CA1263781A - Coating composition containing polymeric surfactant - Google Patents
Coating composition containing polymeric surfactantInfo
- Publication number
- CA1263781A CA1263781A CA000505423A CA505423A CA1263781A CA 1263781 A CA1263781 A CA 1263781A CA 000505423 A CA000505423 A CA 000505423A CA 505423 A CA505423 A CA 505423A CA 1263781 A CA1263781 A CA 1263781A
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- vinyl
- anhydride
- graft
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/06—Copolymers with vinyl aromatic monomers
Abstract
ABSTRACT
A costing composition comprising:
(a) A graft copolymer, having surfactant properties, comprising the reaction product of (i) a vinyl copolymer comprising vinyl chloride, a vinyl carboxylate ester, and a source of hydroxyl groups, such that the hydroxyl content prior to reaction is about 0.5 to about 8% by weight of the vinyl copolymer and of which about 1 to about 75% of said hydroxyl groups have been reacted with (ii) an anhydride copolymer comprising the reaction product of an aromatic monomer and a dicarboxylic acid anhydride, such that the graft copolymer has a molecular weight of about 2,000 to about 30,000, and 8 vinyl copolymer/anhydride copolymer weight ratio of about 20 to about 2, of which a sufficient number of carboxyl groups have been hydrolyzed to produce surfactant properties;
(b) a dispersible powder, (c) optionally, other hard resins, (d) optionally, a rubbery polymer, (e) optionally, 8 supplemental surfactant, all mixed in an organic solvent.
A costing composition comprising:
(a) A graft copolymer, having surfactant properties, comprising the reaction product of (i) a vinyl copolymer comprising vinyl chloride, a vinyl carboxylate ester, and a source of hydroxyl groups, such that the hydroxyl content prior to reaction is about 0.5 to about 8% by weight of the vinyl copolymer and of which about 1 to about 75% of said hydroxyl groups have been reacted with (ii) an anhydride copolymer comprising the reaction product of an aromatic monomer and a dicarboxylic acid anhydride, such that the graft copolymer has a molecular weight of about 2,000 to about 30,000, and 8 vinyl copolymer/anhydride copolymer weight ratio of about 20 to about 2, of which a sufficient number of carboxyl groups have been hydrolyzed to produce surfactant properties;
(b) a dispersible powder, (c) optionally, other hard resins, (d) optionally, a rubbery polymer, (e) optionally, 8 supplemental surfactant, all mixed in an organic solvent.
Description
COATING COMPQSITIO~I
CONTAINING POLYMERIC SURFACTANT
BACKGROUND OF THE INVENTION
Coating composltions containing dispersi~le powders typically must include R dispersing agent for such powders. It ls essential that such dispersing agent be compa ible both with any binder resin in ~he coating, and with the end use o~ ~he coa~ed product~ For example, magnetiç recording tape is produced by coating a dispersion of magnetic -- particles in a binder solution onto a thermoplastic substrate~ usually polyethylene terephthalate. The quality of the tape is determlned by many factors, on~ of the most important of which is the degree to which the magnetlc pigment has been uniformly dispersed.
It is well known that the binder of a typical magnetic tape comprises a combinaeion of a soft, rubbery polymer, such as a thermoplas~ic polyurethane te.g., ~srane*5701F-l from B.F.
Goodrich) and a hard resin, such as a vinyl chloride/vinyl acet2te~vinyl alcohol terpolymer ~e.g., UCAR*Solution Vinyl Resin VAG~*from Union Carbide Corporation), in a weight ratio of about 30/70 to 70/30. Of these two types of polymers, the hard resin is typically a far better pigment-dispersing medium for the magnetic pigment, as Judged by gloss measurements, microscopic ob ervation and magnetic proper~y evaluations.
~ Nevertheless, it has s~ill been necessary to add low molecular weight, monomeric dispersing agents to formulations of magnetlc pigment in * Tr a de Ma r k s , -~
. .
D-14, 272 ~ 3~1 solutions of VAGH in order adequately to disperse the pigment.
The need for these low moiecular weight dispersants ln order to achieve a high degree of dispersion is a sericus problem since these materials are capable of exudin~ to the tape surface on aging, resulting in "dropouts," plasticization of the tspe surface, fouling of the record~playbsck heads, and other problems.
SUMMARY OF THE INVENTION
It has now been found that excellent dispersion of dispersible powder, e~g., magnetic pigment, can be achleved by use of the graft polymeric surfactant of this invention.
Accordingly, this invention provldes a coating composition comprising:
(a) a graft copolymer? having surfactant properties, comprising the reaction product of (i) a vinyl copolymer comprising vinyl chloride, a vinyl carboxylate ester, and a source of hydroxyl 8roUPs~ such that the hydroxyl content prior to reaction is about 0.5 to about 8 by weight of the vinyl copolymer and of which about 1 to about 75% of said hydroxyl groups have been reacted with (ii~ an anhydride copolymer comprising the reaction product of an aromatic monomer and a dicarboxylic acid anhydrlde, such that the ~raft copolymer has a molecular weight of about 2,000 to about 30,000, pref rably abut 15,000 to about 25,000, and a vinyl D-14,272 .~
copolymer/anhydride copolymer weight ratio of about 20 ~o about 2, preferably about 5 to ~bout Z, of which a sufficlent number of car~oxyl groups have been hydrolyzed to produce surfactant properties~
(ba ~ dlsperslble powder, (c) option~lly, ~ rubbery polymer, (d) optionally, other h~rd reslns, (e) optionally, a supplemental surfactant, and (f) optionally, other material~ known to the art, all mixed in an organic solvent.
As used herein, the term "molecular weight"
refers tn the number ~verage molecul~r welght (Mn).
The 8ra~ copolymer of this lnven~ion ~chieves lts benefits b~ incorporating an effective level of s~rfactant properties ~nto a relatively high molecu~r weight polymeric structure, thereby eliminating or greatly reducln~ unwanted migration of the dispersant.
DESCRIPTION OF THE INVENTION
The procedures for preparing the graf t copolymer of this inventlon are described in detail ln U.S. Pate.~t No. 4,511,682. The graft copolymer may be prepared, as desired, in solvent-borne (i~e., solution) form suitable for direct use, or in dry powder form suitable direct use, or in dry powder form suitable addition to an appropriate liquid medium.
D-14.272 ~37'8~
The general procedure for preparing the solvent-borne graf e copolymer involves mixing the vinyl copolymer ~ith the anhydride copolymer in a suitable nonreactive solvent, in the presence of a catalyst, raising the temperature to a po~nt a~
which the grafting reaction will occur, and carrying out the reaction essentially to completion. The reaction product is thereafter hydrolyzed by addition of water, followed by dehydration ~e.g., under vacuum), to produce a solvent solution ~Xnown as a "varnish"). While the vinyl copolymer can be a tetrapolymer, thé preferred materials are terpolymers, especially of vinyl chloride, vinyl acetate, and vinyl alcohol. Examples of suitable terpolymers are those sold by Union Carbide Corporation under the trade designations UCAR "VAGH"
and "VYES*" The molecular weight of the vinyl copolymer may range of from about 2,000 to about 25,000; however, the range about 3,500 to about 24,000 is especially preferred. The grafting reaction occurs through the hydroxyl ~roups (preferably, secondary alcohol groups) of the vinyl copolymer; accordingly, it should contain at least about 0.5Z, preferably about 2 to about 3%, hydroxyl functionallty. For example, resin VAGH has a number average molecular weight of about 23,000 and a secondary hydroxyl content of about 2.3~, and resin VYES has a number average molecular weight of about 4,000 and a hydroxyl content of about 3.0~. Sources for tne hydroxyl functlonality include, e.g., vinyl elcohol and hydroxyalkyl esters, such as hydroxyethyl and hydroxypropyl acrylates and * ~rade Mark D-14,Z72 3, ., ~26~8~
methacrylates. The anhydride copolymer may be a terpolymer, but is pre~erably a reaction product of, e.g., styrene and maleic anhydride, having a molecular weight ranging from about 1200 to ~bout 250Q, preferably about 1500 to about 2000, and an aromatic/anhydride molar ratio ranging from about 4/1 to about 0.5/1, preferably from about 3/1 to about 1/1. Of particular interest are those copolymers of styrene ~nd maleic ~nhydride, and styrene-maleic anhydride half-ester terpolymers, sold under the trade designation "SMA." For example, SMA-300U has a styrene/maleic anhydride ratio of about 3/1 and a number average molecular weight of about 1,900, while SMA-1000 has a styrene/maleic anhydride ratio of ~bout 1/1 and a number average molecular weight of about 1600.
While the choice of nonreactive solvent is not narrowly cri~ical, some routine experimentation may be desirable in order ~o optimize the solvent in any particular reaction system. Cyclohexanone is especi~lly preferred, although other common solvents, such as methyl acetate (MeAc), tetr~hydrofuran (THF), and methylethyl ketone (MEK), may also be used; acetone is considered less desirable since it tends to produce erratic results as to the degree of grafting (i.e., esterification).
The catalyst may be any material suitable for catalyzlng the gra~ting reaction; preferred, however, are amines, especially the alkyl amines, such as triethylamine (TEA). The amines have the additional advantage ~hat, when used in sufficient quantlty, they will provide formation of a water-soluble salt, should such be desired.
D-14,272 ~26~3781 ~ 6 -The general procedure for producing a dry powder of the graft surfactant of this invention is similar to that described above, except that the hydrolysis ls followed by neutrali~ation, precipitation and recovery Or the solids. In the preparation of the powder form, it is desirable to utilize a very volatile solvent, such`as acetone, as the reaction medium. The use of acetone, in particular, can be facilitated by use of a relatively low molecular weight anhydride copolymer, such as SMA-1000. Neutralization can be readily accomplished by addit~on of a reasonably strong acid, e.g., a 50~ aqueous solution of an inorganic acid, such as HCl. Precipitation may be performed by adding the varnish to a rapidly agitated mixture of an alcohol and water. Recovery of the solids is by routine techniques of flltration, washing, and drying. The dry powder is then suitable for long-term storage, and eventual use in a liquid medium as a dispersant.
Although the graft copolymeric dispersant of this invention is not necessarily limited to use in connection with magnetic powder-containing coatings, it is particularly useful for that purpose, and will be so illust.ated.
It has been found that percent gloss of a magnetic pigment-bearing film is a reliable indicator of the uniformity of the pigment dispersion, and thus of the efficiency of the dispersant. Percent gloss is measured by the well-known procedure using a Garnder "Glossgard" IIA
60 gloss meter, available from Pacific Scientific.
* Trade Mark ~-14,272 ~2~
In the examples which follow, "Pferrox"
2228-HC is a gPmma-ferric oxlde powder, ~nd "Pferrox" 2566 is a cobalt-modified ferric oxlde powder, both available from Pfizer, Inc. "Estane"
5701 ls a rubbery urethane resin available from B.F.
Goodrich. "Gafac~' RE-510 is a monomeric surfactant available from GAF Corporation. Dispersions were prepared in a Premier SMA RS II*mill using 1.0-1.3 mm glass beads as the grindIng medium and a grlnd time of one hour. Cyclohexanone was used as the solvent for the system, and was ~djus~ed to give a final viscoslty of i,000-20,000 cs (Brookfield LVT, , 12 rpm at roo~ temperature).
ExamPle 1 Resin SYnthesis Vinyl/SMA grafts were made as either resin solutions or preclpitated powders. Resin formulations are shown in Table 1. Procedures are described below:
Graft A - The reaction was carried out ~or
CONTAINING POLYMERIC SURFACTANT
BACKGROUND OF THE INVENTION
Coating composltions containing dispersi~le powders typically must include R dispersing agent for such powders. It ls essential that such dispersing agent be compa ible both with any binder resin in ~he coating, and with the end use o~ ~he coa~ed product~ For example, magnetiç recording tape is produced by coating a dispersion of magnetic -- particles in a binder solution onto a thermoplastic substrate~ usually polyethylene terephthalate. The quality of the tape is determlned by many factors, on~ of the most important of which is the degree to which the magnetlc pigment has been uniformly dispersed.
It is well known that the binder of a typical magnetic tape comprises a combinaeion of a soft, rubbery polymer, such as a thermoplas~ic polyurethane te.g., ~srane*5701F-l from B.F.
Goodrich) and a hard resin, such as a vinyl chloride/vinyl acet2te~vinyl alcohol terpolymer ~e.g., UCAR*Solution Vinyl Resin VAG~*from Union Carbide Corporation), in a weight ratio of about 30/70 to 70/30. Of these two types of polymers, the hard resin is typically a far better pigment-dispersing medium for the magnetic pigment, as Judged by gloss measurements, microscopic ob ervation and magnetic proper~y evaluations.
~ Nevertheless, it has s~ill been necessary to add low molecular weight, monomeric dispersing agents to formulations of magnetlc pigment in * Tr a de Ma r k s , -~
. .
D-14, 272 ~ 3~1 solutions of VAGH in order adequately to disperse the pigment.
The need for these low moiecular weight dispersants ln order to achieve a high degree of dispersion is a sericus problem since these materials are capable of exudin~ to the tape surface on aging, resulting in "dropouts," plasticization of the tspe surface, fouling of the record~playbsck heads, and other problems.
SUMMARY OF THE INVENTION
It has now been found that excellent dispersion of dispersible powder, e~g., magnetic pigment, can be achleved by use of the graft polymeric surfactant of this invention.
Accordingly, this invention provldes a coating composition comprising:
(a) a graft copolymer? having surfactant properties, comprising the reaction product of (i) a vinyl copolymer comprising vinyl chloride, a vinyl carboxylate ester, and a source of hydroxyl 8roUPs~ such that the hydroxyl content prior to reaction is about 0.5 to about 8 by weight of the vinyl copolymer and of which about 1 to about 75% of said hydroxyl groups have been reacted with (ii~ an anhydride copolymer comprising the reaction product of an aromatic monomer and a dicarboxylic acid anhydrlde, such that the ~raft copolymer has a molecular weight of about 2,000 to about 30,000, pref rably abut 15,000 to about 25,000, and a vinyl D-14,272 .~
copolymer/anhydride copolymer weight ratio of about 20 ~o about 2, preferably about 5 to ~bout Z, of which a sufficlent number of car~oxyl groups have been hydrolyzed to produce surfactant properties~
(ba ~ dlsperslble powder, (c) option~lly, ~ rubbery polymer, (d) optionally, other h~rd reslns, (e) optionally, a supplemental surfactant, and (f) optionally, other material~ known to the art, all mixed in an organic solvent.
As used herein, the term "molecular weight"
refers tn the number ~verage molecul~r welght (Mn).
The 8ra~ copolymer of this lnven~ion ~chieves lts benefits b~ incorporating an effective level of s~rfactant properties ~nto a relatively high molecu~r weight polymeric structure, thereby eliminating or greatly reducln~ unwanted migration of the dispersant.
DESCRIPTION OF THE INVENTION
The procedures for preparing the graf t copolymer of this inventlon are described in detail ln U.S. Pate.~t No. 4,511,682. The graft copolymer may be prepared, as desired, in solvent-borne (i~e., solution) form suitable for direct use, or in dry powder form suitable direct use, or in dry powder form suitable addition to an appropriate liquid medium.
D-14.272 ~37'8~
The general procedure for preparing the solvent-borne graf e copolymer involves mixing the vinyl copolymer ~ith the anhydride copolymer in a suitable nonreactive solvent, in the presence of a catalyst, raising the temperature to a po~nt a~
which the grafting reaction will occur, and carrying out the reaction essentially to completion. The reaction product is thereafter hydrolyzed by addition of water, followed by dehydration ~e.g., under vacuum), to produce a solvent solution ~Xnown as a "varnish"). While the vinyl copolymer can be a tetrapolymer, thé preferred materials are terpolymers, especially of vinyl chloride, vinyl acetate, and vinyl alcohol. Examples of suitable terpolymers are those sold by Union Carbide Corporation under the trade designations UCAR "VAGH"
and "VYES*" The molecular weight of the vinyl copolymer may range of from about 2,000 to about 25,000; however, the range about 3,500 to about 24,000 is especially preferred. The grafting reaction occurs through the hydroxyl ~roups (preferably, secondary alcohol groups) of the vinyl copolymer; accordingly, it should contain at least about 0.5Z, preferably about 2 to about 3%, hydroxyl functionallty. For example, resin VAGH has a number average molecular weight of about 23,000 and a secondary hydroxyl content of about 2.3~, and resin VYES has a number average molecular weight of about 4,000 and a hydroxyl content of about 3.0~. Sources for tne hydroxyl functlonality include, e.g., vinyl elcohol and hydroxyalkyl esters, such as hydroxyethyl and hydroxypropyl acrylates and * ~rade Mark D-14,Z72 3, ., ~26~8~
methacrylates. The anhydride copolymer may be a terpolymer, but is pre~erably a reaction product of, e.g., styrene and maleic anhydride, having a molecular weight ranging from about 1200 to ~bout 250Q, preferably about 1500 to about 2000, and an aromatic/anhydride molar ratio ranging from about 4/1 to about 0.5/1, preferably from about 3/1 to about 1/1. Of particular interest are those copolymers of styrene ~nd maleic ~nhydride, and styrene-maleic anhydride half-ester terpolymers, sold under the trade designation "SMA." For example, SMA-300U has a styrene/maleic anhydride ratio of about 3/1 and a number average molecular weight of about 1,900, while SMA-1000 has a styrene/maleic anhydride ratio of ~bout 1/1 and a number average molecular weight of about 1600.
While the choice of nonreactive solvent is not narrowly cri~ical, some routine experimentation may be desirable in order ~o optimize the solvent in any particular reaction system. Cyclohexanone is especi~lly preferred, although other common solvents, such as methyl acetate (MeAc), tetr~hydrofuran (THF), and methylethyl ketone (MEK), may also be used; acetone is considered less desirable since it tends to produce erratic results as to the degree of grafting (i.e., esterification).
The catalyst may be any material suitable for catalyzlng the gra~ting reaction; preferred, however, are amines, especially the alkyl amines, such as triethylamine (TEA). The amines have the additional advantage ~hat, when used in sufficient quantlty, they will provide formation of a water-soluble salt, should such be desired.
D-14,272 ~26~3781 ~ 6 -The general procedure for producing a dry powder of the graft surfactant of this invention is similar to that described above, except that the hydrolysis ls followed by neutrali~ation, precipitation and recovery Or the solids. In the preparation of the powder form, it is desirable to utilize a very volatile solvent, such`as acetone, as the reaction medium. The use of acetone, in particular, can be facilitated by use of a relatively low molecular weight anhydride copolymer, such as SMA-1000. Neutralization can be readily accomplished by addit~on of a reasonably strong acid, e.g., a 50~ aqueous solution of an inorganic acid, such as HCl. Precipitation may be performed by adding the varnish to a rapidly agitated mixture of an alcohol and water. Recovery of the solids is by routine techniques of flltration, washing, and drying. The dry powder is then suitable for long-term storage, and eventual use in a liquid medium as a dispersant.
Although the graft copolymeric dispersant of this invention is not necessarily limited to use in connection with magnetic powder-containing coatings, it is particularly useful for that purpose, and will be so illust.ated.
It has been found that percent gloss of a magnetic pigment-bearing film is a reliable indicator of the uniformity of the pigment dispersion, and thus of the efficiency of the dispersant. Percent gloss is measured by the well-known procedure using a Garnder "Glossgard" IIA
60 gloss meter, available from Pacific Scientific.
* Trade Mark ~-14,272 ~2~
In the examples which follow, "Pferrox"
2228-HC is a gPmma-ferric oxlde powder, ~nd "Pferrox" 2566 is a cobalt-modified ferric oxlde powder, both available from Pfizer, Inc. "Estane"
5701 ls a rubbery urethane resin available from B.F.
Goodrich. "Gafac~' RE-510 is a monomeric surfactant available from GAF Corporation. Dispersions were prepared in a Premier SMA RS II*mill using 1.0-1.3 mm glass beads as the grindIng medium and a grlnd time of one hour. Cyclohexanone was used as the solvent for the system, and was ~djus~ed to give a final viscoslty of i,000-20,000 cs (Brookfield LVT, , 12 rpm at roo~ temperature).
ExamPle 1 Resin SYnthesis Vinyl/SMA grafts were made as either resin solutions or preclpitated powders. Resin formulations are shown in Table 1. Procedures are described below:
Graft A - The reaction was carried out ~or
2 hours at 82C, after which 30g. water were added and hydrolysls conducted for 4 hours at 74~C. The product was then vacuum dehydrated to remove the remaining water. The product was A clear amber solution with 8 solids content of 17.8~ and viscoslty of 38~ cP.
Graft B - The reaction was conducted for 2 hours at 56C, after which 4.3g. water were added snd the product allowed to cool overnight. The next day, 6g. of HCl/H20 (1/1 wt.) were added and stirred for 15 minutes. The product was precipitated by adding lOOg. portions to 100 cc of a * Trade Mark D-14,272 4/l (vol.) blend of methanol/H20 in a Waring blender. After one minute of mixing, 100 cc H20 were added ~nd mixlng continued another minute. The precipitate was washed tw~ce with 150 cc water, mixing for 1 minute in the blender and filtering.
The precipitate was broken up and dried at ~mbient temperature and pressure.
Graft C - The reaction was carried out for 2 hours at reflux (57c), after whi~h 23.0 grams water were added and reflux continued for 4 l/4 hours. The product was precipitated as in Graft B.
Graft D - The reaction was carried out for 2 hours at 81C, after which 21.5g. H20 were ~dded ~nd heating continued for 2 more hours at 76C. The excess water was removed by vacuum distlllation.
Graft E - The reaction was carried out for 2 hours at 81C, after which $4~5g. H20 were added and heating continued for 2 more hours at 81C. The excess water was removed by vacuum distillation.
raft F - The reaction was carried out for 2 hours at reflux (66C). Half the trlethylamine was added at ~he start and the other half after 1 1/4 hours. Water (26g,) was added and heating continued for 3 hours snd 10 minutes, at which point 150g. cyclohexanone were ~dded. The acetone and water were removed by vacuum distillatlon, following which 150g. cyclohexanone were added. A clear solution with solids content of 33.9~ was obtained.
Graft G - The reaction was conducted for 2 hours and 20 minutes ~t 66-69C, after which 26.0 grams water were added and reacted for 3 hours ~t 68C. The excess water was removed by vacuum distill~tion.
.. .
D-14,272 All graft resins were obtained as clear solutions except resins B and C; these latter resins were powders which then were dissolved in the solvent for coating.
Example 2 Ma~netic Media Coatin~ Formulation - The general procedure used to prepared the magnetic media formulations describ~d below is as follows:
l. 160g of cyclohexanone, the indicated amount of binder resin solution (as a 15~ total solids solution in cyclohexanone), and the indicated amount of GAFAC RE-610 dispersant are added to a quart ~ar and mixed wlth an air stirrer.
2. 200g of magnetic pigment are added slowly with stirring and stirring is continued for 5-lO minutes.
Graft B - The reaction was conducted for 2 hours at 56C, after which 4.3g. water were added snd the product allowed to cool overnight. The next day, 6g. of HCl/H20 (1/1 wt.) were added and stirred for 15 minutes. The product was precipitated by adding lOOg. portions to 100 cc of a * Trade Mark D-14,272 4/l (vol.) blend of methanol/H20 in a Waring blender. After one minute of mixing, 100 cc H20 were added ~nd mixlng continued another minute. The precipitate was washed tw~ce with 150 cc water, mixing for 1 minute in the blender and filtering.
The precipitate was broken up and dried at ~mbient temperature and pressure.
Graft C - The reaction was carried out for 2 hours at reflux (57c), after whi~h 23.0 grams water were added and reflux continued for 4 l/4 hours. The product was precipitated as in Graft B.
Graft D - The reaction was carried out for 2 hours at 81C, after which 21.5g. H20 were ~dded ~nd heating continued for 2 more hours at 76C. The excess water was removed by vacuum distlllation.
Graft E - The reaction was carried out for 2 hours at 81C, after which $4~5g. H20 were added and heating continued for 2 more hours at 81C. The excess water was removed by vacuum distillation.
raft F - The reaction was carried out for 2 hours at reflux (66C). Half the trlethylamine was added at ~he start and the other half after 1 1/4 hours. Water (26g,) was added and heating continued for 3 hours snd 10 minutes, at which point 150g. cyclohexanone were ~dded. The acetone and water were removed by vacuum distillatlon, following which 150g. cyclohexanone were added. A clear solution with solids content of 33.9~ was obtained.
Graft G - The reaction was conducted for 2 hours and 20 minutes ~t 66-69C, after which 26.0 grams water were added and reacted for 3 hours ~t 68C. The excess water was removed by vacuum distill~tion.
.. .
D-14,272 All graft resins were obtained as clear solutions except resins B and C; these latter resins were powders which then were dissolved in the solvent for coating.
Example 2 Ma~netic Media Coatin~ Formulation - The general procedure used to prepared the magnetic media formulations describ~d below is as follows:
l. 160g of cyclohexanone, the indicated amount of binder resin solution (as a 15~ total solids solution in cyclohexanone), and the indicated amount of GAFAC RE-610 dispersant are added to a quart ~ar and mixed wlth an air stirrer.
2. 200g of magnetic pigment are added slowly with stirring and stirring is continued for 5-lO minutes.
3. The resulting slurry is charge~ to the ; Premier Mill and ground in the mlll for one hour.
4. The formulation is discharged and applied with a draw-down bar to produce a l-mil wet coating on glass.
5. After air drying, the 60 gloss of the coating ~s tested.
In the Tables below, the amounts of resin and dispersant are shown as welght percen~ of the component, on a solids basis, relative to the amount of pigment in the formulation. Therefore, 8 formulation described RS VAGH (10), GAFAC (l), Pferrico 2566 would actually contain the following ingredients:
D-14,272 ~Z6~7~1 In~redient Amount Solids Cyclohexanone 160g VAGH ~15~ in Cyclohexanone 134g 20g GAFAC RE-610 2g 2g Pferrico 2566 200g ~OOg D-14,272 ~63'7~
TABLE I
MAGNETIC PIGMENT COATINGS
Binder Graft Final Composltion Components ~%)~ Resin SMA** ~%) Gloss 1 VAGH/SMA (10) A 3000(20~101 2 VAGH/SMA, VAGH, Estane A 3000(20)79 5701 ~3.8,2.2,4) 3 VAGH/SMA, Estane B 3000(20) 95 5701F (6,4) 4 VAGH~SMA (10) D 3000~5) 71 VAGH/SMA (10) E 3000(40)90
In the Tables below, the amounts of resin and dispersant are shown as welght percen~ of the component, on a solids basis, relative to the amount of pigment in the formulation. Therefore, 8 formulation described RS VAGH (10), GAFAC (l), Pferrico 2566 would actually contain the following ingredients:
D-14,272 ~Z6~7~1 In~redient Amount Solids Cyclohexanone 160g VAGH ~15~ in Cyclohexanone 134g 20g GAFAC RE-610 2g 2g Pferrico 2566 200g ~OOg D-14,272 ~63'7~
TABLE I
MAGNETIC PIGMENT COATINGS
Binder Graft Final Composltion Components ~%)~ Resin SMA** ~%) Gloss 1 VAGH/SMA (10) A 3000(20~101 2 VAGH/SMA, VAGH, Estane A 3000(20)79 5701 ~3.8,2.2,4) 3 VAGH/SMA, Estane B 3000(20) 95 5701F (6,4) 4 VAGH~SMA (10) D 3000~5) 71 VAGH/SMA (10) E 3000(40)90
6 VAGH/SMA, Estane C 1000~20) 90 7501F-1 (6,4)
7 VAGH/SMA, Estane C 1000(20) 86 5701F-1 (4,6)
8 VAGH/SMA, Estane C 1000(20) 80 5701F-1 (2.5,7.5~
Binder components are recorded as weight percent based on magnetic pigment, Pferrox 2566. Final gloss is 60 degree gloss messured after 1 Aour milling time.
** SMA is recorded as the S~A type and the weight percent based on vinyl.
D-14,272 ~ ~37~31 It is an additional feature of the graft resins of ~his invention that their benefits as dispersants are retained even when they are blended with other binder materi~ls. This feature is lllustrated in example 3.
Example 3 Magnetic media coatings were prepared as described above, except that the graft ~opolymer w~s blended with a non-grafted binder polymer of the prior art, i.e., VAGH. The data are shown in Table II.
TABLE II
Gloss of CoatinRs with Mixed Graft/Non-~raft Binders Estane 5701/
VAGH VA~H/Graft Graft/VAGH, GAFAC(Control2 l/l 2/211 2~ lO0 103 --1% 30-50 90 90 From the results shown in Examples l and 2 it is apparent that the degree of dispersion, as ~udged by gloss (or by microscoplc ex~min~tion), is excellent even in the absence of a supplemental dispersant.
It has been observed that the effectiveness of the graft copolymer as a dispersant appears to decresse when the molecular weight of vi~yl copolymer ls too low. This effect is illustrated in Exsmple 4.
D-14,272 ~2~378 ExamPle 4 Magnetic media coatings were prepared as described above, except that the graft copolymer was prepared from relatively low molecular weight vinyl polymers. The data are shown in Table III.
TABLE III
CoatinRs from Grafts of Lower_Molecular Wei~ht Vlnyls Binder Components Molecular* SMA Final (%) Wei~ht (%) Gloss XVO-6/SMA(10) ~,000 300~(20) 60 VYES/SMA (10) 4,000 3000(20) 107 * Molecular weight ~Mn) of vinyl component prior to gr~ftin~.
T~ble III 111ustrates that gloss is unsatisf2ctory when a vlnyl polymer of molec~lar weight 2,000 or lower is used in preparing the grsft copolymer.
D-14,272
Binder components are recorded as weight percent based on magnetic pigment, Pferrox 2566. Final gloss is 60 degree gloss messured after 1 Aour milling time.
** SMA is recorded as the S~A type and the weight percent based on vinyl.
D-14,272 ~ ~37~31 It is an additional feature of the graft resins of ~his invention that their benefits as dispersants are retained even when they are blended with other binder materi~ls. This feature is lllustrated in example 3.
Example 3 Magnetic media coatings were prepared as described above, except that the graft ~opolymer w~s blended with a non-grafted binder polymer of the prior art, i.e., VAGH. The data are shown in Table II.
TABLE II
Gloss of CoatinRs with Mixed Graft/Non-~raft Binders Estane 5701/
VAGH VA~H/Graft Graft/VAGH, GAFAC(Control2 l/l 2/211 2~ lO0 103 --1% 30-50 90 90 From the results shown in Examples l and 2 it is apparent that the degree of dispersion, as ~udged by gloss (or by microscoplc ex~min~tion), is excellent even in the absence of a supplemental dispersant.
It has been observed that the effectiveness of the graft copolymer as a dispersant appears to decresse when the molecular weight of vi~yl copolymer ls too low. This effect is illustrated in Exsmple 4.
D-14,272 ~2~378 ExamPle 4 Magnetic media coatings were prepared as described above, except that the graft copolymer was prepared from relatively low molecular weight vinyl polymers. The data are shown in Table III.
TABLE III
CoatinRs from Grafts of Lower_Molecular Wei~ht Vlnyls Binder Components Molecular* SMA Final (%) Wei~ht (%) Gloss XVO-6/SMA(10) ~,000 300~(20) 60 VYES/SMA (10) 4,000 3000(20) 107 * Molecular weight ~Mn) of vinyl component prior to gr~ftin~.
T~ble III 111ustrates that gloss is unsatisf2ctory when a vlnyl polymer of molec~lar weight 2,000 or lower is used in preparing the grsft copolymer.
D-14,272
Claims (7)
1. A coating composition comprising:
(a) a graft copolymer, having surfactant properties, comprising the reaction product of (i) a vinyl copolymer comprising vinyl chloride, a vinyl carboxylate ester, and a source of hydroxyl groups, such that the hydroxyl content prior to reaction is about 0.5 to about 8% by weight of the vinyl copolymer and of which about 1 to about 75% of said hydroxyl groups have been reacted with (ii) an anhydride copolymer comprising the reaction product of styrene and a dicarboxylic acid anhydride, such that the graft copolymer has a molecular weight of about 2,000 to about 30,000, and a vinyl copolymer/anhydride copolymer weight ratio of about 20 to about 2, of which a sufficient number of carboxyl groups have been hydrolyzed to produce surfactant properties and a magnetic powder.
(a) a graft copolymer, having surfactant properties, comprising the reaction product of (i) a vinyl copolymer comprising vinyl chloride, a vinyl carboxylate ester, and a source of hydroxyl groups, such that the hydroxyl content prior to reaction is about 0.5 to about 8% by weight of the vinyl copolymer and of which about 1 to about 75% of said hydroxyl groups have been reacted with (ii) an anhydride copolymer comprising the reaction product of styrene and a dicarboxylic acid anhydride, such that the graft copolymer has a molecular weight of about 2,000 to about 30,000, and a vinyl copolymer/anhydride copolymer weight ratio of about 20 to about 2, of which a sufficient number of carboxyl groups have been hydrolyzed to produce surfactant properties and a magnetic powder.
2. A composition of claim 1 wherein the vinyl carboxylate ester is vinyl acetate.
3. A composition of claim 1 wherein about 2 to about 20% of the hydroxyl groups have been reacted.
4. A composition of claim 1 wherein the acid anhydride is maleic anhydride.
5. A composition of claim 4 wherein the anhydride copolymer has a molecular weight of about 1,500 to about 2,000.
6. A composition of claim 1 wherein the graft copolymer has a molecular weight of about 15,000 to about 25,000.
7. A composition of claim 1 wherein the vinyl copolymer/anhydride copolymer ratio is about 5 to about 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US718,369 | 1985-04-01 | ||
| US06/718,369 US4558095A (en) | 1985-04-01 | 1985-04-01 | Coating composition containing polymeric surfactant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1263781A true CA1263781A (en) | 1989-12-05 |
Family
ID=24885846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000505423A Expired CA1263781A (en) | 1985-04-01 | 1986-03-27 | Coating composition containing polymeric surfactant |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4558095A (en) |
| EP (1) | EP0198307B1 (en) |
| JP (1) | JPS61264064A (en) |
| KR (1) | KR910005682B1 (en) |
| AT (1) | ATE48440T1 (en) |
| AU (1) | AU588295B2 (en) |
| BR (1) | BR8601427A (en) |
| CA (1) | CA1263781A (en) |
| DE (1) | DE3667295D1 (en) |
| DK (1) | DK146886A (en) |
| ES (1) | ES8801327A1 (en) |
| NO (1) | NO861278L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL134482A (en) * | 1999-02-16 | 2002-12-01 | Dainichiseika Color Chem | Pigment dispersions and writing instruments and printers with the dispersions stored therein |
| ATE414132T1 (en) | 2003-06-11 | 2008-11-15 | Ciba Spec Chem Water Treat Ltd | POLYMERIC SURFACTANT |
| WO2016122648A1 (en) | 2015-01-30 | 2016-08-04 | Hewlett-Packard Development Company, L.P. | Ink composition including a modified polymer or copolymer additive |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3219729A (en) * | 1961-09-27 | 1965-11-23 | Glidden Co | Mixed neutral vinyl resin/reactive vinyl resin coating compositions, and cans and/or container components coated therewith |
| US3296230A (en) * | 1963-10-31 | 1967-01-03 | Goodrich Co B F | Process for making heat-stable hydroxyl-containing vinyl polymer |
| US3914333A (en) * | 1973-12-19 | 1975-10-21 | Ford Motor Co | Powder coating compositions comprising a blend of coreactive polymers - II |
| US3966672A (en) * | 1974-11-20 | 1976-06-29 | Atlantic Richfield Company | Preparation of carboxyl-containing polymers and composites thereof with hydroxyl-containing materials |
| US4452948A (en) * | 1980-09-10 | 1984-06-05 | The International Paint Company Limited | Coating composition comprising a hydroxy component, an anhydride component and a catalyst |
| JPS58114330A (en) * | 1981-12-28 | 1983-07-07 | Denki Kagaku Kogyo Kk | Magnetic coating for magnetic recording medium |
| JPS59177727A (en) * | 1983-03-25 | 1984-10-08 | Tdk Corp | Magnetic recording medium |
| US4511682A (en) * | 1983-06-28 | 1985-04-16 | Union Carbide Corporation | Water-dispersible coating compositions and process |
-
1985
- 1985-04-01 US US06/718,369 patent/US4558095A/en not_active Expired - Fee Related
-
1986
- 1986-03-27 CA CA000505423A patent/CA1263781A/en not_active Expired
- 1986-03-31 BR BR8601427A patent/BR8601427A/en unknown
- 1986-04-01 NO NO861278A patent/NO861278L/en unknown
- 1986-04-01 AU AU55523/86A patent/AU588295B2/en not_active Ceased
- 1986-04-01 JP JP61072665A patent/JPS61264064A/en active Granted
- 1986-04-01 DK DK146886A patent/DK146886A/en not_active Application Discontinuation
- 1986-04-01 AT AT86104393T patent/ATE48440T1/en not_active IP Right Cessation
- 1986-04-01 DE DE8686104393T patent/DE3667295D1/en not_active Expired - Lifetime
- 1986-04-01 KR KR1019860002459A patent/KR910005682B1/en not_active IP Right Cessation
- 1986-04-01 ES ES553581A patent/ES8801327A1/en not_active Expired
- 1986-04-01 EP EP86104393A patent/EP0198307B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| KR910005682B1 (en) | 1991-08-01 |
| EP0198307A1 (en) | 1986-10-22 |
| AU588295B2 (en) | 1989-09-14 |
| BR8601427A (en) | 1986-12-09 |
| NO861278L (en) | 1986-10-02 |
| JPS61264064A (en) | 1986-11-21 |
| DK146886D0 (en) | 1986-04-01 |
| DK146886A (en) | 1986-10-02 |
| ES553581A0 (en) | 1987-12-16 |
| KR860008228A (en) | 1986-11-14 |
| DE3667295D1 (en) | 1990-01-11 |
| AU5552386A (en) | 1986-10-09 |
| EP0198307B1 (en) | 1989-12-06 |
| US4558095A (en) | 1985-12-10 |
| ES8801327A1 (en) | 1987-12-16 |
| JPH0353343B2 (en) | 1991-08-14 |
| ATE48440T1 (en) | 1989-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5147934A (en) | Thermosetting powdery coating composition | |
| US5661207A (en) | Carboxylic-acid functional polyurethane polymers and their use in magnetic recording media | |
| JP3664728B2 (en) | Comb pigment dispersant | |
| EP0690883B1 (en) | Aqueous graft copolymer pigment dispersants | |
| JP2002179978A (en) | Aqueous graft copolymer dispersing agent for pigment | |
| US5492959A (en) | Blends of polyesters and alkylhydroxy (meth)acrylate compounds | |
| US4209435A (en) | Dispersion preparation | |
| US4059557A (en) | Polymer dispersions | |
| CA1263781A (en) | Coating composition containing polymeric surfactant | |
| US5512651A (en) | Strong carboxylic acid functional polyurethane polymers and blends thereof used in magnetic recording media | |
| US4770941A (en) | Magnetic recording medium and a coating composition therefor | |
| JPH09188823A (en) | Crosslinkable composition | |
| US3887642A (en) | Powdered thermosetting compositions | |
| US6114439A (en) | Crosslinkable aqueous polyester emulsion and process for preparing the same | |
| EP0702709A1 (en) | Anhydride-epoxy coating composition modified with a fluoropolymer | |
| US3642510A (en) | Process for preparing titanium oxide pigment having high dispersibility in hydrophobic systems | |
| US3758428A (en) | Acrylic coating compositions | |
| US3790523A (en) | Process for preparing acrylic organosol coating compositions | |
| US3349050A (en) | Coating composition | |
| CA1288881C (en) | Phosphorylated reaction products and compositions incorporating such products | |
| JPH0734255B2 (en) | Magnetic recording medium | |
| JPS6083219A (en) | Binder for magnetic recording body | |
| JPH0422188B2 (en) | ||
| JPH06295424A (en) | Binder for magnetic recording body | |
| JPH08291263A (en) | Powder coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |