Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component

Information

  • Patent Grant
  • 6441058
  • Patent Number
    6,441,058
  • Date Filed
    Tuesday, January 16, 2001
    23 years ago
  • Date Issued
    Tuesday, August 27, 2002
    22 years ago
Abstract
The present invention involves the use of powder coating methods to form coated abrasives. In one embodiment, the powder is in the form of a multiplicity of binder precursor particles comprising a radiation curable component. In other embodiments, the powder comprises at least one metal salt of a fatty acid and optionally an organic component that may be a thermoplastic macromolecule, a radiation curable component, and/or a thermally curable macromolecule. In either embodiment, the powder exists as a solid under the desired dry coating conditions, but is easily melted at relatively low temperatures and then solidified also at reasonably low processing temperatures. The principles of the present invention can be applied to form make coats, size coats, and/or supersize coats, as desired.
Description




FIELD OF THE INVENTION




This invention is in the field of abrasive articles. More specifically, this invention relates to abrasive articles in which a powder of fusible particles is dry coated, liquefied, and then cured to form at least a portion of the bond system of the abrasive article.




BACKGROUND OF THE INVENTION




Coated abrasive articles generally comprise a backing to which a multiplicity of abrasive particles are bonded by a suitable bond system. A common type of bond system includes a make coat, a size coat, and optionally a supersize coat. The make coat includes a tough, resilient polymer binder that adheres the abrasive particles to the backing. The size coat, also including a tough resilient polymer binder that may be the same or different from the make coat binder, is applied over the make coat to reinforce the particles. The supersize coat, including one or more antiloading ingredients or perhaps grinding aids, may then be applied over the size coat if desired.




In a conventional manufacturing process, the ingredients that are used to form the make coat are dispersed or dissolved, as the case may be, in a sufficient amount of a solvent, which may be aqueous or nonaqueous, to provide the make coat formulation with a coatable viscosity. The fluid formulation is then coated onto the backing, after which the abrasive particles are applied to the make coat formulation. The make coat formulation is then dried to remove the solvent and at least partially cured. The ingredients that are used to form the size coat are also dispersed in a solvent, and the resultant fluid formulation is then applied over the make coat and abrasive particles, dried and cured. A similar technique is then used to apply the supersize coat over the size coat.




The conventional manufacturing process has some drawbacks, however, because all of the coating formulations are solvent-based. Typical make and size coat formulations may include 10 to 50 weight percent of solvent. Supersize coating formulations, in particular, require even more solvent in order to form useful coatings having the desired coating weight and viscosity. Solvents, however, can be expensive to purchase and/or to handle properly. Solvents also must be removed from the coatings, involving substantial drying costs in terms of capital equipment, energy costs, and cycle time. There are also further costs and environmental concerns associated with solvent recovery or disposal. Solvent-based coating formulations also typically require coating methods involving contact with underlying layers at the time of coating. Such contact can disrupt the orientation of the coated abrasive particles, adversely affecting abrading performance.




Not surprisingly, solventless manufacturing techniques have been investigated. One promising approach involves powder coating techniques in which a coating is formed by dry coating a powder of extremely fine, curable binder particles onto a suitable backing, melting the coated powder so that the particles fuse together to form a uniform melt layer, and then curing the melt layer to form a solid, thermoset, binder matrix. For example, PCT patent publication WO 97/25185 describes forming a binder for abrasive particles from dry powders. The dry powders comprise thermally curable phenolic resins that are dry coated onto a suitable backing. After coating, the particles are melted. Abrasive particles are then applied to the melted formulation. The melted formulation is then thermally cured to form a solid, make coat binder matrix. A size coat may be applied in the same way. Significantly, the make and size coats are formed without any solvent, and the size coat powder may be deposited without contacting, and hence disrupting, the underlying abrasive particles.




Notwithstanding the advantages offered by powder coating techniques described in PCT patent publication WO 97/25185, the powders described in this document incorporate resins that are thermally cured. The use of such resins poses substantial challenges during manufacture. Thermally cured resins generally tend to be highly viscous at reasonable processing temperatures, and thus are difficult to get to flow well. This makes it somewhat challenging to cause the binder particles to melt and fuse together in a uniform manner. The thermally curable resins also typically require relatively high temperatures to achieve curing. This limits the kinds of materials that can be incorporated into an abrasive article. In particular, many kinds of otherwise desirable backing materials could be damaged or degraded upon exposure to the temperatures required for curing. It is also difficult to control the start and rate of thermal curing. Generally, thermal curing begins as soon as heat is applied to melt the powder particles. As a consequence, the cure reaction may proceed too far before the powder particles are adequately fused. Further, the resultant bond between the cured binder and the adhesive particles may end up being weaker than is desired.




Accordingly, there is still a need for a solventless manufacturing technique for making abrasive articles that avoids disrupting abrasive particle orientation as the various component layers of the abrasive bond system are formed.




SUMMARY OF THE INVENTION




The present invention involves the use of powder coating methods to form coated abrasives. In one embodiment, the powder is in the form of a multiplicity of binder precursor particles comprising a radiation curable component. In other embodiments, the powder comprises at least one metal salt of a fatty acid and optionally an organic component that may be a thermoplastic macromolecule, a radiation curable component, and/or a thermally curable macromolecule. In either embodiment, the powder exists as a solid under the desired dry coating conditions, but is easily melted at relatively low temperatures and then solidified also at reasonably low processing temperatures. The principles of the present invention can be applied to form make coats, size coats, and/or supersize coats, as desired.




The present invention offers several advantages. Firstly, because melting and curing occur at relatively low temperatures, abrasive articles prepared in accordance with the present invention can be used with a wider range of other components, for example, backing materials, that otherwise would be damaged at higher temperatures. The ability to use lower processing temperatures also means that the present invention has lower energy demands, making the invention more efficient and economical in terms of energy costs. Additionally, the powder coatings can be applied at 100% solids with no solvent whatsoever. Therefore, emission controls, solvent handling procedures, solvent drying, solvent recovery, solvent disposal, drying ovens, energy costs associated with solvents, and the significant costs thereof, are entirely avoided. Powder coating is a noncontact coating method. Unlike many solvent coating techniques, for example, roll coating or the like, powder coating methods are noncontact and, therefore, avoid the kind of coating contact that might otherwise disrupt coated abrasive particles. This advantage is most noticeable when applying size and supersize coats over underlying make coat and abrasive particles. Powder coating methods are versatile and can be applied to a broad range of materials.




The use of dry powder particles comprising a radiation curable component and/or a metal salt of a fatty acid is particularly advantageous in that excellent control is provided over the curing process. Specifically, one can precisely control not only when cure begins, but the rate of cure as well. Thus, the premature crosslinking problems associated with conventional thermosetting powders is avoided. The result is that a binder derived from binder particles and/or powders of the present invention tends to bond more strongly to abrasive particles and is more consistently fully fused prior to curing, making manufacture much easier. As another advantage, the binder particles of the present invention comprising a radiation curable component can be formed using low molecular weight, radiation curable materials that have relatively low viscosity when melted, providing much better flow and fusing characteristics than thermally curable, resinous counterparts.




In one aspect, the present invention relates to an abrasive article comprising a plurality of abrasive particles incorporated into a bond system, wherein at least a portion of the bond system comprises a cured binder matrix derived from ingredients comprising a plurality of solid, binder precursor particles, said binder precursor particles comprising a radiation curable component that is fluidly flowable at a temperature in the range from about 35° C. to about 180° C.




In another aspect, the present invention relates to a method of forming an abrasive article, comprising the steps of (a) incorporating a plurality of abrasive particles into a bond system; and (b) deriving at least a portion of the bond system from a plurality of solid, binder precursor particles, said binder precursor particles comprising a radiation curable component that is fluidly flowable at a temperature in the range from about 35° C. to about 180° C.




In still yet another aspect, the present invention provides a powder, comprising a radiation curable component that is a solid at temperatures below about 35° C. and is fluidly flowable at a temperature in the range from about 35° C. to about 180° C.




The present invention also provides a fusible powder, comprising 100 parts by weight of a metal salt of a fatty acid and 0 to 35 parts by weight of a fusible organic component.




The present invention also relates to a method of forming a supersize coating on an underlying abrasive layer of an abrasive article. A fusible powder is dry coated onto the abrasive layer, wherein the fusible powder comprises at least one metal salt of a fatty acid. The fusible powder is liquefied to form a supersize melt layer. The supersize melt layer is solidified, whereby the supersize coating is formed.




As used herein, the term “cured binder matrix” refers to a matrix comprising a crosslinked, polymer network in which chemical linkages exist between polymer chains. A preferred cured binder matrix is generally insoluble in solvents in which the corresponding, crosslinkable binder precursor(s) is readily soluble. The term “binder precursor” refers to monomeric, oligomeric, and/or polymeric materials having pendant functionality allowing the precursors to be crosslinked to form the corresponding cured binder matrix.




If desired, the cured binder matrix of the present invention may be in the form of an interpenetrating polymer network (IPN) in which the binder matrix includes separately crosslinked, but entangled networks of polymer chains. As another option, the cured binder matrix may be in the form of a semi-IPN comprising uncrosslinked components, for example, thermoplastic oligomers or polymers that generally do not participate in crosslinking reactions, but nonetheless are entangled in the network of crosslinked polymer chains.




As used herein, the term “macromolecule” shall refer to an oligomer, a polymer, and combinations thereof.











BRIEF DESCRIPTION OF THE DRAWINGS




The above mentioned and other advantages of the present invention, and the manner of attaining them, will become more apparent and the invention itself will be better understood by reference to the following description of the embodiments of the invention taken in conjunction with the accompanying drawings, wherein:





FIG. 1

is a sectional side view of a coated abrasive article according to one embodiment of the present invention.





FIG. 2

schematically shows a reaction scheme for making one kind of radiation curable monomer suitable in the practice of the present invention.





FIG. 3

is a preferred embodiment of radiation curable monomer prepared using the reaction scheme of FIG.


2


.





FIG. 4

schematically shows a reaction scheme for making another class of radiation curable monomer suitable in the practice of the present invention.





FIG. 5

is a preferred embodiment of radiation curable monomer prepared using the reaction scheme of FIG.


4


.





FIG. 6

is a preferred embodiment of another radiation curable monomer of the present invention.





FIG. 7

schematically shows a reaction scheme for making the class of radiation curable monomers including the monomer of FIG.


6


.





FIG. 8A

is a preferred embodiment of another radiation curable monomer of the present invention.





FIG. 8B

is a cyanate ester novolak oligomer suitable in the practice of the present invention.





FIG. 9

shows a general formula for a metal salt of a fatty acid suitable in the practice of the present invention.





FIG. 10

shows the formula for one embodiment of a radiation curable novolak type phenolic oligomer suitable in the practice of the present invention.





FIG. 11

shows a formula for one type of a radiation curable epoxy oligomer suitable in the practice of the present invention.





FIG. 12

is a schematic representation of an apparatus for making a coated abrasive of the present invention having make, size and supersize coatings.











DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS




The radiation curable, fusible binder precursor particles of the present invention may be incorporated into a wide range of different kinds of abrasive articles with beneficial results. For purposes of illustration, the radiation curable, fusible binder precursor particles will be described with respect to the particular flexible, coated abrasive article


10


illustrated in FIG.


1


. The embodiments of the present invention described in connection with

FIG. 1

are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather the embodiments are chosen and described so that others skilled in the art may appreciate and understand the principles and practices of the present invention.




Abrasive article


10


generally includes backing


12


and abrasive layer


14


bonded to backing


12


. Backing


12


may be any suitable backing and typically may be comprised of paper, vulcanized rubber, a polymeric film (primed or unprimed), a woven or nonwoven fibrous material, composites of these, and the like. Backings made from paper typically may have a basis weight in the range from 25 g/m


2


to 300 g/m


2


or more. Backings made from paper or fibrous materials optionally may be treated with a presize, backsize, and/or saturant coating in accordance with conventional practices. Specific materials suitable for use as backing


12


are well known in the art and have been described, for example, in U.S. Pat. Nos. 5,436,063; 4,991,362; and 2,958,593, incorporated herein by reference.




Abrasive coating


14


includes a plurality of abrasive particles


16


functionally distributed in bond system


18


generally comprising make coat


20


, size coat


22


, and optional supersize coat


24


. Abrasive particles


16


may comprise any suitable abrasive material or combination of materials having abrading capabilities. Abrasive particles


16


preferably comprise at least one material having a Mohs hardness of at least about 8, more preferably at least about 9. Examples of such materials include fused aluminum oxide, heat treated aluminum oxide, white fused aluminum oxide, black silicon carbide, green silicon carbide, titanium diboride, boron carbide, tungsten carbide, titanium carbide, diamond, silica, iron oxide, chromia, ceria, zirconia, titania, silicates, tin oxide, cubic boron nitride, garnet, fused alumina zirconia, sol gel abrasive particles, combinations of these, and the like. As an option, abrasive particles


16


may include a surface coating to enhance the performance of the particles in accordance with conventional practices. In some instances, the surface coating can be formed from a material, such as a silane coupling agent, that increases adhesion between abrasive particles


16


and the binders used in make coat


20


, size coat


22


, and/or supersize coat


24


.




Abrasive particles


16


can be present in any suitable size(s) and shape(s). For example, with respect to size, preferred abrasive particles


16


typically have an average size in the range from about 0.1 micrometers to 2500 micrometers, more preferably from about 1 micrometer to 1300 micrometers. Abrasive particles


16


may also have any shape suitable for carrying out abrading operations. Examples of such shapes include rods, triangles, pyramids, cones, solid spheres, hollow spheres, combinations of these, and the like. Abrasive particles


16


may be present in substantially nonagglomerated form or, alternatively, may be in the form of abrasive agglomerates in which individual particles are adhered together. Examples of abrasive agglomerates are described in U.S. Pat. No. 4,652,275 and U.S. Pat. No. 4,799,939, which patents are incorporated herein by reference.




Make coat


20


helps adhere abrasive particles


16


to backing


12


. Size coat


22


is applied over make coat


20


and abrasive particles


16


in order to reinforce particles


16


. Optional supersize coat


24


may be included over size coat


22


in order to prevent or reduce the accumulation of swarf (the material abraded from a workpiece) among abrasive particles


16


during abrading operations. Swarf accumulation might otherwise dramatically reduce the cutting ability of abrasive article


10


over time. Alternatively, supersize coat


24


may also be included over size coat


22


in order to incorporate grinding aids into abrasive article


10


. Supersize coatings are further described in European Patent Publication No. 486, 308, which is incorporated herein by reference.




In the practice of the present invention, at least portions of one or more of make coat


20


, size coat


22


, and/or supersize coat


24


constituting bond system


18


comprise a cured binder matrix derived from the binder precursor particles of the present invention. The binder precursor particles of the present invention generally include a radiation curable component that may be formed from any one or more radiation curable, fusible materials that can be dry coated in particulate form, then liquefied to convert the precursor material into a fluid, melt layer, and then cured by exposure to a suitable source of curing energy to convert the fluid melt layer into a thermoset, solid, cured binder matrix component of bond system


18


.




In the practice of the present invention, “radiation curable” refers to functionality directly or indirectly pendant from a monomer, oligomer, or polymer backbone (as the case may be) that participate in crosslinking reactions upon exposure to a suitable source of curing energy. Such functionality generally includes not only groups that crosslink via a cationic mechanism upon radiation exposure but also groups that crosslink via a free radical mechanism. Representative examples of radiation crosslinkable groups suitable in the practice of the present invention include epoxy groups, (meth)acrylate groups, olefinic carbon-carbon double bonds, allyloxy groups, alpha-methyl styrene groups, (meth)acrylamide groups, cyanate ester groups, vinyl ethers groups, combinations of these, and the like.




The energy source used for achieving crosslinking of the radiation curable functionality may be actinic (for example, radiation having a wavelength in the ultraviolet or visible region of the spectrum), accelerated particles (for example, electron beam radiation), thermal (for example, heat or infrared radiation), or the like. Preferably, the energy is actinic radiation or accelerated particles, because such energy provides excellent control over the initiation and rate of crosslinking. Additionally, actinic radiation and accelerated particles can be used for curing at relatively low temperatures. This avoids degrading components of abrasive article


10


that might be sensitive to the relatively high temperatures that might be required to initiate crosslinking of the radiation curable groups when using thermal curing techniques. Suitable sources of actinic radiation include a mercury lamp, a xenon lamp, a carbon arc lamp, a tungsten filament lamp, sunlight, and the like. Ultraviolet radiation, especially from a medium pressure mercury arc lamp, is most preferred.




The amount of curing energy to be used for curing depends upon a number of factors, such as the amount and the type of reactants involved, the energy source, web speed, the distance from the energy source, and the thickness of the bond layer to be cured. Generally, the rate of curing tends to increase with increased energy intensity. The rate of curing also may tend to increase with increasing amounts of photocatalyst and/or photoinitiator being present in the composition. As general guidelines, actinic radiation typically involves a total energy exposure from about 0.1 to about 10 J/cm


2


, and electron beam radiation typically involves a total energy exposure in the range from less than 1 Megarad to 100 Megarads or more, preferably 1 to 10 Mrads. Exposure times may be from less than about 1 second up to 10 minutes or more. Radiation exposure may occur in air or in an inert atmosphere such as nitrogen.




The particle size of the binder precursor particles of the present invention is not particularly limited so long as the particles can be adequately fused and then cured to form desired portions of bond system


18


with the desired level of uniformity and performance. If the particles are too big, it is more difficult to control the uniformity of coating thickness. Larger particles are also not as free flowing as smaller particles. Therefore, particles with a smaller average particle size such that the particles are in the form of a free flowing powder are preferred. However, extremely small particles may pose a safety hazard. Additionally, control over coating thickness also may become more difficult when using extremely small particles. Accordingly, as general guidelines, preferred binder precursor particles generally have an average particle size of less than about 500 micrometers, preferably less than about 125 micrometers, and more preferably 10 to 90 micrometers. In the practice of the present invention, the average particle size of the particles may be determined by laser diffraction using an instrument commercially available under the trade designation “HORIBA LA-910” from Horiba Ltd.




In preferred embodiments of the invention, the radiation curable component of the fusible binder precursor particles comprises one or more radiation curable monomers, oligomers, and/or polymers that, at least in combination, exist as a solid at about room temperature, for example, 20° C. to about 25° C., to facilitate dry coating under ambient conditions, but then melt or otherwise become fluidly flowable at moderate temperatures in the range from about 35° C. to about 180° C., preferably 40° C. to about 140° C., to facilitate fusing and curing without resort to higher temperatures that might otherwise damage other components of abrasive article


10


. The term “monomer” as used herein refers to a single, one unit molecule capable of combination with itself or other monomers to form oligomers or polymers. The term “oligomer” refers to a compound that is a combination of 2 to 20 monomer units. The term “polymer” refers to a compound that is a combination of 21 or more monomer units.




Of course, in alternative, less preferred embodiments of the invention, the radiation curable component may exist as a solid only at relatively cool temperatures below ambient conditions. However, such embodiments would involve carrying out dry coating at correspondingly cool temperatures to ensure that the radiation curable component was solid during dry coating. Similarly, in other alternative embodiments of the invention, the radiation curable component may exist as a solid up to higher temperatures above about 180° C. However, such embodiments would involve carrying out melting and curing at correspondingly higher temperatures as well, which could damage other, temperature sensitive components of abrasive article


10


.




Generally, any radiation curable monomer, oligomer, and/or polymer, or combinations thereof, that is solid under the desired dry coating conditions and that may be melted under the desired melt processing conditions may be incorporated into the radiation curable component. Accordingly, the present invention is not intended to be limited to specific kinds of radiation curable monomers, oligomers, and polymers so long as these processing conditions are satisfied. However, particularly preferred radiation curable components that have excellent flow characteristics when liquefied generally comprise at least one polyfunctional, radiation curable monomer and at least one polyfunctional, radiation curable macromolecule (that is, an oligomer or polymer, preferably an oligomer), wherein at least one of the monomer and/or the macromolecule has a solid to nonsolid phase transition at a sufficiently high temperature such that the combination of the monomer and macromolecule is a solid below about 35° C., but is liquefied at a temperature in the range from about 35° C. to about 180° C., preferably 40° C. to about 140° C. More preferably, it is the monomer that is a solid, by itself, and the macromolecule, by itself, may or may not be a solid under the noted temperature ranges. In the practice of the present invention, radiation curable components comprising one or more monomers and one or more oligomers are preferred over embodiments including polymers. Blends of oligomers and monomers tend to have lower viscosity and better flow characteristics at lower temperatures, thus easing melting and fusing of the particles during processing.




For example, representative embodiments of radiation curable components suitable in the practice of the present invention include the following components:
















Embodiment




Compounds
























1




a solid, radiation curable, polyfunctional monomer having a







melting point in the range from 35° C. to 180° C.






2




a solid, radiation curable, polyfunctional macromolecule having







a glass transition temperature in the range from 35° C. to 180° C.






3




a solid blend including 10 to 90 parts by weight of a solid,







radiation curable, polyfunctional monomer and 10 to 90 parts







by weight of a solid, radiation curable, polyfunctional







macromolecule






4




a solid blend including 10 to 90 parts by weight of a solid,







radiation curable, polyfunctional monomer and 10 to 90 parts







by weight of a liquid, radiation curable, polyfunctional







macromolecule






5




a solid blend including 10 to 80 parts by weight of a liquid,







radiation curable, polyfunctional monomer and 10 to 80 parts







by weight of a solid, radiation curable, polyfunctional







macromolecule






6




a solid blend comprising 0.1 to 10 parts by weight of a liquid,







radiation curable, polyfunctional monomer and 100 parts by







weight of a metal salt of a fatty acid (make coat and/or size







coat)






7




a solid blend comprising 0 to 30 parts by weight of a liquid,







radiation curable, polyfunctional macromolecule and 100 parts







by weight of a metal salt of a fatty acid (supersize coat)






8




a solid blend comprising 100 parts by weight of a solid,







radiation curable, polyfunctional monomer and 0.1 to 10 parts







by weight of a metal salt of a fatty acid (make coat and/or size







coat)






9




a solid blend comprising 0 to 30 parts by weight of a solid,







radiation curable, polyfunctional macromolecule and 100 parts







by weight of a metal salt of a fatty acid (supersize coat)














With respect to the monomer, the solid to nonsolid phase transition is typically the melting point of the monomer. With respect to the macromolecule, the solid to nonsolid phase transition is typically the glass transition temperature of the macromolecule. In the practice of the present invention, glass transition temperature, Tg, is determined using differential scanning calorimetry (DSC) techniques. The term “polyflnctional” with respect to the monomer or macromolecule means that the material comprises, on average, more than 1 radiation curable group, preferably two or more radiation curable groups, per molecule. Polyfunctional monomers, oligomers, and polymers cure quickly into a crosslinked network due to the multiple radiation curable groups available on each molecule. Further, polyfunctional materials are preferred in this invention to encourage and promote polymeric network formation in order to provide bond system


18


with toughness and resilience.




Preferred monomers, oligomers, and polymers of the present invention are aromatic and/or heterocyclic. Aromatic and/or heterocyclic materials generally tend to be thermally stable when melt processed and also tend to have melting point and/or Tg characteristics in the preferred temperature ranges noted above. As an option, at least one of the monomer and the macromolecule, preferably the macromolecule, further comprises OH, that is, hydroxyl, functionality. While not wishing to be bound by theory, it is believed that the OH functionality helps promote adhesion between abrasive particles


16


and the corresponding portion of bond system


18


. Preferably, the macromolecule includes, on average, 0.1 to 1 OH groups per monomeric unit incorporated into the macromolecule.




For purposes of illustration, representative examples of suitable radiation curable monomers, oligomers, and polymers will now be described.




One representative class of polyfunctional, radiation curable, aromatic monomers and/or oligomers is shown in FIG.


2


.

FIG. 2

schematically shows reaction scheme


30


by which hydroxyl functional (meth)acrylate reactant


32


reacts with dicarboxylic acid reactant


34


to form radiation curable, poly(meth)acrylate functional polyester monomer


36


. The moiety W of reactant


34


desirably comprises an aromatic moiety for the reasons described above. The moiety Z is any suitable divalent linking group. Any kinds of hydroxyl functional (meth)acrylate reactant


32


and such aromatic dicarboxylic acid reactant


34


may be reacted together so long as the resultant radiation curable component is a solid under the desired dry coating conditions and has a melting point in the desired processing range. Examples of hydroxyl functional (meth)acrylate reactant


32


include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, combinations of these, and the like. Examples of aromatic dicarboxylic acid reactant


34


include terephthalic acid, isophthalic acid, phthalic acid, combinations of these, and the like. Although reactant


34


is shown as a dicarboxylic acid, an acid dihalide, diester, or the like could be used instead. The moiety X in monomer


36


is a divalent linking group typically identical to Z. R is hydrogen or a lower alkyl group of 1 to 4 carbon atoms, preferably —H or —CH


3


.





FIG. 3

shows a particularly preferred embodiment of a radiation curable monomer


38


prepared in accordance with the reaction scheme of FIG.


2


. Radiation curable monomer


38


has a melting point of 97° C. The radiation curable monomers


36


and


38


of

FIGS. 2 and 3

, and methods of making such monomers are further described in U.S. Pat. No. 5,523,152, incorporated herein by reference.




Another representative class of monomers in the form of radiation curable vinyl ether monomer


40


suitable in the practice of the present invention is shown as the product in

FIG. 4

of a reaction between diisocyanate reactant


42


and hydroxyl functional vinyl ether reactant


44


. The moiety W′ desirably includes an aromatic moiety in the backbone for the reasons described above, and Z′ is a suitable divalent linking group. R is as defined above in FIG.


2


. Any kinds of hydroxyl functional vinyl ether reactant


44


and diisocyante reactant


42


may be reacted together so long as the resultant radiation curable component is a solid under the desired dry coating conditions and has a melting point in the desired processing range. Examples of hydroxyl functional vinyl ether reactant


44


include 4-hydroxybutyl vinyl ether (HO CH


2


CH


2


CH


2


CH


2


OCH═CH


2


) and the like. Examples of diisocyanate reactant


42


include diphenylmethane-4,4-diisocyanate, toluene diisocyanate, combinations of these, and the like. The reaction scheme of

FIG. 4

may also be carried out using a compound such as a hydroxyl functional (meth)acrylate in place of hydroxyl functional vinyl ether reactant


44


.





FIG. 5

shows a particularly preferred embodiment of a radiation curable vinyl ether monomer


50


prepared in accordance with the reaction scheme of FIG.


4


. Radiation curable vinyl ether monomer


50


has a melting point of 60-65° C.





FIG. 6

shows another example of a suitable radiation curable, aromatic monomer


60


commonly referred to in the art as tris (2-hydroxyethyl) isocyanurate triacrylate, or “TATHEIC” for short. This monomer has a melting point in the range from 35° C. to 40° C. The TATHEIC monomer is generally formed by reaction scheme


70


of

FIG. 7

in which hydroxyl functional isocyanurate


72


is reacted with carboxylic acid


74


to form acrylated isocyanurate


76


. The X″ moiety may be any suitable divalent linking group such as —CH


2


CH


2


— or the like. The acrylate form is shown in

FIG. 6

, but monomer


60


could be a methacrylate or the like as well.





FIG. 8A

shows another example of a radiation curable, aromatic monomer in the form of an aromatic cyanate ester


80


. This monomer has a melting point of 78° C. to 80° C. This and similar monomers have been described in U.S. Pat. No. 4,028,393. Other cyanate esters are described in U.S. Pat. Nos. 5,215,860; 5,294,517; and 5,387,492, the cyanate ester descriptions incorporated by reference herein.




Other examples of radiation curable monomers that may be incorporated into the radiation curable component of the present invention include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, glycerol triacrylate, glycerol trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, neopentylglycol diacrylate, and neopentylglycol dimethacrylate. Mixtures and combinations of different types of polyfunctional (meth)acrylates also can be used. Although some of these other monomer examples might not be solids under ambient conditions by themselves, blends of these monomers with other radiation curable ingredients may nonetheless provide particles having the desired solid characteristics.




Preferred radiation curable oligomers of the present invention generally have a number average molecular weight in the range from about 400 to 5000, preferably about 800 to about 2500 and either are solid at ambient conditions, or if not solid under ambient conditions, nonetheless form solid blends in combination with other ingredients of the radiation curable component. In addition to radiation curable functionality, preferred oligomers of the present invention also preferably include pendant hydroxyl functionality and are aromatic.




One preferred class of radiation curable, hydroxyl functional, aromatic oligomers found to be suitable in the practice of the present invention includes the class of radiation curable, novolak-type phenolic oligomers. A representative radiation curable, aromatic novolak-type phenolic oligomer


90


having pendant cyanate ester functionality is shown in

FIG. 8B

, wherein n has a value in the range from about 3 to about 20, preferably 3 to 10. Another representative, radiation curable oligomer 100 having pendant acrylamide functionality and hydroxyl functionality (a combination of functionality that is particularly beneficial when incorporated into a make coat formulation) is shown in

FIG. 10

, wherein n has an average value in the range from about 3 to 20, preferably 3 to 10. In a particularly preferred embodiment, n has an average value of about 3 to 5. Interestingly, the resultant oligomer for which the average value of n is about 3 to 5 tends to have a taffy-like consistency under ambient conditions. Advantageously, however, such oligomer readily forms solid particles when combined with other solid, radiation curable monomers, oligomers, and polymers to facilitate dry coating, but flows easily when heated after dry coating, facilitating formation of uniform, fused binder matrices. The class of radiation curable, novolak-type phenolic oligomers, including the particular oligomer


100


shown in

FIG. 10

has been described generally in U.S. Pat. Nos. 4,903,440 and 5,236,472, incorporated herein by reference.




Another preferred class of radiation curable, hydroxyl functional, aromatic oligomers found to be suitable in the practice of the present invention includes the class of epoxy oligomers obtained, for example, by chain extending bisphenol A up to a suitable molecular weight and then functionalizing the resultant oligomer with radiation curable functionality. For example,

FIG. 11

illustrates such an epoxy oligomer


110


which has been reacted with an acrylic acid to provide radiation curable functionality. Preferably, n of

FIG. 11

has a value such that oligomer


110


has a number average molecular weight in the range from about 800 to 5000, preferably about 1000 to 1200. Such materials typically are viscous liquids under ambient conditions but nonetheless form solid powders when blended with other solid materials such as solid monomers, solid macromolecules, and/or calcium and/or zinc stearate. Accordingly, such materials also can be easily dry coated in solid form under ambient conditions, but then demonstrate excellent flow characteristics upon heating to facilitate formation of binder matrices having desired performance characteristics. Indeed, any oligomer that has this dual liquid/solid behavior under ambient conditions would be particularly advantageous with respect to achieving such processing advantages. Acrylate oligomers according to

FIG. 11

are available under the trade designations “RSX29522” and “EBECRYL 3720”, respectively, from UCB Chemicals Corp., Smyrna, Ga.




Of course, the oligomers suitable in the practice of the present invention are not limited solely to the preferred novolak-type phenolic oligomers or epoxy oligomers described above. For instance, other radiation curable oligomers that are solid at room temperature, or that form solids at room temperature in blends with other ingredients, include polyether oligomers such as polyethylene glycol


200


diacrylate having the trade designation “SR259” and polyethylene glycol


400


diacrylate having the trade designation “SR344,” both being commercially available from Sartomer Co., Exton, Pa.; and acrylated epoxies available under the trade designations “CMD 3500,” “CMD 3600,” and “CMD 3700,” from Radcure Specialties.




A wide variety of radiation curable polymers also can be beneficially incorporated into the radiation curable component, although polymers tend to be more viscous and do not flow as easily upon heating as compared to monomers and oligomers. Representative radiation curable polymers of the present invention comprise vinyl ether functionality, cyanate ester functionality, (meth)acrylate functionality, (meth)acrylamide functionality, cyanate ester functionality, epoxy functionality, combinations thereof, and the like. Representative examples of polymers that may be functionalized with one or more of these radiation curable groups include polyamides, phenolic resins, epoxy resins, polyurethanes, vinyl copolymers, polycarbonates, polyesters, polyethers, polysulfones, polyimides, combinations of these, and the like.




For example, in one embodiment, the radiation curable polymer may be an epoxy functional resin having at least one oxirane ring polymerizable by a ring opening reaction. These materials generally have, on the average, at least two epoxy groups per molecule (preferably more than two epoxy groups per molecule). The polymeric epoxides include linear polymers having terminal epoxy groups (for example, a diglycidyl ether of a polyoxyalkylene glycol), polymers having skeletal oxirane units (for example, polybutadiene polyepoxide), and polymers having pendent epoxy groups (for example, a glycidyl methacrylate polymer or copolymer). The number average molecular weight of the epoxy functional resin most typically may vary from about 1000 to about 5000 or more.




Another useful class of epoxy functional macromolecules includes those which contain cyclohexene oxide groups derived from monomers such as the epoxycyclohexanecarboxylates, typified by 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane carboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate. For a more detailed list of useful epoxides of this nature, reference may be made to U.S. Pat. No. 3,117,099, incorporated herein by reference.




Further epoxy functional macromolecules which are particularly useful in the practice of this invention include resins incorporating glycidyl ether monomers of the formula











where R′ is alkyl or aryl and n is an integer of 1 to 6. Examples are the glycidyl ethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of chlorohydrin such as epichlorohydrin, for example, the diglycidyl ether of 2,2-bis-2,3-epoxypropoxyphenol propane. Further examples of epoxides of this type are described in U.S. Pat. No. 3,018,262, incorporated herein by reference.




There are also several commercially available epoxy macromolecules that can be used in this invention. In particular, epoxides which are readily available include octadecylene oxide, epichlorohydrin, styrene oxide, vinyl cyclohexene oxide, glycidol, glycidyl-methacrylate, diglycidyl ether of Bisphenol A (for example, those available under the trade designations “EPON 828,” “EPON 1004,” and “EPON 1001F” from Shell Chemical Co., and “DER-332” and “DER-334,” from Dow Chemical Co.), diglycidyl ether of Bisphenol F (for example, “ARALDITE GY281” from Ciba-Geigy), vinylcyclohexene dioxide (for example, having the trade designation “ERL 4206” from Union Carbide Corp.), 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexene carboxylate (for example, having the trade designation “ERL-4221” from Union Carbide Corp.), 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane (for example, having the trade designation “ERL-4234” from Union Carbide Corp.), bis(3,4-epoxy-cyclohexyl) adipate (for example, having the trade designation “ERL-4299” from Union Carbide Corp.), dipentene dioxide (for example, having the trade designation “ERL-4269” from Union Carbide Corp.), epoxidized polybutadiene (for example, having the trade designation “OXIRON 2001” from FMC Corp.), silicone resin containing epoxy functionality, epoxy silanes, for example, beta-3,4-epoxycyclohexylethyltri-methoxy silane and gamma-glycidoxypropyltrimethoxy silane, commercially available from Union Carbide, flame retardant epoxy resins (for example, having the trade designation “DER-542,” a brominated bisphenol type epoxy resin available from Dow Chemical Co.), 1,4-butanediol diglycidyl ether (for example, having the trade designation “ARALDITE RD-2” from Ciba-Geigy), hydrogenated bisphenol A-epichlorohydrin based epoxy resins (for example having the trade designation “EPONEX 1510” from Shell Chemical Co.), and polyglycidyl ether of phenol-formaldehyde novolak (for example, having the trade designation “DEN-431” and “DEN-438” from Dow Chemical Co.).




It is also within the scope of this invention to use an epoxy functional macromolecule that has both epoxy and (meth)acrylate functionality. For example, one such resin having such dual functionality is described in U.S. Pat. No. 4,751,138 (Tumey et al.), which is incorporated herein by reference.




In addition to the radiation curable component, the binder precursor particles of the present invention may also include a thermoplastic resin in order to adjust the properties of the particles and/or the resultant cured binder matrix. For example, thermoplastic resins can be incorporated into the particles in order to adjust flow properties of the particles upon being melted, to allow the melt layer to display pressure sensitive adhesive properties so that abrasive particles more aggressively adhere to the melt layer prior to curing (desirable for a make coat), to adjust the flexibility characteristics of the resultant cured binder matrix, combinations of these objectives, and the like. Just a few examples of the many different kinds of thermoplastic polymers useful in the present invention include polyester, polyurethane, polyamide, combinations of these, and the like. When used, the binder precursor particles may include up to 30 parts by weight of a thermoplastic component per 100 parts by weight of the radiation curable component.




In alternative embodiments of the present invention, rather than using binder precursor particles as described above to form supersize coat


24


, at least a portion of supersize coat


24


can be made from a fusible powder comprising at least one metal salt of a fatty acid. Advantageously, metal salts of a fatty acid function as an antiloading agent, a binder component, and/or a flow control agent, when incorporated into supersize coat


24


. Although not required, the fusible powder may also include a binder comprising one or more monomers and/or macromolecules that may be thermoplastic, thermally curable, and/or radiation curable as described above in connection with the binder precursor particles. In typical embodiments, the fusible powder comprises 70 to 95 parts by weight of at least one metal salt of a fatty acid and 0 to 30 parts by weight of the binder.




The metal salts of a fatty acid ester suitable for use in the fusible powder generally may be represented by formula


90


shown in

FIG. 9

wherein R′ is a saturated or unsaturated moiety, preferably an alkyl group having at least 10, preferably 12 to 30, carbon atoms, M is a metal cation having a valence of n, wherein n typically is 1 to 3. Specific examples of compounds according to formula


90


of

FIG. 9

include lithium stearate, zinc stearate, calcium stearate, magnesium stearate combinations of these, and the like. The metal salt of a fatty acid preferably is calcium stearate, zinc stearate, or a combination thereof wherein the weight ratio of calcium stearate to zinc stearate is in the range from 1:1 to 9:1. The use of a powder comprising a combination of calcium and zinc stearates also provides an excellent way to control the melting characteristics of the powder. For example, if it is desired to increase the melting temperature of the powder, the amount of calcium stearate being used can be increased relative to the amount of zinc stearate. Conversely, if it is desired to lower the melting temperature of the powder, the amount of zinc stearate being used can be increased relative to the amount of calcium stearate. Calcium stearate is unique in that this material never truly melts. However, in fine powder form, for example, a powder having an average particle size of less than about 125 micrometers, calcium stearate can be used by itself, or in combination with other materials, to provide powders that readily flow when heated at moderately low processing temperatures.




Uniquely, solid embodiments of metal salts of fatty acids, for example, the metal stearates, may be blended with liquid monomers, oligomers, and/or polymers to form blends that, nonetheless, are solid and can be ground to form fine powders. Such powders have excellent viscosity, fusing, and flow characteristics when melt processed at reasonably low melt processing temperatures. Embodiments demonstrating this advantage of the invention will be described further below in the examples.




Optimally, the fusible powder of the present invention may include one or more fatty acids. Advantageously, the presence of a fatty acid makes it easier to melt process the fusible powder at reasonably low processing temperatures, for example, 35° C. to 180° C. For example, a preferred embodiment of a fusible powder of the present invention might include calcium stearate (a metal salt of a fatty acid) as a major component. A fusible powder including just calcium stearate by itself tends to be difficult to melt process, because calcium stearate never truly melts. However, if a fatty acid is incorporated into the fusible powder along with calcium stearate, the resultant blend can be readily melt processed at convenient temperatures.




Generally, preferred embodiments of the present invention include a sufficient amount of a fatty acid so that the fusible powder can be melt processed at the desired temperature, for example a temperature in the range from 35° C. to 180° C. Preferred fusible powders of the present invention incorporate up to 30, preferably about 10, parts by weight of one or more fatty acids per 70 to 100, preferably about 90, parts by weight of the metal salt of a fatty acid. Although any fatty acid can be used in the present invention, a preferred fatty acid is the corresponding acid form of the metal salt of a fatty acid being used. For instance, stearic acid is a preferred fatty acid when the metal salt of a fatty acid is a stearate, for example, zinc stearate or calcium stearate.




The binder precursor particles and/or fusible powder of the present invention may also include one or more grinding aids. Useful examples of classes of grinding aids include waxes, organic halide compounds, halide salts, metals, and alloys of metals. Organic halide compounds typically break down during abrading and release a halogen acid or a gaseous halide compound. Examples of organic halides include chlorinated waxes, such as tetrachloronapthalene, pentachloronapthalene, and polyvinyl chloride. Chlorinated waxes can also be considered to be waxes. Examples of halide salts include sodium chloride (NaCl), potassium chloride (KCl), potassium fluoroborate (KBF


4


), ammonium cryolite (NH4)


3


AlF


6


), cryolite (Na


3


AlF


6


),and magnesium chloride (MgCl


2


). Examples of metals include tin, lead, bismuth, cobalt, antimony, cadmium, iron, and titanium. Other grinding aids include sulfur and organic sulfur compounds, graphite, and metallic sulfides. Combinations of grinding aids can be used. The preferred grinding aid for stainless steel is potassium fluoroborate. The preferred grinding aid for mild steel is cryolite. The ratio of the fusible organic component to grinding aid ranges from 0 to 95, preferably ranges from about 10 to about 85, more preferably about 15 to about 60, parts by weight of a fusible organic component to about 5 to 100, preferably about 15 to about 85, more preferably about 40 to about 85, parts by weight grinding aid.




The binder precursor particles and/or fusible powder of the present invention additionally may comprise one or more optional additives, such as, plasticizers, other antiloading agents (that is, materials useful for reducing or preventing swarf accumulation), grinding aids, surface modification agents, fillers, flow agents, curing agents, hydroxyl containing additives, tackifiers, grinding aids, expanding agents, fibers, antistatic agents, lubricants, pigments, dyes, UV stabilizers, fungicides, bacteriocides, and the like. These additional kinds of additives may be incorporated into the binder precursor particles in according to conventional practices.




Selecting a suitable composition of the binder precursor particles and/or fusible powder for a particular application will depend, to a large extent, upon the portion of bond system


18


into which the particles will be incorporated. Different compositions may be more desirable depending upon whether the binder precursor particles are to be incorporated into make coat


20


, size coat


22


, and/or supersize coat


24


. Further, not all binder precursor particles to be incorporated into bond system


18


need be the same. Binder precursor particles of one composition, for instance, may be incorporated into make coat


20


and size coat


22


, while binder precursor particles of a second composition are incorporated into supersize coat


24


.




In one embodiment of the present invention suitable for use in make coat


20


and/or size coat


22


, a preferred binder precursor particle composition (Make/Size Composition I) comprises 100 parts by weight of a radiation curable binder component, about 1 to 5 parts by weight of a flow control agent, and about 0.5 to 5 parts by weight of a photoinitiator or photocatalyst. The preferred radiation curable binder component comprises a (i) solid, radiation curable monomer and (ii) a solid radiation curable oligomer and/or polymer, wherein the weight ratio of the monomer to the oligomer/polymer is in the range from 1:10 to 10:1, preferably 1:4 to 4:1, more preferably about 1:1. Preferred examples of the solid monomer include the monomer of

FIG. 3

, the cyanate ester of

FIG. 8

, and the TATHEIC monomer of FIG.


6


. Preferred examples of the solid oligomer/polymer include the epoxy functional resin commercially available under the trade designation “EPON 1001F” from Shell Chemical Co. and the acrylate functional oligomer available under the trade designation “RSX 29522” from UCB Chemicals Corp. Preferred flow control agents include waxes and acrylic copolymers commercially available under the trade designation Modarez MFP-V from Synthron, Inc., metal stearates such as zinc stearate and/or calcium stearate, combinations of these, and the like. These ingredients may be melt blended together, cooled, and then ground into a free flowing powder of the desired average particle size.




In an alternative embodiment of the present invention suitable for forming make coat


20


and size coat


22


, a composition (Make/Size Composition II) identical to Make/Size Composition I is used, except that a liquid oligomer and/or polymer is substituted for the solid oligomer/polymer. Most preferably, the liquid oligomer or polymer is highly viscous. “Highly viscous” means that the material is a liquid at 25° C. and has a weight average molecular weight of at least about 5000, preferably at least about 8000, more preferably at least about 10,000. Preferred examples of highly viscous oligomers and polymers include the oligomer of

FIG. 10

in which n is about 5, as well as the acrylate functional resin of FIG.


11


.




For another embodiment of the present invention suitable for use in supersize coat


24


, a preferred binder precursor particle composition (Supersize Composition I) comprises 75 to 95 parts by weight of a solid metal salt of a fatty acid, about 5 to 25 parts by weight of a liquid, radiation curable monomer, oligomer and/or polymer, and about 1 to 5 parts by weight of a photoinitiator or photocatalyst. Notwithstanding the liquid character of the radiation curable monomer, oligomer, and/or polymer, the ingredients can be melt blended, cooled, and then ground to form a free flowing, solid powder. Preferred metal salts of a fatty acid include zinc stearate, calcium stearate, and combinations of these. Preferred liquid materials include acrylate functional epoxy oligomers available under the trade designations “EBECRYL 3720 and 302”, acrylate functional polyester available under the trade designation “EBECRYL 450”, acrylate functional polyurethanes available under the trade designation “EBECRYL 8804 and 270”, ethoxylated trimethylol propane triacrylate, and the novolak-type phenolic oligomer of

FIG. 10

, wherein n is about 5.




For another embodiment of the present invention suitable for use in supersize coat


24


, a preferred binder precursor particle composition (Supersize Composition II) is identical to Supersize Composition I except that one or more solid radiation curable monomers, oligomers, and/or polymers is substituted for the liquid radiation curable materials. Preferred examples of the solid radiation curable material include the monomer of

FIG. 3

, the cyanate ester of

FIG. 8

, and the TATHEIC monomer of FIG.


6


. Preferred examples of the solid oligomer/polymer include the epoxy functional resin commercially available under the trade designation “EPON 1001F” and the acrylate functional oligomer available under the trade designation “RSX 29522”.




For another embodiment of the present invention suitable for use in supersize coat


24


, a preferred binder precursor particle composition (Supersize Composition III) comprises 70 to 95 parts by weight of a metal salt of a fatty acid as described above, 5 to 30 parts by weight of a thermoplastic resin, and optionally 5 to 30 parts by weight of a solid or liquid radiation curable component as described above. Preferred examples of thermoplastic resins include polyamides, polyesters, ethylene vinyl acetate copolymers, combinations of these, and the like. A particularly preferred resin is available from Union Camp Chemical Product Division under the trade designation “UNIREZ 2221”.




For another embodiment of the present invention suitable for use in supersize coat


24


, a preferred binder precursor particle composition (Supersize Composition IV) comprises 70 to 95 parts by weight of the metal salt of a fatty acid as described above and 5 to 20 parts by weight of a thermosetting resin other than a radiation curable resin. Preferred examples of the thermosetting resin include phenol-formaldehyde resins (that is, novolak type phenolic resins and powdered resole resins) such as the resin available under the trade designation “VARCUM 29517” from the Durez Division of the Occidental Chemical Corp. (“Oxychem”), and urea-formaldehyde resins such as the resin available under the trade designation “AEROLITE UP4145” from Dynochem UK, Ltd.; and the EPON™ 1001F epoxy resin.




The binder precursor particles and/or fusible powder of the present invention are easily made by a process in which all of the ingredients to be incorporated into the particles or powder, as the case may be, are first blended together to form a homogeneous, solid admixture. Blending can be accomplished by dry blending the ingredients together in powder form, but more preferably is accomplished by melt processing in which at least the radiation curable ingredients of the particles are liquefied during blending. Typically, melt processing occurs at a temperature above the glass transition temperatures and/or melting points of at least some of the radiation curable ingredients, while nonetheless occurring at a sufficiently low temperature to avoid premature crosslinking of the binder components. The melt processing temperature is also below temperatures that might degrade any temperature sensitive ingredients of the particles. The particular technique used to accomplish melt processing and blending is not critical, and any convenient technique can be used. As one example, processing the ingredients through an extruder to form a solid, blended extrudate is suitable, so long as extruder temperature is carefully monitored to avoid premature crosslinking of, and degradation to, the ingredients.




After the solid blend is formed, the resultant solid can then be milled, for example, ground, into particles of the desired particle size. The type of milling technique is not critical and representative examples include cryogenic grinding, hammer milling (either cold or at room temperature), using a mortar and pestle, using a coffee grinder, ball milling, and the like. Hammer milling at room temperature is presently preferred.




Depending upon the composition of the particles, the dry particles can then be used, without use of any solvent whatsoever, to form the binder matrix component of make coat


20


, size coat


22


, and/or supersize coat


24


, as desired. Generally, the particles may be applied to an underlying surface of abrasive article


10


using any convenient dry coating technique such as drop coating, electrostatic spraying, electrostatic fluidized bed coating, hot melt spraying, and the like. After coating, the particles are liquefied, preferably by heating, in a manner such that the particles fusibly flow together to form a uniform, fluid melt layer. The melt layer can then be exposed to a suitable source of energy in order to cure the melt layer so that a thermoset, solid, binder matrix is formed. In the case of forming make coat


20


, abrasive particles


16


to be incorporated may be codeposited with the dry binder precursor particles if desired. Alternatively, it is also possible to sequentially and separately apply the binder precursor particles and abrasive particles


16


in any order. For example, the binder precursor particles can be dry coated and liquefied first, after which abrasive particles


16


are coated into the melt layer prior to curing. In order to promote the adhesion of make coat


20


to backing


12


, it may be desirable to modify, for example, prime, the surface of backing


12


to which make coat


20


is applied. Appropriate surface modifications include corona discharge, ultraviolet light exposure, electron beam exposure, flame discharge and scuffing.




With reference to abrasive article


10


of

FIG. 1

,

FIG. 12

is a schematic representation of an apparatus


200


suitable for forming abrasive article


10


. For purposes of illustrating the versatility of the present invention,

FIG. 12

shows forming each of make coat


20


, size coat


22


, and supersize coat


24


of abrasive article


10


from binder precursor particles of the present invention. However, it is to be understood that the present invention is not limited to the illustrated application in which the entirety of bond system


18


is formed from the binder precursor particles, but rather is applicable to circumstances in which any one or more portions of bond system


18


is derived from such binder precursor particles.





FIG. 12

shows backing


202


being transported from supply roll


204


to take-up roll


206


. Typically, backing


202


may be transported at a speed in the range from


0


.


1


m/min to as much as


100


m/min or more. During transit between supply roll


204


and take up roll


206


, backing


202


is supported upon suitable number of guide rollers


208


as backing


202


passes through coating stations


210


,


212


, and


214


. Make coat


20


, size coat


22


, and supersize coat


24


are applied at stations


210


,


212


, and


214


, respectively. Firstly, at station


210


, binder precursor particles


216


corresponding to the binder matrix of make coat


20


are drop coated onto backing


202


from dry coating apparatus


220


. Backing


202


then passes through oven


224


in which particles


216


are heated to form a liquefied make coat melt layer. Abrasive particles


16


are then electrostatically coated into the make coat melt layer from mineral coater


226


. The coated backing then passes ultraviolet light source


228


, where the make coat melt layer is exposed to ultraviolet radiation to crosslink and cure the make coat. The crosslinked make coat now firmly bonds abrasive particles


16


to backing


202


.




Next, the coated backing


202


passes through station


212


to form size coat


22


. Binder precursor particles


230


corresponding to the binder matrix of size coat


22


are drop coated onto make coat


20


from dry coating apparatus


232


. The coated backing


202


then passes through oven


234


in which particles


230


are heated to form a liquefied size coat melt layer. The coated backing then passes ultraviolet light source


238


, where the size coat melt layer is exposed to ultraviolet radiation to crosslink and cure the size coat. The crosslinked size coat now helps reinforce the attachment of abrasive particles


16


to backing


202


.




Next, the coated backing


202


passes through station


214


to form supersize coat


24


. Binder precursor particles


240


corresponding to the binder matrix of supersize coat


24


are drop coated onto size coat


22


from dry coating apparatus


242


. The coated backing


202


then passes through oven


244


in which particles


240


are heated to form a liquefied supersize coat melt layer. The coated backing


202


then passes ultraviolet light source


248


, where the supersize coat melt layer is exposed to ultraviolet radiation to crosslink and cure the supersize coat. The crosslinked supersize coat now helps provide abrasive article


10


with desired performance characteristics, for example, anti-loading capabilities if supersize coat


24


incorporates an antiloading agent.




The finished abrasive article


10


is then stored on take-up roll


206


, after which abrasive article may be cut into a plurality of sheets, discs or the like, depending upon the desired application. Of course, instead of being directly stored on take-up roll


206


, abrasive article


10


may be transported directly to a cutting apparatus to form sheets or discs, after which the sheets or discs may be stored, packaged for distribution, used, or the like.




The invention will be more fully understood with reference to the following nonlimiting examples in which all parts, percentages, ratios, and so forth, are by weight unless otherwise indicated.




Abbreviations for the materials defined in the above detailed description and used in the following samples are shown in the following schedule.

















Thermoplastic












DS1227




High molecular weight polyester commercially available







from Creanova, Piscataway, NJ under the trade







designation “DYNAPOL S1227”






Elvax 310




Ethylene vinyl acetate copolymer commercially available







from E. I. Du Pont de Nemours and Company Inc.,







Willmington, DE






Unirez 2221




Dimer acid hot melt polyamide commercially available







form Union Camp, Chemical Products Division,







Jacksonville, FL











Thermosetting Resins












DZ1




Novolak type powdered phenolic resin commercially







available from OxyChem, Occidental Chemical







Corporation, Durez EngineeringMaterials, Dallas,







TX under the trade designation “Durez 12687”






DZ2




Novolak type powdered phenolic resin commercially







available from OxyChem, Occidental Chemical







Corporation, Durez Engineering Materials, Dallas,







TX under the trade designation “Durez 12608”






VM1




Novolak type powdered phenolic resin commercially







available from OxyChem, Occidental Chemical







Corporation, Durez Engineering Materials, Dallas,







TX under the trade designation “Varcum 29517”






UF1




Powdered urea-formaldehyde resin available from







Dynochem UK Ltd, Cambridge, UK. under the trade







designation “Aerolite UP 4145”






UF2




Urea-formaldehyde liquid resin commercially available







from Borden Chemical Inc., Louisville, KY under







the trade designation “Durite Al-3029 R”











Radiation Curable or thermally curable epoxy resins












EP1




Bisphenol A epoxy resin commercially available from







Shell Chemical, Houston, TX under the trade designation







“EPON 828” (epoxy equivalent weight of 185-192 g/eq.)






EP2




Bisphenol A epoxy resin commercially available from







Shell Chemical, Houston, TX under the trade designation







“EPON 828” (epoxy equivalent weight of 185-192 g/eq.)






ERL 4221




Cycloaliphatic epoxy resin commercially available from







Union Carbide Chemicals and Plastics Company Inc.,







Danbury, CT











Radiation Curable Momomers, Oligomers and Polymers












EB1




Bisphenol A epoxy acrylate commercially available from







UCB Chemicals Corp., Smyrna, GA under the trade







designation “Ebecryl 3720”






EB2




Fatty acid modified epoxy acrylate commercially available







from UCB Chemicals Corp., Smyrna, GA under the trade







designation “Ebecryl 3702”






EB3




Polyester hexa-acrylate commercially available from UCB







Chemicals Corp., Smyrna, GA under the trade designation







“Ebecryl 450”






RSX 29522




Experimental solid acrylated epoxy oligomer obtained







from UCB Chemicals Corp, Smyrna, GA






TRPGDA




Tripropylene glycol diacrylate commercially available







from Sartomer Co., Exton, PA under the trade







designation “SR306”






TMPTA




Trimethylol propane triacrylate commercially available







from Sartomer Co., Exton, PA under the trade







designation “SR351”






AMN




Acrylamidomethyl novolak resin in U.S. Pat. 4,903,440







and 5,236,472






PDAP




p-Di(acryloyloxyethyl)terephthalate, prepared as described







below at IIA






PAN




O-Acrylated novolak resin, prepared as described below







at IIA






PT 60




Cyanate ester novolak commercially available from Lonza







Inc., Fair Lawn, NJ under the tradename “Primaset







PT 60”











Metal salts of fatty acids/Antiloading agents












ZnSt2




Zinc stearate commercially available from Witco







Chemical Corporation, Memphis, TN under the







tradename “Lubrazinc W”






CaSt2




Calcium stearate commercially available from Witco







Chemical Corporation, Memphis, TN under the







tradename “Calcium Stearate Extra Dense G”






LiSt




Lithium stearate commercially available from Witco







Chemical Corporation, Memphis, TN under the







tradename “Lithium Stearate 304”






StA




Stearic acid commercially available from Aldrich







Chemical of Milwaukee, WI











Grinding Aids












KBF4




Potassium Fluoroborate commercially available from







Aerotech USA Inc., under the trade designation







“POTASSIUM FLUOROBORATE SPEC. 102.”











Abrasive particles












P180 AlO




Grade P180 aluminum oxide particles, commercially







available from Triebacher Schleifmittel AG, Villach,







Austria






P400 SiC




Grade P400 silicon carbide particles, commercially







available from Triebacher Schleifmittel AG,







Villach, Austria






P80 CUB




Grade P80 ceramic aluminum oxide particles,







commercially available from Minnesota Mining and







Manufacturing Company, St. Paul, MN






P80 AO




Grade P80 aluminum oxide particles, commercially







available from Triebacher Schleifmittel AG, Villach,







Austria






50 AZ




Grade 50 ceramic aluminum oxide particle commercially







available from Norton, WHERE











Hydroxyl containing materials












CHDM




Cyclohexanedimethanol commercially available from







Eastman Chemical Company, Kingsport, CT






SD 7280




Novolak type powdered phenolic resin (uncatalyzed)







commercially available from Borden Chemical Inc.,







Louisville, KY











Initiators/Catalysts












“KB1”




2,2-Dimethoxy-1,2-diphenyl-1-ethanone commercially







available from Sartomer Co., Exton, PA under the trade







designation “KB1”






IRG1




2,2-Dimethoxy-1,2-diphenyl-1-ethanone commercially







available from Ciba Speciality Chemicals, under the trade







designation “IRGACURE 651”






COM




Eta


6


-[xylenes(mixed isomers)]eta


5









cyclopentadienyliron (1+) hexafluoroantimonate (1−)







(acts as a photocatalyst) as described in







U.S. Pat. Nos. 5,059,701; 5,191,101 and 5,252,694






AMOX




Di-t-amyloxalate (acts as an accelerator) as described in







U.S. Pats. 5,252,694 and 5,436,063






IMID




2-Ethyl-4-methylimidazole, commercially available from







Aldrich Chemical, Milwaukee, WI






PTSOH




p-Toloune sulfonic acid , commercially available from







Aldrich Chemical Milwaukee, WI






ACL




Aluminum chloride, commercially available from Aldrich







Chemical, Milwaukee, WI











Fillers












FLDSP




Feldspar, commercially available from K-T Feldstar







Corporation, GA under the trade designation “Minspar 3”






CRY




Crolite commercially available from TR International







Trading Company Inc., Houston, TX under the trade







designation “RTNC CRYOLITE”






CaCO


3






Calcium carbonate






FEO




Iron oxide











Flow control agents












MOD




Powder coating flow agent commercially available from







Sythron Inc, Moganton, NC under the trade designation







“Modarez MFP-V”






CAB-O-SIL




Hydrophobic treated amorphous fumed silica,







commercially available from Cabot Corporation, Tuscola,







IL, under the trade designation “CAB-O-SIL TS-720”











Solvents












Ethyl Acetate




Ethyl acetate is commercially available from Aldrich







Chemical, Milwaukee, WI














EXAMPLE I




Preparation of Abrasive Articles Comprising a Backing Layer and Abrasive Coating Comprising a Supersize Coat




A. Preparation of Abrasive Articles Comprising a Backing Layer and an Abrasive Coating




1. Abrasive Article A




These abrasive articles used a backing that was a 95 g/m


2


paper backing C90233 EX commercially available from Kimberly-Clark, Neenah, Wis. For each, a make coat precursor was prepared from DS1227 (20.7 parts), EP1 (30.5 parts), EP2 (33.7 parts), CHDM (2.9 parts), COM (0.6 part), KB1 (1.0 part) and AMOX (0.6 parts). The batch was prepared by melting DS 1227 and EP2 together at 140° C., mixing, then adding EP1 and CHDM. Then, TMPTA (4.5 parts) was added with mixing at 100° C. To this sample was added COM, AMOX, and KB1 followed by mixing at 100° C. The make coat precursor was applied at 125° C. by means of a knife coater to the paper backing at a weight of about 20 g/m


2


. The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb immediately before P180 AO abrasive particles were electrostatically projected into the make coat precursor at a weight of about 85 g/m


2


. The intermediate product was thermally cured for 15 minutes at a temperature of 100° C.




A size coat precursor was roll coated over the abrasive grains at a weight of about 50 g/m


2


. The size coat precursor included a 100% solids blend of EP1 (40 parts), ERL 4221 (30 parts), TMPTA (30 parts), KB1 (1 part), and COM (1 part). The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb followed by a thermal cure for 10 minutes at 100° C.




2. Abrasvie Article B




Abrasive article B was prepared by the same methodology as described above using the formulations shown in Table 1.




3. Comparative Samples B, D, F, H, J, K, N, P, BB, DD, FF, HH, JJ




Abrasive articles used a backing that was a 95 g/m


2


paper backing C90233 EX commercially available from Kimberly-Clark, Neenah, Wis. For each, a make coat precursor was prepared from DS1227 (20.7 parts), EP1 (30.5 parts), EP2 (33.7 parts), CHDM (2.9 parts), COM (0.6 part), KB1 (1.0 part) and AMOX (0.6 parts). The batch was prepared by melting DS1227 and EP2 together at 140° C., mixing, then adding EP1 and CHDM. Then, TMPTA (4.5 parts) was added with mixing at 100° C. To this sample was added COM, AMOX, and KB1 followed by mixing at 100° C. Make coat precursors were applied at 125° C. by means of a knife coater to the paper backing at a weight of about 20 g/m


2


. The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb immediately before P180 AO abrasive particles were electrostatically projected into the make coat precursor at a weight of about 85 g/m


2


. The intermediate product was thermally cured for 15 minutes at a temperature of 100° C.




A size coat precursor was roll coated over the abrasive grains at a weight of about 50 g/m


2


. The size coat precursor included a 100% solids blend of EP1 (40 parts), ERL 4221 (30 parts), TMPTA (30 parts), KB1 (1 part), and COM (1 part). The samples were then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb followed by a thermal cure for 10 minutes at IOO° C. The sample was supersized at a weight of about 35 g/m


2


with a calcium stearate solution (50% solids aqueous calcium stearate/acrylic binder solution) available from Witco Chemical Corporation, Memphis, Tenn.




4. Comparative Sample L




Comparative Article L was prepared by the same methodology as described above for Abrasive Article A using the formulations shown in Table 1.




5. Comparative Samples A, C, G, I, O, AA, CC




Comparative Articles A, C, G, I, O, AA, CC are commercially available from Minnesota Mining and Manufacturing Company, St. Paul, Minn. under trade designation “216U P180 Fre-Cut Production Paper A Weight”.












TABLE 1











Formulation of Abrasive Articles


















Comparative Abrasive










Articles B, D, F,, H, J, K, N,




Comparative Abrasive







Abrasive Article A




Abrasive Article B




P, BB, DD, FF, HH, JJ




Article L



















Backing type






a


Paper, C90233 EX






a


Paper, S-44165






a


Paper, 90233 EX






a


Paper, S-44165






Backing wt. (g/m


2


)




95




70




95




20






Make resin type




DS1227(20.7 parts),




DS1227(20.7 parts), EP1(30.5




DS1227(20.7 parts), EP1(30.5




DS1227(20.7 parts), EP1(30.5







EP1(30.5 parts), EP2




parts), EP2(33.7 parts), CHDM




parts), EP2(33.7 parts), CHDM




parts), EP2(33.7 parts), CHDM







(33.7 parts), CHDM




(2.9 parts), COM(0.6 part),




(2.9 parts), COM(0.6 part),




(2.9 parts), COM(0.6 part),







(2.9 parts), COM(0.6




KB1(1.0 part) and AMOX(0.6




KB1(1.0 part) and AMOX(0.6




KB1(1.0 part) and AMOX(0.6







part), KB1(1.0 part)




parts).




parts).




parts).







and AMOX(0.6







parts).






Make resin wt. (g/m


2


)




20




12.5




20




12.5






Mineral Type




P180 AO




P400 SiC




P180 AO




P400 SiC






Mineral Wt. (g/m


2


)




85




40




85




40






Size resin Type




EP1/ERL 4221/SR321




EP1/ERL 4221/TMTPA




EP1/ERL 4221/TMTPA




EP1/ERL 4221/TMTPA







(40/30/30)




(40/30/30)




(40/30/30)




(40/30/30)






Size Resin wt. (g/m


2


)




50




35




50




35






Supersize coating




none




none




Calcium Stearate/acrylic binder




Calcium Stearate/acrylic binder






type






solution (50% solids)




solution (50% solids)






Supersize wt. (g/m


2


)






35




20














B. Preparation of Binder Percursor Particles for Use in a Supersize Coat




Samples of binder precursor particles according to the present invention were prepared from the formulations in Table 2. To make each sample, the ingredients were either (1) melt blended together, solidified, and ground into a powder or (2) dry blend mixed and ground into powders. The samples were ground into fine powders by mortar and pestle or hammer mill, unless otherwise indicated. A few examples are given below to illustrate the methodology.




1. Preparation of Binder Precursor Particles Comprising a Combination of ZnSt2/CaSt2/EB1/IRG1 (45/45/10/1)




A 0.5 L. jar was charged with 45 g of ZnSt2, 45 g of CaSt2 and 10 g of EB1. The materials were melted at 120-160° C., mixed, and 1 g of IRG1 was added. The material was cooled, and the resultant solid was ground into a fine powder.




2. Preparation of Binder Precursor Particles Comprising a Combination of ZnSt2/UF1(80/20)




A 0.5 L. jar was charged with 80 g of ZnSt2 and 20 g of UF1. The solids were dry blended in a grinder.




3. Preparation of Binder Precursor Particles Comprising a Combination of ZnSt2/CaSt2/EP2/IMID (50/50/14/1)




A 0.5 L. jar was charged with 50 g of ZnSt2, 50 g of CaSt2 and 14 g of EP2, The materials were melted at 120-140° C., mixed, and 1 g of IMID was added. The material was cooled, and the resultant solid was ground into a fine powder.












TABLE 2











Binder Precursor Particles Formulations
















Metal Salt of





Radiation/








Fatty




Weight of




Thermally




Weight Radiation/







Acid/Fatty




Metal Salt of




Curable




Thermally Curable






Sample No.




Acid




Fatty Acid (g)




Component




Component (g)*


















Sample 1, 15 & 37




ZnSt2




No binder




None




0






Sample 2, 16 & 38A




ZnSt2




88




EB1




12






Sample 3




ZnSt2




85




EB3




15






Sample 4




ZnSt2




85




EB1




15






Sample 5




ZnSt2




85




EB1




7.5









EB3




7.5






Sample 6




ZnSt2




70




EB1




7.5









Elvax 310




7.5






Sample 7




ZnSt2




95




EB1




5






Sample 8




ZnSt2




95




EB2




5






Sample 9




ZnSt2




95




EB3




5






Sample 10 & 12




CaSt2




90




EB1




10






Sample 11




CaSt2




100




None




0






Sample 13




CaSt2




90




EB3




10






Sample 14




CaSt2




90




EB1




10






Sample 17




CaSt2




25




TRPGDA




31






Sample 18




ZnSt2




25




TRPGDA




57






Sample 19




CaSt2




25




TRPGDA




44






Sample 20




ZnSt2




25




TRPGDA




45






Sample 21




LiSt




25




TRPGDA




68








a


Sample 22 & 26




 50% CaSt2




73.6




EB1




23.4







 50% ZnSt2








b


Sample 23 & 27




 50% CaSt2




73.6




EB1




23.4







 50% ZnSt2








a


Sample 24, 28 & 29




 75% CaSt2




73.6




EB1




23.4







 25% ZnSt2








b


Sample 25 & 30




 75% CaSt2




73.6




EB1




23.4







 25% ZnSt2






Sample 31 & 32




 73% CaSt2




89




EB1




10







 27% StA






Sample 33 & 34




 80% CaSt2




89




EB1




10







 20% StA






Sample 35 & 36




 90% CaSt2




89




EB1




10







 10% StA






Sample 38B




 50% CaSt2




80




PDAP




14







 50% ZnSt2






Sample 38C




 50% CaSt2




90




RSX 29522




10







 50% ZnSt2






Sample 38D




 50% CaSt2




90




Et-TMPTA




10







 50% ZnSt2






Sample 38E




100% ZnSt2




90




UP4145




10






Sample 38F




100% ZnSt2




90




V1




10






Sample 38G




 50% CaSt2




100




EP2




14







 50% ZnSt2






Sample 38H




100% CaSt2




90




Unirez 2221




10













a


Particle size of powder was 45-90 um.












b


Particle size of powder was 0-45 um.













C. Preparation of Abrasive Articles Comprising Supersize Coat




Binder precursor particle samples 1-38H were dry coated onto Abrasive Articles A and/or B (see Table 3), melted, and then solidified to form supersize coats according to the following procedures. The details of the resultant abrasive articles are disclosed in Table 3.




The binder precursors samples 2-15,16, 22-36, and 38A-38B were respectively coated onto Abrasive Article A or B. Specifically, the binder precursor particles were powder coated at about 7.0 to 23g/m


2


onto the abrasive articles by drop coating with a mesh sifter, spray coating with a fluidized or electrostatic fluidized spray gun, or coating with an electrostatic fluidized bed coater. The binder precursor particles were then melted by placing the abrasive article in an oven at a temperature of from about 120° to about 165° C. for about 5-15 minutes. The resultant melt layer was then cured by passing the abrasive article through a UV lamp (1 pass at 7.6 m/min. with 157 w/cm bulb). Adhesive sheeting was attached to the backside of the abrasive article and 10.2 cm or 15.2 cm discs were died out of the abrasive articles. The discs were used for Schiefer or Off hand DA testing, described below.




Supersize coat samples formed from binder precursor particles 1 15, 37 and 38H, respectively, were prepared identically to samples 2-14, 16, 22-36, and 38A, except that the materials were not cured after removing the resultant melt layer form the oven. Adhesive sheeting was attached to the backside of the abrasive article and 10.2 cm or 15.2 cm discs were died out of the abrasive articles. The discs were used for Schiefer or Offhand DA testing, describe below.




Supersize coat samples formed from binder precursor particles 38B-G, respectively, were prepared identically to samples 2-14,16 22-36, and 38A except that the amount of time that the samples were placed in the oven was extended to 30-90 minutes to thermally cure the resultant melt layer. Adhesive sheeting was attached to the backside of the abrasive articles and 10.2 cm or 15.2 cm discs were died out of the abrasive articles. The discs were used for Schiefer tests, described below.




Supersize coat samples formed from binder precursor particles 17-21, respectively, were prepared identically to samples 2-14,16 22-36, and 38A except that, prior to powder coating, a composition comprising 50 g of radiation curable monomer (TRPGDA), 50 g of ethyl acetate and 1 g of initiator (IRG1) were combined and placed in a spray bottle. The solution was sprayed onto 15.2 cm×20.3 cm sections of Abrasive Article A and allowed to air dry. About 8 g/m


2


were then applied to the corresponding abrasive article by electrostatic fluidizing spray gun. The abrasive article was then placed in an oven at a temperature in the range of from about 120° to about 165° C. to melt the particles. Finally, the resultant melt layer was cured by passing the abrasive article through a UV lamp (1 pass at 7.6 M/min. with a 157 w/cm bulb). Adhesive sheeting was attached to the backside of the abrasive article and 10.2 cm or 15.2 cm discs were died out of the abrasive articles. The discs were used in testing, described below.












TABLE 3











Samples of Abrasive Articles Powder Coated with Supersize Coat















Supersize Coat




Abrasive







Sample No.




Weight (g/m


2


)




Article




Powder Coat Method

















Sample 1-2




21.9




A




Drop coating






Sample 3




20.7




A




Drop coating






Sample 4-6




21.9




A




Drop coating






Sample 7




22.6




A




Drop coating






Sample 8-9




21.3




A




Drop coating






Sample 10




21.3




A




Drop coating






Sample 11




22.3




A




Drop coating






Sample 12-14




22.6




A




Drop coating






Sample 15




7.4




A




Electrostatic fluidized









spraying






Sample 16




16.8




A




Electrostatic fluidized









spraying






Sample 17-21




8.1




A




Electrostatic fluidized









spraying






Sample 22




17.4




A




Electrostatic fluidized bed









coating






Sample 23




19.2




A




Electrostatic fluidized bed









coating






Sample 24




16.1




A




Electrostatic fluidized bed









coating






Sample 25




22.3




A




Electrostatic fluidized bed









coating






Sample 26




8.7




B




Electrostatic fluidized bed









coating






Sample 27




7.4




B




Electrostatic fluidized bed









coating






Sample 28




12.4




B




Electrostatic fluidized bed









coating






Sample 29




NA




B




Electrostatic fluidized bed









coating






Sample 30




8.7




B




Electrostatic fluidized bed









coating






Sample 31-36




22.6




A




Drop Coating






Sample 37-38




22.6




A




Drop Coating






Sample 38B




22.6




A




Drop Coating






Sample 38C




22.6




A




Drop Coating






Sample 38D




16.1




A




Drop Coating






Sample 38E




16.1




A




Drop Coating






Sample 38F




16.1




A




Drop Coating






Sample 39G




16.1




A




Drop Coating






Sample 39H




16.1




A




Drop Coating














D. Evaluation of Abrasive Articles Comprising a Supersize Coat




1. Test Procedures




a. Schiefer Testing Procedure




Each 10.2 cm diameter disc of the abrasive articles of each Sample 1-38H and Comparative Samples A-O and AA-JJ(See Tables 4-7) was secured to a foam back-up pad by means of a pressure sensitive adhesive. Each coated abrasive disc and back-up pad assembly was installed on a Schiefer testing machine, and the coated abrasive disc was used to abrade a cellulose acetate butyrate polymer of predetermined weight. The load was 4.5 kg. The test was considered complete after 500 revolution cycles of the coated abrasive disc. The cellulose acetate butyrate polymer was then weighed, and the amount of cellulose acetate butyrate polymer removed was recorded. The results of the test procedures are tabulated hereinbelow with the appropriate Comparative Samples. Briefly, the results illustrated below in Tables 4-7 illustrated that supersize coats derived from radiation curable binder precursor particles, thermal curable binder precursor particles and thermoplastic binder precursor particles exhibited superior performance to conventional aqueous calcium stearate/acrylic binder supersize coats. In addition to the superior performance, these binder precursor particles for supersize coats have environmental and processing advantages over conventional supersize coats prepared from solvent-containing solutions.












TABLE 4A











Schiefer Testing of Samples 1-6 and Comparative Samples A and B
















Comparative Ranking




Comparative Ranking






Sample No.




Cut (g)




Relative to A




Relative to B

















Comparative A




3.324




100




106






Comparative B




3.150




95




100






Sample 1




3.362




101




107






Sample 2




3.052




92




97






Sample 3




3.218




97




102






Sample 4




3.024




91




96






Sample 5




2.818




85




89






Sample 6




2.803




84




89






















TABLE 4A











Schiefer Testing of Samples 1-6 and Comparative Samples A and B
















Comparative Ranking




Comparative Ranking






Sample No.




Cut (g)




Relative to A




Relative to B

















Comparative A




3.324




100




106






Comparative B




3.150




95




100






Sample 1




3.362




101




107






Sample 2




3.052




92




97






Sample 3




3.218




97




102






Sample 4




3.024




91




96






Sample 5




2.818




85




89






Sample 6




2.803




84




89






















TABLE 4C











Schiefer Testing of Samples 12-14 and Comparative Samples E and F
















Comparative Ranking




Comparative Ranking






Sample No.




Cut (g)




Relative to E




Relative to F

















Comparative E




3.016




100




91






Comparative F




3.317




110




100






Sample 12




3.495




116




105






Sample 13




3.392




112




102






Sample 14




3.596




119




108






















TABLE 4C











Schiefer Testing of Samples 12-14 and Comparative Samples E and F
















Comparative Ranking




Comparative Ranking






Sample No.




Cut (g)




Relative to E




Relative to F

















Comparative E




3.016




100




91






Comparative F




3.317




110




100






Sample 12




3.495




116




105






Sample 13




3.392




112




102






Sample 14




3.596




119




108






















TABLE 4C











Schiefer Testing of Samples 12-14 and Comparative Samples E and F
















Comparative Ranking




Comparative Ranking






Sample No.




Cut (g)




Relative to E




Relative to F

















Comparative E




3.016




100




91






Comparative F




3.317




110




100






Sample 12




3.495




116




105






Sample 13




3.392




112




102






Sample 14




3.596




119




108






















TABLE 6











Schiefer Testing for Samples 22-30 and Comparative Samples K and L













Sample No




Cut (g)


















Comparative Ranking








Relative to K






Comparative K




2.990




100






Sample 22




3.183




106






Sample 23




3.159




105






Sample 24




3.632




121






Sample 25




3.641




122








Comparative Ranking








Relative to L






Comparative L




1.000




100






Sample 26




1.196




120






Sample 27




0.955




 96






Sample 28




1.237




124






Sample 29




1.242




124






Sample 30




1.191




119






















TABLE 6











Schiefer Testing for Samples 22-30 and Comparative Samples K and L













Sample No




Cut (g)


















Comparative Ranking








Relative to K






Comparative K




2.990




100






Sample 22




3.183




106






Sample 23




3.159




105






Sample 24




3.632




121






Sample 25




3.641




122








Comparative Ranking








Relative to L






Comparative L




1.000




100






Sample 26




1.196




120






Sample 27




0.955




 96






Sample 28




1.237




124






Sample 29




1.242




124






Sample 30




1.191




119






















TABLE 7B











Schiefer Testing for Samples 38B-38D and Comparative






Sample BB, DD and FF













Sample No.




Cut (g)


















Comparative Ranking Relative to BB.






Comparative BB




2.916




100






Sample 38B




3.408




117








Comparative Ranking Relative to DD






Comparative DD




2.932




100






Sample 38C




3.236




110








Comparative Ranking Relative to FF






Comparative FF




2.756




100






Sample 38D




3.219




117






















TABLE 7B











Schiefer Testing for Samples 38B-38D and Comparative






Sample BB, DD and FF













Sample No.




Cut (g)


















Comparative Ranking Relative to BB.






Comparative BB




2.916




100






Sample 38B




3.408




117








Comparative Ranking Relative to DD






Comparative DD




2.932




100






Sample 38C




3.236




110








Comparative Ranking Relative to FF






Comparative FF




2.756




100






Sample 38D




3.219




117














2. Offhand DA Test Method




A paint panel, that is, a steel substrate with an e-coat, primer, base coat, and clear coat typically used in automotive paints, was abraded in each case with coated abrasives made in accordance with the invention and with coated abrasives as comparative examples. Each coated abrasive had a diameter of 15.2 cm and was attached to a random orbital sander (available under the trade designation “DAQ”, from National Detroit, Inc., Rockford, Ill.). The abrading pressure was about 0.2 kg/cm


2


, while the sander operated at about 60 PSI@TOOL (413 kPa). The painted panels were purchased from ACT Company of Hillsdale, Mich. The cut in grams was computed in each case by weighing the primer-coated substrate before abrading and after abrading for a predetermined time, for example, 1 or 3 minutes. The DA test data for samples 37, 38A, and Comparative Samples O and P are shown in Table 8.












TABLE 8











DA Testing (3 min.) for Samples 37, 38A and Comparative






Sample O and P
















Ranking Relative




Ranking Relative to








to Comparative




Comparative






Sample No.




Cut




Abrasive Article O




Abrasive Article P

















Comparative O




11.7




100




101






Comparative P




11.6




 99




100






Example 37




10.15




 87




 88






Example 38A




11.75




100




101














EXAMPLE II




Preparation of Abrasive Articles Comprising a Backing Layer and Abrasive Coating Comprising a Size Coat




A. Preparation of Abrasive Articles Comprising a Backing Layer and Abrasive (Table 9)




1. Abrasive Article C




These abrasive articles used a backing that was a 95 g/m


2


paper backing C90233 EX commercially available from Kimberly-Clark, Neenah, Wis. To make each, a make coat precursor was prepared from DS1227 (20.7 parts), EP1 (30.5 parts), EP2 (33.7 parts), CHDM (2.9 parts), COM (0.6 part), KB1 (1.0 part) and AMOX (0.6 parts). The batch was prepared by melting DS1227 and EP2 together at 140° C., mixing, and then adding EP1 and CHDM and mixing. Then, TMPTA (4.5 parts) was added with mixing at 100° C. To this sample was added COM, AMOX, and KB1 followed by mixing at 100° C. The make coat precursor was applied at 125° C. by means of a knife coater to the paper backing at a weight of about 20 g/m


2


. The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb immediately before P180 AO abrasive particles were electrostatically projected into the make coat precursor at a weight of about 85 g/m


2


. The intermediate product was thermally cured for 15 minutes at a temperature of 100° C.




2. Abrasive Article D




An abrasive article used a 5 mil thick polyester backing that can be obtained commercially from Minnesota Mining and Manufacturing Company, St. Paul, Minn. A make coat precursor comprising an aqueous solution of UF2, a 75% solid aqueous resole phenolic resin with a formaldehyde/phenol ratio of approximately 1.1-3.0/1 and a pH of 9, ACL and PTSOH (85/15/2/1) was roll coated onto the backing at an approximate weight of 40 g/m


2


. Next, a blend of P180 and AlO/CUB abrasive particles (50-90/10-50) was electrostatically projected into the make coat precursor at a weight of about 155 g/m


2


. The make resin was cured in an oven at 100° C. for 60 minutes.




3. Comparative Samples Q and R




These abrasive articles used a backing that was a 95 g/m


2


paper backing C90233 EX commercially available from Kimberly-Clark, Neenah, Wis. To make each article, a make coat precursor was prepared from DS1227 (20.7 parts), EP1 (30.5 parts), EP2 (33.7 parts), CHDM (2.9 parts), COM (0.6 part), KB1 (1.0 part) and AMOX (0.6 parts). The batch was prepared by melting DS1227 and EP2 together at 140° C., mixing, and then adding EPI and CHDM. Then, TMPTA (4.5 parts) was added with mixing at 100° C. To this sample was added COM, AMOX, and KB1 followed by mixing at 100° C. Make coat precursors were applied at 125° C. by means of a knife coater to the paper backing at a weight of about 20 g/m


2


. The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb immediately before P180 AO abrasive particles were electrostatically projected into the make coat precursor at a weight of about 85 g/m


2


. The intermediate product was thermally cured for 15 minutes at a temperature of 100° C.




A size coat precursor was roll coated over the abrasive grains at a weight of about 50 g/m


2


. The size coat precursor included a 100% solids blend of EP1 (40 parts), ERL 4221 (30 parts), TMPTA (30 parts), KB1 (1 part), and COM (1 part). The samples were then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb followed by a thermal cure for 10 minutes at 100° C.




4. Comparative Abrasive Articles S,T,U,V




An abrasive article used a 5 mil thick polyester backing with a backing that can be obtained commercially from Minnesota Mining and Manufacturing Company, Paul, Minn. A make coat precursor comprising an aqueous solution of UF2, a 75% solid aqueous resole phenolic resin with a with a formaldehyde/phenol ratio of approximately 1.1-3.)/1 and pH of 9, ACL, and PTSOH (85/15/2/1) was roll coated onto the backing at an approximate weight of 40 g/m


2


. Next, a blend of P180 and AlO/CUB abrasive particles (50-90/10-50) was electrostatically projected into the make coat precursor at a weight of about 155g/m


2


. The make resin was cured in an oven at 93 C for 30 minutes. Next, a size coat precursor comprising a 75% solids aqueous solution of resole phenolic resin with a formaldehyde/phenol ratio of approximately 1.1-3.0/1, pH of 9 and feldspar (70/35) was coated onto the make coat at an approximate weight of 200 g/m


2


. The size resin was cured by placing the sample in an oven at 100-110° C. for 1-2 hours.




The formulations for Abrasive Articles C and D and Comparative Abrasive Articles Q-V are shown below in Table 9.












TABLE 9











Formulation of Abrasive Articles


















Comparative




Comparative








Abrasive Article




Abrasive




Abrasive







Abrasive Article C




D




Articles Q,R




Articles S,T,U,V



















Backing type






a


C90233 EX






b


Polyester film






a


C90233 EX






b


Polyester film






Backing wt.




95




5 mil




95




5 mil






(g/m


2


)






Make resin




DS1227 (20.7 parts),




UF2/Resole




DS1227 (20.7




UF2/Resole






type




EP1 (30.5 parts),




phenolic




parts), EP1 (30.5




phenolic







EP2 (33.7 parts),




resin/ACL/PTSO




parts), EP2 (33.7




resin/ACL/PTSO







CHDM (2.9 parts),




H (85/15/12/1)




parts), CHDM




H (85/15/12/1)







COM (0.6 part),





(2.9 parts), COM







KB1 (1.0 part) and





(0.6 part), KB1







AMOX (0.6 parts).





(1.0 part) and









AMOX (0.6









parts).






Make resin




20




40




20




40






wt. (g/m


2


)






Mineral Type




P180 AO




P180 AO/CUB




P180 AO




P180 AO/CUB








(50-90/10-50)





(50-90/10-50)






Mineral Wt.




85




155




85




155






(g/m


2


)






Size resin




none





EP1/ERL




Resole Phenolic






Type






4221/TMPTA




resin filled with









(40/30/30)




35% FLSPR






Size Resin




none





50




200






wt. (g/m


2


)













a


Commercially available from Kimberly-Clark, Neenah, WI












b


Commercially available from Minnesota Mining and Manufacturing Company, St. Paul, MN













B. Preparation of Radiation Curable Binders




1. p-Di(acryloyloxyethyl)Terephthalate (PDAP)




To a 2 liter, 3-necked round bottomed flask equipped with a dropping addition funnel, thermometer, ice bath and paddle stirrer was added 500 ml of dry tetrahydrofuran (THF), 103 g (1.02 mol) of triethylamine and 117 g (1 mol) of 2-Hydroxyethylacrylate. Stirring was begun. To the dropping addition funnel was added a solution of 102.5 g (0.5 mol, plus slight excess) terephthaloyl chloride in 500 ml of dry THF. This solution was added to the reaction vessel contents such that the temperature of the contents did not exceed 30° C. When the addition was completed, the reaction was stirred for an hour longer at ambient temperature and filtered through a sintered Buchner-type funnel. The formed triethylamine hydrochloride was rinsed thoroughly with dry THF, and discarded. The THF solution was concentrated on a rotoevaporator, using a 60° C. water bath, until the volume of solvent was reduced by approximately one half. Then, the concentrate was quenched with twice its volume in heptane and triturated. The solid product quickly precipitated. The pasty solid was cooled to ambient temperature and filtered. The cake was rinsed with additional heptane and spread out to dry in a glass cake pan. Isolated yield: 85-90% of theoretical. The product was found to have a T


m


of about 97° C., by DSC. Thin layer chromatography showed the product to be pure, as evidenced by a single spot (elution solvent of 10% methanol/90% chloroform, using F254 silica gel coated glass plates). The infrared spectrum showed a characteristic ester peak at 1722 cm


−1


.




2. O-Acrylated Novolak (PAN)




To a 1 liter, 3-necked round bottomed flask equipped with a paddle stirrer, thermometer, ice bath and a dropping addition funnel was added 200 g of Borden SD-7280 phenolic novolak resin, followed by 400 ml of dry tetrahydrofuran (THF). Stirring was begun. When solution was obtained, 52.6 g (0.52 mol) of triethylamine was added. The contents of the flask were cooled to 10° C. To the dropping addition funnel were added 45.3 g (0.5 mol) of acryloyl chloride. This acid chloride was added to the novolak solution over 30 minutes, at such a rate that allowed the temperature of the contents to rise to ambient. The triethylamine hydrochloride readily formed. The contents were stirred for an additional 2 hours at ambient temperature, then filtered. The filter cake was rinsed with dry THF and concentrated to a viscous, resinous-like syrup on a rotoevaporator, while heating the concentrate to 70° C. The resinous product was transferred to a glass jar, with gentle heating of the flask walls to aid in its flow. NMR analysis of this resin showed some traces of triethylamine hydrochloride still present, and approximately 10 weight percent of THF. The main product showed approximately 0.2 mol of acrylate ester per ring of phenol. The novolak had a calculated formaldehyde to phenol ratio of about 0.8




3. Acrylamidomethyl Novolak (AMN)




AMN was prepared as described in U.S. Pat. Nos. 4,903,440 and 5,236,472.




C. Preparation of Radiation Curable Binder Precursor Particles for Use in Size Coat (See Table 10 for Formulation Summary)




1. Preparation of Binder Precursor Particles Comprising a Combination of AMN/PDAP/CAB-O-SIL/IRG1 (50/50/0.2/2)




A 0.5 L. jar was charged with 100 g of AMN (a viscous liquid), 100 g of PDAP and 0.4 g of CAB-O-SIL. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 4 g of IRG1 was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder.




2. Preparation of Binder Precursor Particles Comprising of a Combination of PAN/PDAP/IRG1/MOD (50/50/2/0.2)




A 0.25 L. jar was charged with 25 g of a viscous liquid ,PAN, and 25g of PDAP. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 1 g. of IRG1 and 0.1 g of MOD was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder. The addition of liquid nitrogen to the cooling solid aided in grinding.




3. Preparation of Binder Precursor Particles Comprising a Combination of AMN/PDAP/CRY/IIRG(50/50/100/2)




A 0.5 L jar was charged with 50 g of AMN (a viscous liquid), 50 g of PDAP, and 100 g of CRY The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 2 g of IRG1 was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder.




4. Preparation of Binder Precursor Particles Comprising a Combination of EP1/EP2/SD 7280/COM (20/60/20/1)




A 0.5 L jar was charged with 20 g of EP 1, 60 g of EP2, and 20 g of SD 7280. The sample was heated to 120° C. for 60 minutes and mixed. Next, 1 g of COM was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder.




5. Preparation of Binder Precursor Particles Comprising a Combination of EP1/EP2/SD 7280/CRY/COM (20/60/20/100/2)




A 0.5 L jar was charged with 20 g of EP1 (a viscous liquid), 60 g of EP2, 20 g of SD 7280 and 100 g of CRY. The sample was heated to 120° C. for 60 minutes and mixed. Next, 2 g of COM was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder.




6. Preparation of Binder Precursor Particles Comprising a Combination of PT60/COM (100/1)




A 0.5 Ljar was charged with 100 g of PT-60 and heated to 90° C. 1 g of COM was added, and the resultant solid was cooled to room temperature. The solid was ground into a fine powder with a grinder.




7. Preparation of Binder Precursor Particles Comprising a Combination PT60/CRY/IRG1 (50/50/1)




A 0.5 L jar was charged with 50 g of 100/1 PT60/COM solid. Next 50 g of CRY was added. The two solids were mixed and ground into a fine powder with a grinder.




8. Preparation of Binder Precursor Particles Comprising a Combination EP2/PDAP/IRG1/COM (70/30/1/1)




A 0.5 L. jar was charged with 70 g EP1 (a solid embodiment), and 30 g PDAP. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 1 g of IRG1 and 1 g of COM was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder.




9. Preparation of Binder Precursor Particles Comprising a Combination EP2/PDAP (70/30/4/2/1/1)




A 0.5 L. jar was charged with 70 g of (EP2), as solid, 30 g of (PDAP), 4g of CaSt2, and 2g of ZnSt2. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 1 g of IRG1 and 1 g of COM was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder.












TABLE 10











Binder Precursor Particle Formulations












Sample No.




Formulation









Sample 39




AMN/PDAP/CAB-O-SIL/IRG1(50/50/0.2/2)






Sample 40




PAN/PDAP/IRG1/MOD(50/50/2/0.2)






Sample 41




AMN/PDAP/CRY/IRG1(50/50/100/2)






Sample 42




EP1/EP2/SD 7280/COM(20/60/20/1)






Sample 43




EP1/EP2/SD 7280/CRY/COM(20/60/20/100/2)






Sample 44




PT60/COM(100/1)






Sample 45




PT60/CRY/COM(100/100/1)






Sample 46




EP2/PDAP/IRG1/COM(70/30/1/1)






Sample 47




EP2/PDAP(70/30/4/2/1/1)






Sample 48




EP1/EP2/SD 7280/COM(38.5/38.5/23/1)






Sample 49




DZ1






Sample 50




DZ2














D. Preparation of Abrasive Articles Comprising a Size Coat




Binder precursor particles sample 39-50 were coated onto one or more of Abrasive Articles C and D to form size coats according to the following procedure.




The binder precursor particle samples 39-46 and 48 were coated onto Abrasive Article D, while binder precursor particle sample 45 and 47 were coated onto Abrasive Article C. Specifically, the binder precursor particles were powder coated onto the abrasive articles at 30 to 160 g/m


2


by drop coating with a mesh sifter. The binder precursor particles were then melted by placing the abrasive article in an oven at a temperature in the range from about 120° C. to about 165° C. for 5-15 minutes. The size coat was then cured by passing the abrasive through a UV lamp (1 pass at 7.6 m/min. with a 157 w/cm bulb). Samples 46 and 47 were placed in an oven for 10 minutes at 100° C. Adhesive sheeting was attached to the abrasive articles and 10.2 cm discs were died out of the abrasive articles.




The binder precursor particle samples 49,and 50 were coated onto Abrasive Article C. Specifically, the binder precursor particles were powder coated onto the abrasive articles by drop coating with a mesh sifter. The abrasive samples were placed in an oven at a temperature in the range from about 105° C. to about 140° C. for about 2 hours. Adhesive sheeting was attached to the abrasive articles and 10.2 cm discs were died out of the abrasive articles.




The details of the resultant abrasive articles are disclosed in Table 11, hereinbelow. All discs were used for Schiefer testing, described below.












TABLE 11











Abrasive Articles Comprising Size Coat















Size Coat





Powder Coat






Sample No.




Weight (g/m


2


)




Abrasive Article




Method

















Sample 39




120




D




Drop Coat






Sample 40




120




D




Drop Coat






Sample 41




171




D




Drop Coat






Sample 42




123




D




Drop Coat






Sample 43




165




D




Drop Coat






Sample 44




123




D




Drop Coat






Sample 45




160




D




Drop Coat






Sample 46A




58.1




C




Drop Coat






Sample 46B




42.0




C




Drop Coat






Sample 47A




61.3




C




Drop Coat






Sample 47B




45.2




C




Drop Coat






Sample 48




123




D




Drop Coat






Sample 49A




42.0




C




Drop Coat






Sample 49B




40.4




C




Drop Coat






Sample 50A




42.0




C




Drop Coat






Sample 50B




32.3




C




Drop Coat














E. Evaluation of Abrasive Articles Comprising a Size Coat




1. Schiefer Test Procedure




Each 10.2 cm diameter disc of the abrasive articles of each Sample 39-50 and Comparative Samples R-V (See Table 11) was secured to a foam back-up pad by means of a pressure sensitive adhesive. Each coated abrasive disc and back-up pad assembly were installed on a Schiefer testing machine, and the coated abrasive disc was used to abrade a properly sized cellulose acetate butyrate polymer of predetermined weight. The load was 4.5 kg. The test was considered completed after 500 revolution cycles of the coated abrasive disc. The cellulose acetate butyrate polymer was then weighed, and the amount of cellulose acetate butyrate polymer removed was recorded. The results of the test procedure are tabulated hereinbelow along with results for the appropriate Comparative Samples. Briefly, the results illustrated in Tables 12-13 illustrated that size coats derived from radiation curable binder precursor particles exhibited superior performance to conventional phenolic size coats. In addition to the superior performance, these binder precursor particles for size coats have environmental and processing advantages over conventional coatings.




Tables 12A, 12B, and 13 show the results of Scheifer Testing for Samples 39-50B and Comparative Samples Q-V.












TABLE 12A











Schiefer Testing for Samples 39-45, 48 and Comparative






Samples S, T, U, V















Sample No.




Cut (g)





















Comparative Ranking Relative to S







Comparative S




2.964




100







Sample 41




3.252




110







Sample 39




3.211




108









Comparative Ranking Relative to T







Comparative T




3.216




100







Sample 44




3.699




115







Sample 45




3.663




114









Comparative Ranking Relative to U







Comparative U




3.421




100







Sample 42




3.776




109







Sample 48




3.831




110









Comparative Ranking Relative to V







Comparative V




3.556




100







Sample 43




4.029




113







Sample 40




2.204




 62























TABLE 12A











Schiefer Testing for Samples 39-45, 48 and Comparative






Samples S, T, U, V















Sample No.




Cut (g)





















Comparative Ranking Relative to S







Comparative S




2.964




100







Sample 41




3.252




110







Sample 39




3.211




108









Comparative Ranking Relative to T







Comparative T




3.216




100







Sample 44




3.699




115







Sample 45




3.663




114









Comparative Ranking Relative to U







Comparative U




3.421




100







Sample 42




3.776




109







Sample 48




3.831




110









Comparative Ranking Relative to V







Comparative V




3.556




100







Sample 43




4.029




113







Sample 40




2.204




 62























TABLE 13











Schiefer Testing for Samples and Comparative Samples Q















Sample No.




Cut (g)




Comparative Ranking Relative to Q











Comparative R




1.223




100 







Sample 49A




1.126




92







Sample 49B




1.289




105 







Sample 50A




1.005




82







Sample 50B




0.793




65















EXAMPLE III




Preparation of Abrasive Article Comprising a Backing Layer and an Abrasive Coating Comprising a Make Coat




A. Preparation of Abrasive Articles Comprising a Backing Layer and Abrasive




1. Comparative Abrasive Article W




Abrasive articles used a backing that was a 95 g/m


2


paper backing C90233 EX commercially available from Kimberly-Clark, Neenah, Wis. A make coat precursor was prepared from DS1227 (20.7 parts), EP1 (30.5 parts), EP2 (33.7 parts), CHDM (2.9 parts), COM (0.6 part), KB1 (1.0 part) and AMOX (0.6 parts). The batch was prepared by melting DS1227 and EP2 together at 140° C., mixing, and then adding EP1 and CHDM followed by further mixing. Then, TMPTA (4.5 parts) was added with mixing at 100° C. To this sample was added COM, AMOX, and KB1 followed by mixing at 100° C. The make coat precursor was applied at 125° C. by means of a knife coater to the paper backing at a weight of about 30 g/m


2


. The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb immediately before P180 AO abrasive particles were electrostatically projected into the make coat precursor at a weight of about 85 g/m


2


. The intermediate product was thermally cured for 15 minutes at a temperature of 100° C.




A size coat precursor was roll coated over the abrasive grains at a wet weight of about 50 g/m


2


. The size coat precursor included a 100% solids blend of EP1 (40 parts), ERL 4221 (30 parts), TMPTA (30 parts), KB1 (1 part), and COM (1 part). The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb followed by a thermal cure for 10 minutes at 100° C.




B. Preparation of Binder Precursors Particles for Use in a Make Coat




1. Preparation of Binder Precursor Particles Comprising a Combination of PDAP/IRG1 (100/1)




A 0.5 L. jar was charged with 100 g of PDAP. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 1 g. of IRG1 was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder.




2. Preparation of Binder Precursor Particles Comprising a Combination of AMN/PDAP/IRG1 (70/30/1)




A 0.5 L. jar was charged with 70 g of AMN (a viscous liquid) and 30 g of PDAP. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 1 g of IRG1 was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder.




3. Preparation of Binder Precursor Particles Comprising a Combination of PAN/PDAP/IRG1 (50/50/1)




A 8oz. jar was charged with 25 g of, a viscous liquid PAN and 25 g of PDAP. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 1 g. of IRGACURE 651 was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder.




4. Preparation of Binder Precursor Particles Comprising a Combination of EP2/PDAP/IRG 1 /COM/(70/30/1/1)




A 0.5 L. jar was charged with 70 g EP2, a solid, and 30 g of PDAP. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 1 g of IRG1 and 1 g of COM was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder












TABLE 14











Binder Precursor Particle Formulations














Sample No.




Formulations











Sample 51A




PDAP/IRG1 (100/10







Sample 51B




PDAP/IRG1 (100/10







Sample 52A




AMN/PDAP (70/30/1)







Sample 52B




AMN/PDAP (70/30/1)







Sample 53A




EP2/PDAP/COM/IRG1 (70/30/1/1)







Sample 53B




EP2/PDAP/COM/IRG1 (70/30/1/1)







Sample 54A




PAN/PDAP/IRG1 (50/50/1)







Sample 54B




PAN/PDAP/IRG1 (50/50/1)















C. Preparation of Abrasvive Articles Comprising a Make Coat




Binder precursor particle samples 51-54 were drop coated onto paper backing EX C90233 which is commercially available from Kimberly-Clark, Neenah, Wis. The specific make weights can be found in Table 15. Next, the binder precursor particles were melted onto the backing in an oven at 100-140° C., and P180 AO mineral was drop coated onto the make coat at a weight of 115 g/m


2


. The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb.




A size coat precursor was roll coated over the abrasive grains at a wet weight of about 100 g/m


2


. The size coat precursor included a 100% solids blend of EP1 (40 parts), ERL 4221 (30 parts), TMPTA (30 parts), KB1 (1 part), and COM (1 part). The sample was then irradiated (3 passes at 18.3 m/min) with one 400 W/cm “D” bulb followed by a thermal cure for 10 minutes at 100° C.












TABLE 15











Abrasive Articles Comprising a Make Coat














Sample No.




Make Coat (g/m


2


)











Sample 51A




16.8







Sample 51B




14.9







Sample 52A




20  







Sample 52B




15.0







Sample 53A




17.1







Sample 53B




16.8







Sample 54A




17.2







Sample 54B




16.9















D. Evaluation of Abrasive Articles Comprising a Make Coat




1. Test Procedures




a. Schiefer Testing Procedure




The coated abrasive article for each example was converted into a 10.2 cm diameter disc and secured to a foam back-up pad by means of a pressure sensitive adhesive. The coated abrasive disc and back-up pad assembly were installed on a Schiefer testing machine, and the coated abrasive disc was used to abrade a cellulose acetate butyrate polymer. The load was 4.5 kg. The endpoint of the test was 500 revolutions or cycles of the coated abrasive disc. The amount of cellulose acetate butyrate polymer removed is recorded.




As illustrated in Table 16, radiation curable binder precursor particles show utility as make coats, especially when the oligomeric material has hydroxyl functionality, for example, AMN and EP2.












TABLE 16











Schiefer Testing






Abrasive Articles Comprising A Make Coat

















Ranking Relative to









Comparative Abrasive Article







Sample No




Cut (g)




W











Comparative W




1.042




100 







Sample 51A




0.036




 3







Sample 51B




0.423




41







Sample 52A




0.840




81







Sample 52B




0.787




76







Sample 53A




0.862




83







Sample 53B




0.946




91







Sample 54A




0.386




37







Sample 54B




0.630




60















EXAMPLE IV




Preparation of Abrasive Article Comprising a Backing Layer and Abrasive Coating Comprising a Grinding Aid Supersize Coat




A. Preparation of Abrasive Articles Comprising a Backing Layer and Abrasive




1. Abrasive Article E




Abrasive articles used a backing that was a 1080 g/m


2


fiber disk (17.8 cm diameter disc) commercially available from Kimberly-Clark, Neenah, Wis. For each, a make coat precursor was prepared from a 75% solids aqueous solution of a phenolic resole (formaldehyde/phenolic ratio of 1.1-3.0/1, pH of about 9), CaCO


2


and FEO (50/50/2). The make coat precursor was applied to the backing with a paint brush. Next, grade 50 AZ mineral was electrostatically projected into the make coat precursor at a weight of about 685 g/m


2


. The intermediate product was thermally cured for 45 minutes at a temperature of 90° C.




A size coat precursor was applied with a paint brush at a weight of 405 g/m


2


. The size coat precursor was prepared from a 75% solids aqueous solution of a phenolic resole (formaldehyde/phenolic ratio of 1.1-3.0/1, pH of about 9), CRY, and FEO (50/60/2)




The sample was cured thermally for 6 hours at 115° C.




2. Comparative Sample X




Abrasive articles used a backing that was a 1080 g/m


2


fiber disk (17.8 cm diameter disc) commercially available from Kimberly-Clark, Neenah, Wis. A make coat precursor was prepared from a 75% solids aqueous solution of a phenolic resole (formaldehyde/phenolic ratio of 1.1-3.0/1, pH of about 9), CaCO


2


and FEO (50/50/2). The make coat precursor was applied to the backing with a paint brush. Next, grade 50 AZ mineral was electrostatically projected into the make coat precursor at a weight of about 685 g/m


2


. The intermediate product was thermally cured for 45 minutes at a temperature of 90° C.




A size coat precursor was applied with a paint brush at a weight of 405 g/m


2


. The size coat precursor was prepared from a 75% solids aqueous solution of a phenolic resole (formaldehyde/phenolic ratio of 1.1-3.0/1, pH of about 9), CRY, and FEO (50/60/2) The sample was cured thermally for 6 hours at 115° C.




B. Preparation of Binder Precursor Particles for Use Grinding Aid Supersize Coat




1. Preparation of Binder Precursor Particles Comprising a Combination of PDAP/KBF4/ZnSt2/IRG1 (30/60/10/1) (Table 17)




A 0.5 L. jar was charged with 30 g of PDAP, 60 g of KBF4, and 10 g of ZnSt2. The sample was heated to 110-115° C. for 30 minutes and mixed. Next, 1 g. of IRG1 was added to the molten mixture, mixed and cooled to room temperature. The resulting solid was ground into a fine powder with a grinder.












TABLE 17











Binder Precursor Particle Formulation














Sample No.




Formulations











Sample 55




PDAP/KBF4/ZnSt2/IRG1 (30/60/10/1)















C. Preparation of Abrasive Articles Comprising a Grinding Supersize Coat




Binder precursor particle sample 55 were drop coated with a mesh sifter onto Abrasive Article E. The specific supersize weights can be found in Table 18. Next, the binder precursor particles were melted onto the abrasive article in an oven at 100-140° C., The samples were then irradiated (1 pass at 18.3 m/min) with one 400 W/cm “D” bulb.












TABLE 18











Abrasive Article Comprising a Supersize Coat














Sample No.




Supersize Coat (g/m


2


)











Sample 55




153















D. Evaluation of Abrasive Articles Comprising a Grinding Aid Supersize Coat




1. Swing Arm Flat Test




Abrasive article samples (17.8 cm diameter discs and 2.2 cm center diameter hole and 0.76 mm thickness) were attached to a backup pad and secured to the Swing Arm tester with a metal screw fastener. A 4130 steel workpiece (35 cm diameter) was weighed and secured to the Swing Arm tester with a metal fastener. The pressure was 4.0 kg. The endpoint of the test was 8 min at 350 rpm. The amount of steel removed was recorded.




As illustrated in Table 19, radiation curable binder precursor particles show utility as grinding aid supersize coats.












TABLE 19











Flat Testing of Sample 55 and Comparative X

















Ranking Relative to









Comparative Abrasive Article







Sample No




Cut (g)




X











Comparative W




128




100







Sample 55




134




105















Numerous characteristics, advantages, and embodiments of the invention have been described in detail in the foregoing description with reference to the accompanying drawings. However, the disclosure is illustrative only and the invention is not intended to be limited to the precise embodiments illustrated. Various changes and modifications may be made in the invention by one skilled in the art without departing from the scope or spirit of the invention.



Claims
  • 1. A powder comprising a radiation curable component that is flowable at a temperature in the range from about 35° C. to about 180° C. containing at least one polyfunctional, radiation curable monomer and at least one polyfunctional, radiation curable macromolecule selected from an oligomer, a polymer, and a combination of at least one oligomer and at least one polymer, wherein the weight ratio of the monomer to the macromolecule is in the range from about 1:10 to about 10:1.
  • 2. The powder of claim 1, wherein the radiation curable component comprises at least one radiation curable macromolecule including a plurality of radiation curable groups and a plurality of OH groups.
  • 3. The powder of claim 1, wherein the radiation curable component comprises at least one radiation curable compound having a backbone containing an aromatic or heterocyclic moiety.
  • 4. The powder of claim 1, wherein at least one of the monomer and macromolecule is a solid at temperatures below about 35° C.
  • 5. The powder of claim 1, wherein the monomer and macromolecule are both solids at temperatures below about 35° C.
  • 6. The powder of claim 1, wherein the monomer is a solid at temperatures below about 35° C. and the macromolecule is a liquid at least under ambient conditions.
  • 7. The powder of claim 1, wherein the monomer is selected from a reaction product of a dicarboxylic acid and a reactant comprising hydroxy and radiation curable functionality, a reaction product of a hydroxyl functional isocyanurate and a carboxylic acid, a reaction product of a diisocyanate and a reactant comprising hydroxy and radiation curable functionality, a cyanate ester, a vinyl ether, and combinations thereof.
  • 8. The powder of claim 1, wherein the oligomer is selected from the group consisting of a novolak phenolic oligomer functionalized with a plurality of radiation curable groups, a chain-extended bishenol A epoxy oligomer functionalized with a plurality of radiation curable groups, an epoxy functional oligomer, a novolak oligomer having cyanate ester functionality and combinations thereof.
  • 9. The powder of claim 1, wherein the binder precursor comprises a radiation curable, monomer and a radiation curable, oligomer, wherein each of said monomer and oligomer independently has a melting point such that a blend of the monomer and oligomer is a solid at a temperature below about 35 C. and such that said blend is a melt at a temperature above about 35 C., wherein the weight ratio of the monomer to the oligomer is in the range from about 1:10 to 10:1.
  • 10. The powder of claim 1, wherein the radiation curable component comprises a monomer of the formula: wherein W is a divalent aromatic moiety, X is divalent linking group, and R is selected from hydrogen or a lower alkyl group of 1 to 4 carbon atoms.
  • 11. The powder of claim 1, wherein the radiation curable component comprises a monomer of the formula: wherein W′ is a divalent, aromatic moiety, Z′ is a divalent linking group, and R is hydrogen or a lower alkyl group of 1 to 4 carbon atoms.
  • 12. The powder of claim 1, wherein the radiation curable component comprises a monomer of the formula: wherein X″ is a divalent linking group.
  • 13. The powder of claim 1, wherein the radiation curable component comprises an oligomer of the formula: wherein n has an average value in the range from about 3 to about 20.
  • 14. The powder of claim 1, wherein the radiation curable component comprises an oligomer of the formula: wherein n has an average value in the range from about 3 to about 20.
  • 15. The powder of claim 1, wherein the radiation curable component comprises an oligomer of the formula: wherein n has a value such that the oligomer has a number average molecular weight in the range from about 800 to about 5000.
  • 16. A powder, comprising a radiation curable component that is a solid at temperatures below about 35° C. and is fluidly flowable at a temperature in the range from about 35° C. to about 180° C. and containing at least one monomer selected from the group consisting of (meth)acrylamide functional polyesters, (meth)acrylate-functional esters of aromatic dicarboxylic acids, (meth)acrylate-functional amides of aromatic dicarboxylic acids, and cyanate esters, and at least one macromolecule selected from the group consisting of cyanate ester oligomers, mixtures of cyanate esters and epoxy resins, and acrylamidomethyl novolaks.
Parent Case Info

This application is a divisional application of U.S. application Ser. No. 09/071,263, filed May 1, 1998, now U.S. Pat. No. 6,228,133, issued May 8, 2001.

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