CA1277080C - Crosslinked polymers with lowered resistivity and materials and methods for their preparation - Google Patents
Crosslinked polymers with lowered resistivity and materials and methods for their preparationInfo
- Publication number
- CA1277080C CA1277080C CA000538066A CA538066A CA1277080C CA 1277080 C CA1277080 C CA 1277080C CA 000538066 A CA000538066 A CA 000538066A CA 538066 A CA538066 A CA 538066A CA 1277080 C CA1277080 C CA 1277080C
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- Prior art keywords
- polymer
- agent
- crosslinking
- crosslinking agent
- ity
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
Abstract
CROSSLINKED POLYMERS WITH
LOWERED RESISTIVITY AND MATERIALS AND
METHODS FOR THEIR PREPARATION
Abstract New crosslinked polymers are prepared from a combination of starting materials comprising a polymer, a crosslinking agent for the polymer, and a conductivity agent containing a quaternary ammonium moiety. The conductivity agent contains at least one functional group which, during an otherwise typical process of crosslinking the polymer through the crosslinking agent, reacts to bond the conductivity agent covalently and pendently to the crosslinking agent or the polymer. The resultant crosslinked polymer has lower electrical resistivity due to inclusion of the conductivity agent.
LOWERED RESISTIVITY AND MATERIALS AND
METHODS FOR THEIR PREPARATION
Abstract New crosslinked polymers are prepared from a combination of starting materials comprising a polymer, a crosslinking agent for the polymer, and a conductivity agent containing a quaternary ammonium moiety. The conductivity agent contains at least one functional group which, during an otherwise typical process of crosslinking the polymer through the crosslinking agent, reacts to bond the conductivity agent covalently and pendently to the crosslinking agent or the polymer. The resultant crosslinked polymer has lower electrical resistivity due to inclusion of the conductivity agent.
Description
708l~) CROSSLINKED POLYMERS WITH
LOWERED RESISTI~ITY ~ND M~TERI~LS ~ND
METHODS FOR THEIR PREP~R~TION
The in~ention relates to cro~slinked polymers that ha~e a desired leuel o~ electrical resistiuity and to methods and combin~tion~ of starting materials useful to prepare such polyrn0rs.
More particularly, the inuention concerns imparting a desired de~ree of permanent conducti~ity to crosslinked polymers simply and accuratel~ during their crosslinking reaction.
Crosslinked polymers are useful for many purposes, such as those where structural integrity, resistance to flow, toughness, or durability are important. One significant area of use is in protectiue or decorative coatings, such as paints.
In many such uses te.g., as paint coatings for electrographic copiers or other electrical apparatus, ~or aircraft, and for high speed manufacturing ~o apparatus such as photographic coating machines) buildup of electrostatic charges on surfaces coated with such paints could cause serious problems. Many crosslinked polymers hauing other desirable properties are found to exhibit a r.elatiuely high degree of electrical resistiuity and thus are susceptible to problems such as undesired accumulation of surface electrostatic charge.
Efforts to lower resisti~ity (i.e., increase conductiuity) of crosslinked polymer compositio~s haue inuolued ~arious approaches.
One approach inuol~es adding a.separate conductiuity agent to an otherwise electrically insulative composition comprising a crosslinked polymer to lower the ouerall resisti~ity of the composition. Howeuer, many con~uctivity agents (e.g., carbon black or metal particles such as steel ~'7708(~
or aluminum) can ad~ersely affect other properties of the composition, for example, by imparting undesirable coloration or by changing reflectiue properties. Other conducti~ity agents {e,~., some organic compou~ds containing qwatern~ry arnrnonium moieties) do not ha~e initial aduerse ef~cts, but sinc~ they are not perrnan0ntly anchored in the cornposition, can euaporate or migrate out of the composition, resulting in a co~tinuous change in th~
resi.stiuity of the composition o~er ~ime and pos~ible aduerse affects on materials that may come into contact with the migrating agent.
- Another approach, which auoids euaporation and migration problems, inuolues bonding quaternary ammonium conducti~ity agents or precursors thereof directly into monomers before polymerizing them to form the backbones of the polymer or bonding such agents into the polymer or crosslinking agent before crosslinking. For example, U.K. Patent 2,066,257~, published 3 ~ugust 1983, describes epoxy resins ha~ing nitrogen atoms as integral parts of the resin backbone. Simultaneous reaction of such an epoxy resin with a crosslinking agent and a quaternizing agent results in crosslinking of the resin and conuersion of the nitrogen atoms into quaternary ammonium conductiue moieties diualently included in the polymer backbone. U.S. Patent 3,011,~18 describes preparing crosslinked vinyl polymers from polymerizable monomers already hauing been specially prepared hauing quaternary ammonium moieties bonded co~alently and pendently thereto. ~lso, published abstracts of Japanese published patent applications 59/024706 and 59/024727 (both applications published 8 February 1984) describe polymerizing and crosslinking certain monomers, each of which already -:
~7 ~ ~
_3_ -contains a quaternary ammonium moiety, to produce eonducti~e crosslinked polymers ha~ing such rnoieties di~alently included in the polymer backbones.
Howeuer, the schemes described in the abo~e-not0d U.K, P~tent, U.S. Patent, an~ Japanese applications also haue drawbacks. The~ r~quire that specialized polymers or monomers containin0 the quaternary ammonium moieties or precursors ~hereof be prepared in separate steps before crosslinking the polymers, thus complicating and lenythening the process of preparation. Furthermore, incorporation of conducti~e moieties directly into poly~er backbones such as in the U.K. Patent and Japanese applications, may effect profound changes in other properties of the polymers in addition to resisti~ity. ~lso, when using specially modified polymer and monomer starting materials, one has little or no leeway to-alter the level of permanent resisti~ity that the resultant polymer wil]. çxhibit after crosslinking; in other words, in order to change the resultant le~el of resistivity, one must often start at the beginning and f~shion new specially modified polymers or monom`ers to be crosslinked.
The present in~ention o~ercomès all o~ the abo~e-noted prior art problems.
The in~ention encompasses new crosslinked polymers and methods and combinations of materials useful for their preparation.
The combination of starting materials essential to the in~ention comprises:
a polymer containing ~t least one fullctional moiety capable of reacting ~o bond to a crosslinkin~
agent, a crosslinking agent for the polymer, and ~ ~70~
a conducti~ity agent containin~ a quaternary ammoni~m moiety and being capable of reacting with the crosslinking agent or the polymer to bond coualently and pendently to the crosslinking agent or the polymer, during a process of crosslinking the polymer through the crosslinking agent.
The process of the in~ention makes use of the abo~e-noted starting materials and comprises, subjecting the combination of starting materials to conditions sufficient to simultaneously crosslink the polymer through the crosslinking agent and bond the conducti~ity agent co~alently and penderltly to the crosslinking agent or the polymer.
~n in~enti~e use of the combination of starting materials is to produce a new polymer crosslinked through the crosslinking agent and hauing the conducti~ity agent bonded covalently and pendently to the crosslinking agent.
The conducti~ity agent containing the quaternary ammonium moiety imparts a degree of condwcti~ity to the new crosslinked polymers.
Because the agent becomes bonded coualerltly to the backbone or crosslinking portion of the polymer, it forms a permanently fixed part of the crosslinke~
polymer and will not euaporate or migrate therefrom.
8ecause the agent is pendently bonded to the backbone or crosslinking portion o~ the polymer, it is much less likely to affect properties of the polymer other than resisti~ity, compared to prior art schemes wherein quaternary ammonium moieties are div~lently incorporated in the polymer chains.
~ lso, since the conducti~ity agent becomes bonded to the polymer backbone or crosslinking agent during crosslinking, there.is no comp].icating nee~ to fashion specially modified starting monomers or polymers, and there are no extra steps t~ be a~ded to 7~8(~
the normal crosslinking process. The conductiuity agent is simply included in the desired amount in the combination of starting materials and bonds to the polymer backbone or crosslinking agent d~ring the - normal process of crosslinking under condltions well known to be sufficient ~o c~se the crosslinking, Furthermore, by simply altering the amoun~ of conductiuity agent included in the combin~tion of starting materials, one can con~eniently alter the degree of conductiuity imparted to the crosslinked polymer without ha~ing to alter the initi~l monomer, polymer or crosslinking agent materials or their amounts in any way, and there is, therefore, also much less chance that properties of the final crosslinked polymer, other than resisti~ity, will also be altered.
The inuention is ad~antageously applicable to ~irtually any polymer capable of being crosslinked through a crosslinking agent by known methods In some preferred embodiments in~oluing protectiue or decoratiue coating compositions such as paints, preferred polymers include polyester, poly~crylic, polyepoxy, and polyamide polymers and copolymers, The initial polyrner must, in accordance with well-known cross~inking mechanisms, contain at least one fwnctional moiety that is reactiue to bond to the crosslinking agent, Such functional moieties include all the moieties known to be functional in this manner, for example, hydroxyl, carboxyl, thiol, epoxide, amide, and amine moieties, In some preferred embodiments, the functional moiety of the polymer is a hydroxyl moiety. For example, when the polymer to be crosslinked is a polyester, its functional moieties can be the result of ha~ing used a polyol such as trimethylolpropane in preparin~ the polyester by condensation of polyacids with polyols, such that two of the three hydroxyl groups of the ~77~:78V
trimethylolpropane participated in forming backbone ester linkages, and the remaining hydroxyl group is still a~ailable to prouide a crosslinking site or bonding site for the conducti~ity agent.
Crosslinking agents use~ul in accordance wlth the in~ention include the chernical c~mpounds known to be useful in general as agents throu~h which polymers can be crosslinked. Such crossllnking agents contain at least two functional moieties to react with functional moieties of tha initial polymer chains in order to crosslink the chains through the crosslinking agent. Such crosslinking agent functional moieties include, for example, ether, hydroxyl, carboxyl, isocyanate, and anhydride moieties. In some preferred embodiments the functional moieties of the crosslinking agent are anhydride or ether groups. ~ specific crosslinking agent included in some preferred embodimellts is hexa(methoxymethyl)melamine.
~nother requirement of the in~ention in regard to the initial polymer and the crosslinking agent, is that, in addition to the functioral moieties necessary for crosslinking the polymer through the crosslinking agent, either the polymer or the crosslinking agent or both must contain a moiety functional to react with the conducti~ity agent in order to bond the conducti~ity agent covalently and pendently to the polymer backbone or the crosslinking agent under conditions known to be su~ficient to 3~ crosslink the polymer chains. Such a moiety can comprise any of the moieties known to be useful in crosslinking reactions, as described abo~e. For example, when the initial polymer is one containing a hydroxyl moiety, and when the crosslinking agent chosen is hexa(methoxymethyl)melamine, then there are six ether moieties a~ailable in the crosslinking ~'~ 7'~0~
agent. ~t least two of these ether moieties will react with the hydroxyl groups of the polymer chains to crosslink them, but there will still be ether moieties available to react with a functional moiety (e.g., a hyd.roxyl moiety or thiol moiety) of the conductivity agent in ord~r to bond the conducti~it~
agent pendently to the crosslinking agent during the process of crosslinking.
Conducti~ity agents useful in accordance with the in~ention ~re chemical compounds containing a quaternary ammonium moiety an~ at least one Functional group that is reactive to bond covalently to the crosslinking agent or the polymer. The quaternary ammonium moiety will usually ha~e an anionic material associated with it and thus be in the form of a quaternary ammonium salt. The group in the conductivity agent that is functional to bond to the crosslinking agent or the polymer can be chosen from arnong the same functional groups described above as useful in crosslinking the polymer through the crosslinking agent. However, the specific functional groups on t~e.polymer or crosslinking agent and the conductivity agent do not have to be the same. In some preferred embodiments the fwnctional group in the conductivity agent is a hydroxyl group. Specific examples of useful conductivity agents are N-butyl-N,N-bis(2-hydroxy-ethyl)-N-methylammonium bromide and N-decyl~
N,N~bis(2-hydroxyethyl)- N-methylammonium bromide.
Other addenda may be included in the combination of starting materials, depending upon the nature in any specific instance of the ~onding reactions intended to take place between the polymer and the crosslinking agent and between the conductivi~y agent and the crosslinking agent or ~'~77~8(~) polymer and also depending on the properties and utility desired for the final crosslinked polymer.
Where the combination of starting materials is intended to be used as a coating composition, it will in many cases also include a catalyst for the reactions and a sol~ent or dispersant mediwm For the starting materials, the natur~ o~ which will depend upon the type of reaction and starting m~teri~l5, E~amples of soluents and dispersant media useful in some of the preFerred embodiments ars xylene, n~butyl alcohol, toluene, 2-ethoxyethanol, 2-ethoxyethyl acetate, isopropanol, methyl ethyl ketone, - 2-propoxyethanol, methyl pyrrolidone, propylene glycol monomethyl ether acetate, and water. Examples of catalysts useful in some of the preferred embodiments are p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid, and dodecylbenzene sulfonic acid.
In the case where the ~oating composition is a paint composition it will usually alço contain a pigment (e.g., a white pigment such as titanium dioxide) and other well-known desirable additives such as flow control agents and leveling agents.
The process of the in~ention corllprises simply following the normal procedures that are well-known for crosslinking a giuen polymer with a given crosslinking agent, while the desired amount of appropriate conducti~ity agent is also included in the combination of starting materials. In the case of some of the paint compositions of the preferred embodiments, the composition is sprayQd onto a surface and allowed to dry and cure, sometimes with application of heat to accelerate the process.
Multiple coatings can also be USRd.
hn inuenti~e product of this process is a polymer crosslinked through the crosslinking agent 7~
and h~ing the conducti~ity ~gent bonded c~alently and pendently to some or all of the crosslinking chains. Depending upon the nature of functional growps present in the polymer and conducti~ity agent, some conductivity agent may also bec~me co~lently and pendently bonded ~t other loc~tions on the polymer.
The degree of conductivity (usually expressed in terms of surface resisti~ity) imp~rted to the polymer will ~ary depending upon the amount of condwctiuity agent included in the combination of starting materials and the inherent properties of the giuen polymer and crosslinking agent ~e.g., the degree of conductiuity the erosslinked polymer would have if no conducti~ity agent were included). I~ one preferred embodiment the resisti~ity of a crosslinked polymeric paint coating in accordance l~ith the in~ention was about 5.5 x 10 ohms per square, while the same crosslinked polymeric paint COAting formed without including any conducti~ity agent had a resisti~ity higher than 10 ohms per sqware. Th~
conducti~ity agents useful in the inuention ~aue been found effecti~e to impro~e conducti~ity of crosslinked polymers when they are included in concentrations of ~t least 1 percent by weight, based on total polymer weight. In some embodiments conducti~ity agent is included in concentrations of 1 to 30 percent, and preferably 2-20 percent, by weight.
The ~ollowing Examples are presented to further illustrate some preferred embodiments of the in~ention.
The conducti~ity agent used in the examples was N-butyl-N,N-bis(2-hydroxyethyl)-N-methylarl~monium bromide.
~27~
-1~
It was prepared ~y mixing one mole of N-methyldiethanolamine with one mole of l-bromobutane, stirring the mixture for 7 hours at ternperature of 95~C, placing the resultant solution uncler ~acuum (0.0133 kPa) ~or 15 minutes to remo~e unreacted material, transferring the hot solution to a tin can, ancl allowing it to cool, whereupon the procluct crystallized out.
Example 1 In this example a typical polyester paint formulation was prepared and coated on ~ surface as a control and was then compared to the same paint formulation to whi&h had been added a concluctivity agent in accordance with the present inuention.
Both the in~entive and the control paint formulations contained an uncrosslinked polyester resin (Aroplaz 6755-~6-80, trademarked by and auailable from Textron, Inc. US~) hauing hydroxyl groups pendently bonded to the polymer backbone, a hexa(methoxymethyl)melarnine crosslinking agent, a p-toluene sulfonic acid catalyst, a flow-control agent comprising fluoroallphatic polymer~c esters, a titanium dioxide white pigment, an àmorphous silica leueling agent, and various soluents. In addition, the inventiue paint formulation contained the conductivity agent, N-butyl-N, N-bis (2-hydroxy-ethyl~-N~methylammonium bromide. The concentrations of ingredients, expressed as percent by weight of each total paint formulation, are listed in Table I.
.770~3~
Table I
Weight Percent W~ight Percent of in~enti~e of control _ paint _ paint polyester resin 32.08 33.36 hexa(methoxymethyl)-melamine 10.S8 11.00 p-toluene sulfonic acid O.09 0.09 fluoroaliphatic polymeric esters 0.43 0.45 titanium dioxide 27.99 29.11 amorphous sili.ca 3.85 ~.00 xylene 0.58 0.60 butyl alcohol 1.92 2.00 toluene 2.87 2.93 2-ethoxyethyl aceta~e 5.21 5.42 isopropyl alcohol 0.13 0.14 propylene glycol mono- .
`20 methyl ether ~cetate 10.4~ lO.90 N-butyl-N, N-bis~2-hydroxy-ethyl)-N-methylammonium bromide 3.85 0 For each paint formulation, the ingredients were mixed together with stirring and applied to a ~lat surface by spraying (to a dry film thickness of 30.5 micrometers). Each coating was heated to 135C
for 20 minutes to accelerate the crosslinkin~
reaction and, in the case of the inuenti~e paint, the bonding reaction between the conducti~ity and crosslinking agents.
Surface resisti~ities of the two coated surfaces were then measured. The surface coated with the control pain~ exhibi~ed a surface resis~i~ity of 1.3 x 10 ohms per square, while the surface ~ ~7~
coated with the inventive paint exhibited a surface resistivity of 5.5x101 ohms per sguare.
ple 2 In this example a typical polyacrylic paint formulation was prepared and coated on a surface as control and was then compared to the s~me paint formulation to which had b~en added a conduc~ivity agent in accordance with the present in~ention, Both the inventi~e and the control paint formulations contained a thermosetting acrylic resin having functional hydroxyl groups pendently bonded to the polymer backbone, a crosslinking agent comprising a resin having anhydride functional gro~ps, a white pigment composition containing titanium dioxide, various leveling agents, and solvents s~ch as methyl pyrrolidone and cellosol~e. In addition, the inventive paint formulation contained the conductivity agent, N-butyl-N,N-bis-(2-hydroxy- .
ethyl)-N-methylarnmoniwm bromide. The concentrations of ingredients, expressed as percent by weight of each total paint formulation, are listed in Table II.
.
able II
Weight percent of Weight percent of Inqredient _i uenti e paint control paint Thermosetting 33.43 3~.79 acrylic resin Crosslinking 4.18 4.3S
agent White pigment 25.07 26.09 composition Leueling a~ents25.06 2~.08 Soluents 8.36 8.70 Conductiuity 3.90 0 agent For each paint formulation, the ingredients were mixed together with stirring and applied to a flat surface by spraying (to a dry ~ilm thickness of 30.5 micrometers). Each coating was allowed to air set for 15 minutes and was then heated to 82C for 20 minutes and finally heated to 163C for 20 minutes.
Surface resistiuities of the two coated surfaces were then measured. The surface coated with the control paint exhibited a surface resisti~ity on the order of lO1 ohms per square, while the surface coated with the inuentive paint exhibited a surface resisti~ity on the order of 10 ohms per sguare .
LOWERED RESISTI~ITY ~ND M~TERI~LS ~ND
METHODS FOR THEIR PREP~R~TION
The in~ention relates to cro~slinked polymers that ha~e a desired leuel o~ electrical resistiuity and to methods and combin~tion~ of starting materials useful to prepare such polyrn0rs.
More particularly, the inuention concerns imparting a desired de~ree of permanent conducti~ity to crosslinked polymers simply and accuratel~ during their crosslinking reaction.
Crosslinked polymers are useful for many purposes, such as those where structural integrity, resistance to flow, toughness, or durability are important. One significant area of use is in protectiue or decorative coatings, such as paints.
In many such uses te.g., as paint coatings for electrographic copiers or other electrical apparatus, ~or aircraft, and for high speed manufacturing ~o apparatus such as photographic coating machines) buildup of electrostatic charges on surfaces coated with such paints could cause serious problems. Many crosslinked polymers hauing other desirable properties are found to exhibit a r.elatiuely high degree of electrical resistiuity and thus are susceptible to problems such as undesired accumulation of surface electrostatic charge.
Efforts to lower resisti~ity (i.e., increase conductiuity) of crosslinked polymer compositio~s haue inuolued ~arious approaches.
One approach inuol~es adding a.separate conductiuity agent to an otherwise electrically insulative composition comprising a crosslinked polymer to lower the ouerall resisti~ity of the composition. Howeuer, many con~uctivity agents (e.g., carbon black or metal particles such as steel ~'7708(~
or aluminum) can ad~ersely affect other properties of the composition, for example, by imparting undesirable coloration or by changing reflectiue properties. Other conducti~ity agents {e,~., some organic compou~ds containing qwatern~ry arnrnonium moieties) do not ha~e initial aduerse ef~cts, but sinc~ they are not perrnan0ntly anchored in the cornposition, can euaporate or migrate out of the composition, resulting in a co~tinuous change in th~
resi.stiuity of the composition o~er ~ime and pos~ible aduerse affects on materials that may come into contact with the migrating agent.
- Another approach, which auoids euaporation and migration problems, inuolues bonding quaternary ammonium conducti~ity agents or precursors thereof directly into monomers before polymerizing them to form the backbones of the polymer or bonding such agents into the polymer or crosslinking agent before crosslinking. For example, U.K. Patent 2,066,257~, published 3 ~ugust 1983, describes epoxy resins ha~ing nitrogen atoms as integral parts of the resin backbone. Simultaneous reaction of such an epoxy resin with a crosslinking agent and a quaternizing agent results in crosslinking of the resin and conuersion of the nitrogen atoms into quaternary ammonium conductiue moieties diualently included in the polymer backbone. U.S. Patent 3,011,~18 describes preparing crosslinked vinyl polymers from polymerizable monomers already hauing been specially prepared hauing quaternary ammonium moieties bonded co~alently and pendently thereto. ~lso, published abstracts of Japanese published patent applications 59/024706 and 59/024727 (both applications published 8 February 1984) describe polymerizing and crosslinking certain monomers, each of which already -:
~7 ~ ~
_3_ -contains a quaternary ammonium moiety, to produce eonducti~e crosslinked polymers ha~ing such rnoieties di~alently included in the polymer backbones.
Howeuer, the schemes described in the abo~e-not0d U.K, P~tent, U.S. Patent, an~ Japanese applications also haue drawbacks. The~ r~quire that specialized polymers or monomers containin0 the quaternary ammonium moieties or precursors ~hereof be prepared in separate steps before crosslinking the polymers, thus complicating and lenythening the process of preparation. Furthermore, incorporation of conducti~e moieties directly into poly~er backbones such as in the U.K. Patent and Japanese applications, may effect profound changes in other properties of the polymers in addition to resisti~ity. ~lso, when using specially modified polymer and monomer starting materials, one has little or no leeway to-alter the level of permanent resisti~ity that the resultant polymer wil]. çxhibit after crosslinking; in other words, in order to change the resultant le~el of resistivity, one must often start at the beginning and f~shion new specially modified polymers or monom`ers to be crosslinked.
The present in~ention o~ercomès all o~ the abo~e-noted prior art problems.
The in~ention encompasses new crosslinked polymers and methods and combinations of materials useful for their preparation.
The combination of starting materials essential to the in~ention comprises:
a polymer containing ~t least one fullctional moiety capable of reacting ~o bond to a crosslinkin~
agent, a crosslinking agent for the polymer, and ~ ~70~
a conducti~ity agent containin~ a quaternary ammoni~m moiety and being capable of reacting with the crosslinking agent or the polymer to bond coualently and pendently to the crosslinking agent or the polymer, during a process of crosslinking the polymer through the crosslinking agent.
The process of the in~ention makes use of the abo~e-noted starting materials and comprises, subjecting the combination of starting materials to conditions sufficient to simultaneously crosslink the polymer through the crosslinking agent and bond the conducti~ity agent co~alently and penderltly to the crosslinking agent or the polymer.
~n in~enti~e use of the combination of starting materials is to produce a new polymer crosslinked through the crosslinking agent and hauing the conducti~ity agent bonded covalently and pendently to the crosslinking agent.
The conducti~ity agent containing the quaternary ammonium moiety imparts a degree of condwcti~ity to the new crosslinked polymers.
Because the agent becomes bonded coualerltly to the backbone or crosslinking portion of the polymer, it forms a permanently fixed part of the crosslinke~
polymer and will not euaporate or migrate therefrom.
8ecause the agent is pendently bonded to the backbone or crosslinking portion o~ the polymer, it is much less likely to affect properties of the polymer other than resisti~ity, compared to prior art schemes wherein quaternary ammonium moieties are div~lently incorporated in the polymer chains.
~ lso, since the conducti~ity agent becomes bonded to the polymer backbone or crosslinking agent during crosslinking, there.is no comp].icating nee~ to fashion specially modified starting monomers or polymers, and there are no extra steps t~ be a~ded to 7~8(~
the normal crosslinking process. The conductiuity agent is simply included in the desired amount in the combination of starting materials and bonds to the polymer backbone or crosslinking agent d~ring the - normal process of crosslinking under condltions well known to be sufficient ~o c~se the crosslinking, Furthermore, by simply altering the amoun~ of conductiuity agent included in the combin~tion of starting materials, one can con~eniently alter the degree of conductiuity imparted to the crosslinked polymer without ha~ing to alter the initi~l monomer, polymer or crosslinking agent materials or their amounts in any way, and there is, therefore, also much less chance that properties of the final crosslinked polymer, other than resisti~ity, will also be altered.
The inuention is ad~antageously applicable to ~irtually any polymer capable of being crosslinked through a crosslinking agent by known methods In some preferred embodiments in~oluing protectiue or decoratiue coating compositions such as paints, preferred polymers include polyester, poly~crylic, polyepoxy, and polyamide polymers and copolymers, The initial polyrner must, in accordance with well-known cross~inking mechanisms, contain at least one fwnctional moiety that is reactiue to bond to the crosslinking agent, Such functional moieties include all the moieties known to be functional in this manner, for example, hydroxyl, carboxyl, thiol, epoxide, amide, and amine moieties, In some preferred embodiments, the functional moiety of the polymer is a hydroxyl moiety. For example, when the polymer to be crosslinked is a polyester, its functional moieties can be the result of ha~ing used a polyol such as trimethylolpropane in preparin~ the polyester by condensation of polyacids with polyols, such that two of the three hydroxyl groups of the ~77~:78V
trimethylolpropane participated in forming backbone ester linkages, and the remaining hydroxyl group is still a~ailable to prouide a crosslinking site or bonding site for the conducti~ity agent.
Crosslinking agents use~ul in accordance wlth the in~ention include the chernical c~mpounds known to be useful in general as agents throu~h which polymers can be crosslinked. Such crossllnking agents contain at least two functional moieties to react with functional moieties of tha initial polymer chains in order to crosslink the chains through the crosslinking agent. Such crosslinking agent functional moieties include, for example, ether, hydroxyl, carboxyl, isocyanate, and anhydride moieties. In some preferred embodiments the functional moieties of the crosslinking agent are anhydride or ether groups. ~ specific crosslinking agent included in some preferred embodimellts is hexa(methoxymethyl)melamine.
~nother requirement of the in~ention in regard to the initial polymer and the crosslinking agent, is that, in addition to the functioral moieties necessary for crosslinking the polymer through the crosslinking agent, either the polymer or the crosslinking agent or both must contain a moiety functional to react with the conducti~ity agent in order to bond the conducti~ity agent covalently and pendently to the polymer backbone or the crosslinking agent under conditions known to be su~ficient to 3~ crosslink the polymer chains. Such a moiety can comprise any of the moieties known to be useful in crosslinking reactions, as described abo~e. For example, when the initial polymer is one containing a hydroxyl moiety, and when the crosslinking agent chosen is hexa(methoxymethyl)melamine, then there are six ether moieties a~ailable in the crosslinking ~'~ 7'~0~
agent. ~t least two of these ether moieties will react with the hydroxyl groups of the polymer chains to crosslink them, but there will still be ether moieties available to react with a functional moiety (e.g., a hyd.roxyl moiety or thiol moiety) of the conductivity agent in ord~r to bond the conducti~it~
agent pendently to the crosslinking agent during the process of crosslinking.
Conducti~ity agents useful in accordance with the in~ention ~re chemical compounds containing a quaternary ammonium moiety an~ at least one Functional group that is reactive to bond covalently to the crosslinking agent or the polymer. The quaternary ammonium moiety will usually ha~e an anionic material associated with it and thus be in the form of a quaternary ammonium salt. The group in the conductivity agent that is functional to bond to the crosslinking agent or the polymer can be chosen from arnong the same functional groups described above as useful in crosslinking the polymer through the crosslinking agent. However, the specific functional groups on t~e.polymer or crosslinking agent and the conductivity agent do not have to be the same. In some preferred embodiments the fwnctional group in the conductivity agent is a hydroxyl group. Specific examples of useful conductivity agents are N-butyl-N,N-bis(2-hydroxy-ethyl)-N-methylammonium bromide and N-decyl~
N,N~bis(2-hydroxyethyl)- N-methylammonium bromide.
Other addenda may be included in the combination of starting materials, depending upon the nature in any specific instance of the ~onding reactions intended to take place between the polymer and the crosslinking agent and between the conductivi~y agent and the crosslinking agent or ~'~77~8(~) polymer and also depending on the properties and utility desired for the final crosslinked polymer.
Where the combination of starting materials is intended to be used as a coating composition, it will in many cases also include a catalyst for the reactions and a sol~ent or dispersant mediwm For the starting materials, the natur~ o~ which will depend upon the type of reaction and starting m~teri~l5, E~amples of soluents and dispersant media useful in some of the preFerred embodiments ars xylene, n~butyl alcohol, toluene, 2-ethoxyethanol, 2-ethoxyethyl acetate, isopropanol, methyl ethyl ketone, - 2-propoxyethanol, methyl pyrrolidone, propylene glycol monomethyl ether acetate, and water. Examples of catalysts useful in some of the preferred embodiments are p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid, and dodecylbenzene sulfonic acid.
In the case where the ~oating composition is a paint composition it will usually alço contain a pigment (e.g., a white pigment such as titanium dioxide) and other well-known desirable additives such as flow control agents and leveling agents.
The process of the in~ention corllprises simply following the normal procedures that are well-known for crosslinking a giuen polymer with a given crosslinking agent, while the desired amount of appropriate conducti~ity agent is also included in the combination of starting materials. In the case of some of the paint compositions of the preferred embodiments, the composition is sprayQd onto a surface and allowed to dry and cure, sometimes with application of heat to accelerate the process.
Multiple coatings can also be USRd.
hn inuenti~e product of this process is a polymer crosslinked through the crosslinking agent 7~
and h~ing the conducti~ity ~gent bonded c~alently and pendently to some or all of the crosslinking chains. Depending upon the nature of functional growps present in the polymer and conducti~ity agent, some conductivity agent may also bec~me co~lently and pendently bonded ~t other loc~tions on the polymer.
The degree of conductivity (usually expressed in terms of surface resisti~ity) imp~rted to the polymer will ~ary depending upon the amount of condwctiuity agent included in the combination of starting materials and the inherent properties of the giuen polymer and crosslinking agent ~e.g., the degree of conductiuity the erosslinked polymer would have if no conducti~ity agent were included). I~ one preferred embodiment the resisti~ity of a crosslinked polymeric paint coating in accordance l~ith the in~ention was about 5.5 x 10 ohms per square, while the same crosslinked polymeric paint COAting formed without including any conducti~ity agent had a resisti~ity higher than 10 ohms per sqware. Th~
conducti~ity agents useful in the inuention ~aue been found effecti~e to impro~e conducti~ity of crosslinked polymers when they are included in concentrations of ~t least 1 percent by weight, based on total polymer weight. In some embodiments conducti~ity agent is included in concentrations of 1 to 30 percent, and preferably 2-20 percent, by weight.
The ~ollowing Examples are presented to further illustrate some preferred embodiments of the in~ention.
The conducti~ity agent used in the examples was N-butyl-N,N-bis(2-hydroxyethyl)-N-methylarl~monium bromide.
~27~
-1~
It was prepared ~y mixing one mole of N-methyldiethanolamine with one mole of l-bromobutane, stirring the mixture for 7 hours at ternperature of 95~C, placing the resultant solution uncler ~acuum (0.0133 kPa) ~or 15 minutes to remo~e unreacted material, transferring the hot solution to a tin can, ancl allowing it to cool, whereupon the procluct crystallized out.
Example 1 In this example a typical polyester paint formulation was prepared and coated on ~ surface as a control and was then compared to the same paint formulation to whi&h had been added a concluctivity agent in accordance with the present inuention.
Both the in~entive and the control paint formulations contained an uncrosslinked polyester resin (Aroplaz 6755-~6-80, trademarked by and auailable from Textron, Inc. US~) hauing hydroxyl groups pendently bonded to the polymer backbone, a hexa(methoxymethyl)melarnine crosslinking agent, a p-toluene sulfonic acid catalyst, a flow-control agent comprising fluoroallphatic polymer~c esters, a titanium dioxide white pigment, an àmorphous silica leueling agent, and various soluents. In addition, the inventiue paint formulation contained the conductivity agent, N-butyl-N, N-bis (2-hydroxy-ethyl~-N~methylammonium bromide. The concentrations of ingredients, expressed as percent by weight of each total paint formulation, are listed in Table I.
.770~3~
Table I
Weight Percent W~ight Percent of in~enti~e of control _ paint _ paint polyester resin 32.08 33.36 hexa(methoxymethyl)-melamine 10.S8 11.00 p-toluene sulfonic acid O.09 0.09 fluoroaliphatic polymeric esters 0.43 0.45 titanium dioxide 27.99 29.11 amorphous sili.ca 3.85 ~.00 xylene 0.58 0.60 butyl alcohol 1.92 2.00 toluene 2.87 2.93 2-ethoxyethyl aceta~e 5.21 5.42 isopropyl alcohol 0.13 0.14 propylene glycol mono- .
`20 methyl ether ~cetate 10.4~ lO.90 N-butyl-N, N-bis~2-hydroxy-ethyl)-N-methylammonium bromide 3.85 0 For each paint formulation, the ingredients were mixed together with stirring and applied to a ~lat surface by spraying (to a dry film thickness of 30.5 micrometers). Each coating was heated to 135C
for 20 minutes to accelerate the crosslinkin~
reaction and, in the case of the inuenti~e paint, the bonding reaction between the conducti~ity and crosslinking agents.
Surface resisti~ities of the two coated surfaces were then measured. The surface coated with the control pain~ exhibi~ed a surface resis~i~ity of 1.3 x 10 ohms per square, while the surface ~ ~7~
coated with the inventive paint exhibited a surface resistivity of 5.5x101 ohms per sguare.
ple 2 In this example a typical polyacrylic paint formulation was prepared and coated on a surface as control and was then compared to the s~me paint formulation to which had b~en added a conduc~ivity agent in accordance with the present in~ention, Both the inventi~e and the control paint formulations contained a thermosetting acrylic resin having functional hydroxyl groups pendently bonded to the polymer backbone, a crosslinking agent comprising a resin having anhydride functional gro~ps, a white pigment composition containing titanium dioxide, various leveling agents, and solvents s~ch as methyl pyrrolidone and cellosol~e. In addition, the inventive paint formulation contained the conductivity agent, N-butyl-N,N-bis-(2-hydroxy- .
ethyl)-N-methylarnmoniwm bromide. The concentrations of ingredients, expressed as percent by weight of each total paint formulation, are listed in Table II.
.
able II
Weight percent of Weight percent of Inqredient _i uenti e paint control paint Thermosetting 33.43 3~.79 acrylic resin Crosslinking 4.18 4.3S
agent White pigment 25.07 26.09 composition Leueling a~ents25.06 2~.08 Soluents 8.36 8.70 Conductiuity 3.90 0 agent For each paint formulation, the ingredients were mixed together with stirring and applied to a flat surface by spraying (to a dry ~ilm thickness of 30.5 micrometers). Each coating was allowed to air set for 15 minutes and was then heated to 82C for 20 minutes and finally heated to 163C for 20 minutes.
Surface resistiuities of the two coated surfaces were then measured. The surface coated with the control paint exhibited a surface resisti~ity on the order of lO1 ohms per square, while the surface coated with the inuentive paint exhibited a surface resisti~ity on the order of 10 ohms per sguare .
Claims (6)
1. A combination of materials comprising:
a polymer containing at least one functional moiety capable of reacting to bond to a crosslinking agent, a crosslinking agent for the polymer, and a conductivity agent containing a quaternary ammonium moiety and being capable of reacting with the crosslinking agent or the polymer to bond covalently and pendently to the crosslinking agent or the polymer, during a process of crosslinking the polymer through the crosslinking agent.
a polymer containing at least one functional moiety capable of reacting to bond to a crosslinking agent, a crosslinking agent for the polymer, and a conductivity agent containing a quaternary ammonium moiety and being capable of reacting with the crosslinking agent or the polymer to bond covalently and pendently to the crosslinking agent or the polymer, during a process of crosslinking the polymer through the crosslinking agent.
2. The combination as defined in claim 1, further comprising a catalyst for the crosslinking process.
3. The combination as defined in claim 2, further comprising a solvent for the polymer.
4. The combination as defined in claim 3, further comprising a pigment.
5. The use of the combination of materials described in claim 1 to produce a polymer crosslinked through a crosslinking agent and having a conductivity agent that contains a quaternary ammonium moiety and is bonded covalently and pendently to the crosslinking agent.
6. A process comprising subjecting the combination of materials described in claim 1 to conditions sufficient to simultaneously crosslink the polymer through the crosslinking agent and bond the conductivity agent covalently and pendently to the crosslinking agent or the polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/892,173 US4698391A (en) | 1986-07-30 | 1986-07-30 | Crosslinked polymers with lowered resistivity and materials and methods for their preparation |
| US892,173 | 1986-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1277080C true CA1277080C (en) | 1990-11-27 |
Family
ID=25399495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000538066A Expired - Fee Related CA1277080C (en) | 1986-07-30 | 1987-05-27 | Crosslinked polymers with lowered resistivity and materials and methods for their preparation |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4698391A (en) |
| EP (1) | EP0254874A3 (en) |
| JP (1) | JPS6337157A (en) |
| CA (1) | CA1277080C (en) |
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| US4962139A (en) * | 1986-02-28 | 1990-10-09 | W. C. Richards Company | Conductive primer compositions with primary resin binder |
| DE3716861A1 (en) * | 1987-05-20 | 1988-12-15 | Flachglas Ag | Curable UP moulding composition having reduced electrical surface resistance |
| DE3809928A1 (en) * | 1988-03-24 | 1989-10-05 | Henkel Kgaa | TOWABLE TEXTILE TOOLS FOR POLYESTER CONTAINING FIBER MATERIALS |
| US4990593A (en) * | 1988-10-14 | 1991-02-05 | Eastman Kodak Company | Water-dissipatable polyester resins and coatings prepared therefrom |
| US4910292A (en) * | 1988-10-14 | 1990-03-20 | Eastman Kodak Company | Water-dissipatable polyester resins and coatings prepared therefrom |
| US4940517A (en) * | 1988-11-10 | 1990-07-10 | Drexel University | Polymerization of aniline and its derivatives |
| US5078913A (en) * | 1989-04-14 | 1992-01-07 | James River Paper Company, Inc. | Deodorization of amine contaminated quaternary ammonium salt conductive resins |
| US5011739A (en) * | 1989-10-02 | 1991-04-30 | Eastman Kodak Company | Moisture stable biasable transfer members and method for making same |
| JPH04122775A (en) * | 1990-09-14 | 1992-04-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for improving electrical conductivity of resin |
| US5281643A (en) * | 1991-05-28 | 1994-01-25 | Istituto Guido Donegani S.P.A. | Thermoplastic polyester molding compositions containing quaternary ammonium compounds |
| US5244944A (en) * | 1991-06-05 | 1993-09-14 | Eastman Kodak Company | Thermosetting powder coating compositions |
| TW218384B (en) * | 1991-08-09 | 1994-01-01 | Eastman Kodak Co | |
| US5420267A (en) * | 1991-08-09 | 1995-05-30 | Eastman Chemical Company | Cellulose acetoacetate esters |
| US5218042A (en) * | 1991-09-25 | 1993-06-08 | Thauming Kuo | Water-dispersible polyester resins and process for their preparation |
| US5217838A (en) * | 1991-11-26 | 1993-06-08 | Eastman Kodak Company | Moisture stable biasable transfer members |
| US5250357A (en) * | 1991-11-26 | 1993-10-05 | Eastman Kodak Company | Moisture stable elastomeric polyurethane biasable transfer members |
| US5212032A (en) * | 1991-11-26 | 1993-05-18 | Eastman Kodak Company | Moisture stable polyurethane biasable transfer members |
| US5349010A (en) * | 1992-09-30 | 1994-09-20 | Eastman Chemical Company | Water-dispersible polyester resins and process for their preparation |
| US5322885A (en) * | 1992-11-02 | 1994-06-21 | Eastman Chemical Company | Aqueous dispersion compositions and coatings prepared therefrom |
| US5378757A (en) * | 1993-11-15 | 1995-01-03 | Eastman Chemical Company | Water-dissipatable alkyd resins and coatings prepared therefrom |
| AU7718496A (en) | 1995-10-20 | 1997-05-07 | Drexel University | End-functionalized aniline-based oligomers, corrosion-resistant copolymers and methods of making the same |
| US6333378B1 (en) | 1997-08-12 | 2001-12-25 | Eastman Chemical Company | Acrylic modified waterborne alkyd or uralkyd dispersions |
| DE69824736T2 (en) | 1997-08-12 | 2004-10-21 | Eastman Chem Co | ACRYLIC MODIFIED AQUEOUS ALKYD DISPERSIONS |
| BR0012014A (en) | 1999-06-29 | 2002-03-26 | Eastman Chem Co | Resin intermediate, process for forming the same, water-dispersible, hydroxyl-functional polyester, process for preparing the same, dispersion free of organic solvent, environmentally curing, from zero, and, article |
| US20050004272A1 (en) * | 2003-06-23 | 2005-01-06 | Thauming Kuo | Small-particle latex compositions based on waterborne alkyd seeds |
| US20060270769A1 (en) * | 2005-05-24 | 2006-11-30 | Shoaf Glenn L | Acrylic-modified alkyd hybrid latexes and their use as viscosity modifiers |
| CN101768415B (en) * | 2008-12-30 | 2013-03-27 | 第一毛织株式会社 | Antistatic adhesive composition, adhesive film using the same, method for producing the adhesive film, and method of fabricating liquid crystal display |
| US8324316B2 (en) * | 2009-02-06 | 2012-12-04 | Eastman Chemical Company | Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom |
| US9029460B2 (en) * | 2009-02-06 | 2015-05-12 | Stacey James Marsh | Coating compositions containing acrylic and aliphatic polyester blends |
| US9029461B2 (en) * | 2009-02-06 | 2015-05-12 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
| US8168721B2 (en) | 2009-02-06 | 2012-05-01 | Eastman Chemical Company | Coating compositions containing tetramethyl cyclobutanediol |
| US8163850B2 (en) | 2009-02-06 | 2012-04-24 | Eastman Chemical Company | Thermosetting polyester coating compositions containing tetramethyl cyclobutanediol |
| US9598602B2 (en) | 2014-11-13 | 2017-03-21 | Eastman Chemical Company | Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds |
| US9487619B2 (en) | 2014-10-27 | 2016-11-08 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
| WO2016069572A1 (en) | 2014-10-27 | 2016-05-06 | Eastman Chemical Company | Resole phenolic resins curable with functional polyesters |
| US9650539B2 (en) | 2014-10-27 | 2017-05-16 | Eastman Chemical Company | Thermosetting compositions based on unsaturated polyesters and phenolic resins |
| US20160340471A1 (en) | 2015-05-19 | 2016-11-24 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
| US20170088665A1 (en) | 2015-09-25 | 2017-03-30 | Eastman Chemical Company | POLYMERS CONTAINING CYCLOBUTANEDIOL AND 2,2 BIS(HYDROXYMETHYL) AlKYLCARBOXYLIC ACID |
| US20170101502A1 (en) | 2015-10-13 | 2017-04-13 | Eastman Chemical Company | Systems and methods for forming polyurethanes |
| US9988553B2 (en) | 2016-02-22 | 2018-06-05 | Eastman Chemical Company | Thermosetting coating compositions |
| US10011737B2 (en) | 2016-03-23 | 2018-07-03 | Eastman Chemical Company | Curable polyester polyols and their use in thermosetting soft feel coating formulations |
| US10667514B2 (en) | 2017-12-12 | 2020-06-02 | International Business Machines Corporation | Antimicrobial ionene compositions with a variety of functional groups |
| US10687530B2 (en) | 2017-12-12 | 2020-06-23 | International Business Machines Corporation | Hydrophilic polymers with antimicrobial functionalities |
| US10836864B2 (en) | 2017-12-12 | 2020-11-17 | International Business Machines Corporation | Chemical compositions with antimicrobial functionality |
| US10653142B2 (en) | 2017-12-12 | 2020-05-19 | International Business Machines Corporation | Polymers with antimicrobial functionalities |
| US10687528B2 (en) | 2017-12-12 | 2020-06-23 | International Business Machines Corporation | Antimicrobial polymers with enhanced functionalities |
| US10743537B2 (en) * | 2017-12-12 | 2020-08-18 | International Business Machines Corporation | Monomer compositions with antimicrobial functionality |
| US10595527B2 (en) | 2017-12-12 | 2020-03-24 | International Business Machines Corporation | Antimicrobial polymers capable of supramolecular assembly |
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|---|---|---|---|---|
| US2832747A (en) * | 1953-02-18 | 1958-04-29 | Du Pont | Polymeric compositions comprising linear polymers united through ionic crosslinkages and through covalent crosslinkages, process for their preparation, and fabrics coated therewith |
| US3011918A (en) * | 1959-05-29 | 1961-12-05 | Dow Chemical Co | Electroconductive coated paper and method of making the same |
| US3804668A (en) * | 1972-03-30 | 1974-04-16 | Rohm & Haas | Electroconductive paper |
| US3617372A (en) * | 1969-08-20 | 1971-11-02 | Rohm & Haas | Electroconductive paper |
| US3674711A (en) * | 1969-12-10 | 1972-07-04 | Varian Associates | Electrically conductive transparent plastic material |
| US3798032A (en) * | 1971-10-06 | 1974-03-19 | Weyerhaeuser Co | Electroconductive coating, electrostatographic copy sheet, and methods of making and using the same |
| US4011176A (en) * | 1975-01-31 | 1977-03-08 | The Dow Chemical Company | Electroconductive coating composition containing cationic latexes |
| CH642670A5 (en) * | 1979-12-21 | 1984-04-30 | Ciba Geigy Ag | METHOD FOR PRODUCING CROSSLINKED PLASTICS AND THEIR USE. |
| JPS5924706A (en) * | 1982-08-02 | 1984-02-08 | Asahi Chem Ind Co Ltd | Liquid composition which can form conductive film |
| JPS5924727A (en) * | 1982-08-02 | 1984-02-08 | Asahi Chem Ind Co Ltd | Yarn, film, or molding having active surface and their production |
-
1986
- 1986-07-30 US US06/892,173 patent/US4698391A/en not_active Expired - Lifetime
-
1987
- 1987-05-27 CA CA000538066A patent/CA1277080C/en not_active Expired - Fee Related
- 1987-06-25 EP EP87109131A patent/EP0254874A3/en not_active Withdrawn
- 1987-07-30 JP JP62191474A patent/JPS6337157A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6337157A (en) | 1988-02-17 |
| EP0254874A2 (en) | 1988-02-03 |
| US4698391A (en) | 1987-10-06 |
| EP0254874A3 (en) | 1990-02-07 |
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