Ici Ltd | Novel dispersants for use in organic media |
| DE3430512A1 (en) * | 1984-08-18 | 1986-02-27 | Bayer Ag, 5090 Leverkusen | AGING AGENTS AND POLYMERS CONTAINING THEM |
| US4656226A (en) * | 1985-09-30 | 1987-04-07 | E. I. Du Pont De Nemours And Company | Acrylic pigment dispersants made by group transfer polymerization |
-
1987
- 1987-12-28 US US07/138,039 patent/US4812517A/en not_active Expired - Fee Related
-
1988
- 1988-12-15 CA CA000586053A patent/CA1304852C/en not_active Expired - Lifetime
- 1988-12-23 EP EP19880312282 patent/EP0323181A3/en not_active Ceased
- 1988-12-26 JP JP63326398A patent/JPH01204914A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0323181A2 (en) | 1989-07-05 |
| JPH01204914A (en) | 1989-08-17 |
| US4812517A (en) | 1989-03-14 |
| EP0323181A3 (en) | 1990-10-03 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |