CA1253700A - Coated abrasive product having radiation curable binder - Google Patents
Coated abrasive product having radiation curable binderInfo
- Publication number
- CA1253700A CA1253700A CA000510630A CA510630A CA1253700A CA 1253700 A CA1253700 A CA 1253700A CA 000510630 A CA000510630 A CA 000510630A CA 510630 A CA510630 A CA 510630A CA 1253700 A CA1253700 A CA 1253700A
- Authority
- CA
- Canada
- Prior art keywords
- group
- abrasive
- coat
- abrasive product
- terminal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/28—Resins or natural or synthetic macromolecular compounds
- B24D3/30—Resins or natural or synthetic macromolecular compounds for close-grained structure
Abstract
Abstract This invention relates to coated abrasive products having a resinous binder which holds and supports abrasive granules on a backing sheet.
In the manufacture of coated abrasives, the make coat resinous binder and abrasive granules are first applied to the backing, then the size coat resinous binder is applied, and finally, the construction is fully cured. Generally, thermally curable binders provide coated abrasives having excellent properties, e.g. heat resistance.
With polyester or cellulose backings, however, curing temperatures are limited to about 130° C. At this temperature, cure times are long. The long cure times necessitate the use of festoon curing areas. Disadvan-tages of festoon curing areas include formation of defects at the suspension rods, inconsistent cure on account of temperature variations in the large festoon ovens, sagging of the binder, and shifting of abrasive granules. Furthermore festoon curing areas require large amounts of space and large amounts of energy.
This invention provides a coated abrasive product comprising abrasive granules adherently bonded to at least one major surface of a backing sheet by a radiation curable resinous binder material. The binder material can be used to form the make coat, size coat, or both coats.
Alternatively, the binder material can be used in embodiments where only a single binder coat is employed.
The radiation curable resinous binder material comprises a copolymer formed from a mixture comprising (1) at least one monomer selected from the group consisting of isocyanurate derivatives having at least one terminal or pendant acrylate group and isocyanate derivatives having at least one terminal or pendant acrylate group, and (2) at least one aliphatic or cycloaliphatic monomer having at least one terminal or pendant acrylate group.
In the manufacture of coated abrasives, the make coat resinous binder and abrasive granules are first applied to the backing, then the size coat resinous binder is applied, and finally, the construction is fully cured. Generally, thermally curable binders provide coated abrasives having excellent properties, e.g. heat resistance.
With polyester or cellulose backings, however, curing temperatures are limited to about 130° C. At this temperature, cure times are long. The long cure times necessitate the use of festoon curing areas. Disadvan-tages of festoon curing areas include formation of defects at the suspension rods, inconsistent cure on account of temperature variations in the large festoon ovens, sagging of the binder, and shifting of abrasive granules. Furthermore festoon curing areas require large amounts of space and large amounts of energy.
This invention provides a coated abrasive product comprising abrasive granules adherently bonded to at least one major surface of a backing sheet by a radiation curable resinous binder material. The binder material can be used to form the make coat, size coat, or both coats.
Alternatively, the binder material can be used in embodiments where only a single binder coat is employed.
The radiation curable resinous binder material comprises a copolymer formed from a mixture comprising (1) at least one monomer selected from the group consisting of isocyanurate derivatives having at least one terminal or pendant acrylate group and isocyanate derivatives having at least one terminal or pendant acrylate group, and (2) at least one aliphatic or cycloaliphatic monomer having at least one terminal or pendant acrylate group.
Description
7~
FN 4Os45cAN3A
COATED ABRASIVE PRODtJCT HAVING
RADIATION CURABLE BINDER
Back~round of the Invention _ _ This invention relate~ to coated abra 8 ive products having a resinous binder which hold~ and supports abrasive granules on a backing sheet.
Coated abrasives generally comprise a flexible backing upon which adhesive hold~ and supports a coating of abrasive granules. The backing may be paper, cloth, Eilm, vulcanized fiber, etc. or a combination of one or more of these materials. The abrasive granules may be formed of flint, garnet, aluminum oxide, alumina-zirconia, diamond, silicon carbide, etc. Popular present day binders are phenolic resins, hide glue, and varniqh. Phenolic resins include those of the phenol-aldehyde type. Besides phenolic resins, hide glue, and varnish, other known re~inous binder materials employed in the preparation of coated abra~ive products include epoxy re~ins, urea-formaldehyde re~ins, and polyurethane resins.
The coated abrasive rnay employ a "make" coat ofresinou~ binder material which is utilized to secure the end~ of the abrasive granules onto the sheet as the granules are oriented and a "size" coat of resinous binder material over the make coat which provides for firm adherent bonding of the abrasive granules to the 3heet.
The size coat resin may be of the same material as the make coat re~in or of a different resinous material.
In the manufacture of coated abrasives, the malce coat resinous binder and abrasive granules are first applied to the backing, then the size coat resinous binder i~ applied, and finally, the construction is fully cured.
Generally, thermally curable binder~ provide coated abra~ive~ having excellent properties, e.g. heat resistance. Thermally curable binders include phenolic .,
FN 4Os45cAN3A
COATED ABRASIVE PRODtJCT HAVING
RADIATION CURABLE BINDER
Back~round of the Invention _ _ This invention relate~ to coated abra 8 ive products having a resinous binder which hold~ and supports abrasive granules on a backing sheet.
Coated abrasives generally comprise a flexible backing upon which adhesive hold~ and supports a coating of abrasive granules. The backing may be paper, cloth, Eilm, vulcanized fiber, etc. or a combination of one or more of these materials. The abrasive granules may be formed of flint, garnet, aluminum oxide, alumina-zirconia, diamond, silicon carbide, etc. Popular present day binders are phenolic resins, hide glue, and varniqh. Phenolic resins include those of the phenol-aldehyde type. Besides phenolic resins, hide glue, and varnish, other known re~inous binder materials employed in the preparation of coated abra~ive products include epoxy re~ins, urea-formaldehyde re~ins, and polyurethane resins.
The coated abrasive rnay employ a "make" coat ofresinou~ binder material which is utilized to secure the end~ of the abrasive granules onto the sheet as the granules are oriented and a "size" coat of resinous binder material over the make coat which provides for firm adherent bonding of the abrasive granules to the 3heet.
The size coat resin may be of the same material as the make coat re~in or of a different resinous material.
In the manufacture of coated abrasives, the malce coat resinous binder and abrasive granules are first applied to the backing, then the size coat resinous binder i~ applied, and finally, the construction is fully cured.
Generally, thermally curable binder~ provide coated abra~ive~ having excellent properties, e.g. heat resistance. Thermally curable binders include phenolic .,
2~ 0 re~in~, epoxy resins, and allcyd resins. With polye~ter or cellulose backings, however, curing temperature3 are limited to about 130C. At this temperature, cure tlmes are long. The long cure tioes nece33itate the u3e oE ~e~toon curing areas. Disadvantage~ of fe~toon curing areas include formation of de~ects at the 3uspension rods, incon~istent cure on account o temperature variation.s in the large fe~toon ovens, sagging of tlle binder, and shifting of abrasive granule.q. Furthermore fe~toon curing areas require larye amounts of ~pace and large amounts of energy.
It has been proposed to use radiation curing processes to avoid the disadvantages of thermal curing processes in the manufacture of coated abrasives. U.S.
Patent 4,047,903 discloses an epoxy-acrylic binder a-nd electron irradiation to manufacture coated abrasivesO U.S.
Patent 4,345,545, U.S. Patent 4,457,766 and ~riti~h Patent 2,087,263A disclose a method for electron beam curing of resin coated webs in the manufacture of coated abrasives.
Examples of electron beam curable resinous binders disclosed therein include urethane-acrylate~ and epoxy-acrylates. The binders disclosed in these patents are inferior to thermally curable binders with respect to thermal ~tability, s~lrface hardnes3, and grinding performanceO
SUMMARY OF THE INVENTION
This invention involves a coated abrasive comprising a backing bearing abrasive grains or granules in combination with a binder compri~ing a copolymer formed ~rom (1) at leaqt one monomer 3elected from the group con3isting of isocyanurate derivatives having at least one terminal or pendant acrylate group and isocyanate deriva-tives having at least one terminal or pendant acrylate group, and (2) at least one aliphatic or cycloaliphatic monomer having at least one terminal or pendant acrylate group. The preferred monomers of the isocyanurate/
isocyanate group have a heterocyclic ring configuration, j3~
It has been proposed to use radiation curing processes to avoid the disadvantages of thermal curing processes in the manufacture of coated abrasives. U.S.
Patent 4,047,903 discloses an epoxy-acrylic binder a-nd electron irradiation to manufacture coated abrasivesO U.S.
Patent 4,345,545, U.S. Patent 4,457,766 and ~riti~h Patent 2,087,263A disclose a method for electron beam curing of resin coated webs in the manufacture of coated abrasives.
Examples of electron beam curable resinous binders disclosed therein include urethane-acrylate~ and epoxy-acrylates. The binders disclosed in these patents are inferior to thermally curable binders with respect to thermal ~tability, s~lrface hardnes3, and grinding performanceO
SUMMARY OF THE INVENTION
This invention involves a coated abrasive comprising a backing bearing abrasive grains or granules in combination with a binder compri~ing a copolymer formed ~rom (1) at leaqt one monomer 3elected from the group con3isting of isocyanurate derivatives having at least one terminal or pendant acrylate group and isocyanate deriva-tives having at least one terminal or pendant acrylate group, and (2) at least one aliphatic or cycloaliphatic monomer having at least one terminal or pendant acrylate group. The preferred monomers of the isocyanurate/
isocyanate group have a heterocyclic ring configuration, j3~
-3-the preferred monomer being the reaction product of a mixture of acrylic acid and methacrylic acid with tris~hydroxyalkyl)i~ocyanurate. The preferred aliphatic or cycloaliphatic monomer of the group having at leaAt one acrylate group i3 trimethylolpropanetriacrylate. The copolymer i9 preferably formed by exposing a mixture containing the aforementioned monomers to conventional sources of electromagnetic radiation, preferably sources o~
ionizing radiation.
The performance of the coated abrasive of the pre~ent invention eguals or exceed~ that of coated abrasives forme~ with thermally curable phenolic resins, particularly with respect to grinding performance, hardness, and thermal ~stability. The coated abrasive of this invention demonstrates improved performance over radiation curable coated abrasive~ heretofore known, particularly with respect to thermal stability, 3urPace hardness, and grinding performance.
DETAIL~D DESCRIPTION
.
The conventionai components going to form the coated abrasive product of the invention will be selected from those typically use(3 in this art. The backing, as previously mentioned, may be formed of paper, cloth, vulcanized fiber, polymeric film or any other backing materlal known ~or this use. The abra~ive granule~ may be of any conventional grade utilized in the formation o~
coated abrasives and may be formed of flint, garnet, aluminum oxide, alumina:zirconia, diamond and ~ilicon carbide, etc., or mixtures thereof. The frequency of the abrasive granules on the sheet will also be conventional.
The abrasive granule may be oriented or may be applied to the backing without orientation, depending upon the requirements of the particular coated abrasive product.
The coated abrasive product of the invention may also include ~uch modifications as are known in this art.
For example, a back coating such as pressure-sensitive ~:5i3~(~3 .
adhe~ive may be applied to the nonabra~ive side oE the backing and various supersizes, such as zinc 3tearate, may be applied to the abrasive surace to prevent abra~ive loading, and other~.
The binders or the coated abrasive of this invention comprise copolymers formed by the copolymeriæation of comonomers selected from two classe~.
The reaction mixture must contain at lea~t one comonomer from each clas~. The fir.st class of monomer3 includes isocyanurate derivatives or i~ocyanate derivatives having at lea3t one terminal or pendant acrylate group. ~9 u.sed herein, "acrylate" includes hoth acrylate and rnethacrylate.
The Aecond class of aliphatic or cycloaliphatic monomers includes acrylic acid e~ters. These monomers must contain at lea~t ons terminal or pendant acrylate group.
The monomer~ of isocyanurate derivatives can be repre~ented by the following structure:
cao R--N ~N--R
O=C~ ~C=O
N
R
where each R can be the ~ame or different and represents a group containing at lea~t one terminal acrylate or methacrylate group.~ Preferably, R repre~ents 1l H
- Rl-0-C-C=C\ (Ia) -Rl-NH-C-o-R6C ~ R7-o-C-C=C 1 (Ib) Rc L R2 \ R3~a - Rl-0-C-NH~R6-C ~ R7-o-C-C-C \ ~ (Ic) S
where Rl repre~ent~ a divalent alkylene group having, for example, ~rom 1 to 20 carbon atoms, prefeeably from 1 to 10 carbon atoms, R2 repre.qent~ -~1 or -C~13, R3 repr-e~entA -ll or -Cl~3, R4 repre~qents hydrogen, an alkyl group having, for example, 1 to 20 carbon atoms, an arylalkyl group having, for example, 6 to 26 carbon atoms, R5 represents hydrogen, an alkyl group having, for example, 1 to 20 carbon atoms, an arylalkyl group having, for example, 6 to 26 carbon atoms, R6 represent~ a divalent alXylene group having, for example, from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, ~2~ R7 represents a covalent bond or a divalent alkylene group having, for example, ~rom 1 to 20 carbon atoms, preferably, 1 to 10 carbon atoms, a represent~ an integer from 1 to 3, inclusive, b represent~ 0 or 1, c repre~ent~ 0 or 1, and a t b + c = 3.
The ~oieties represented by Rl, R6, R7 can be straight chain, branched, or cyclic. If cyclic, the cyclic r;ng can con~ain 5 or 6 ring atoms.
I30cyanurate monomers 3uitable for the pre~ent invention can be prepared according to methods described in U.S. Patents 3,932,401, 4,145,544, 4,288,586, 4,324,879,
ionizing radiation.
The performance of the coated abrasive of the pre~ent invention eguals or exceed~ that of coated abrasives forme~ with thermally curable phenolic resins, particularly with respect to grinding performance, hardness, and thermal ~stability. The coated abrasive of this invention demonstrates improved performance over radiation curable coated abrasive~ heretofore known, particularly with respect to thermal stability, 3urPace hardness, and grinding performance.
DETAIL~D DESCRIPTION
.
The conventionai components going to form the coated abrasive product of the invention will be selected from those typically use(3 in this art. The backing, as previously mentioned, may be formed of paper, cloth, vulcanized fiber, polymeric film or any other backing materlal known ~or this use. The abra~ive granule~ may be of any conventional grade utilized in the formation o~
coated abrasives and may be formed of flint, garnet, aluminum oxide, alumina:zirconia, diamond and ~ilicon carbide, etc., or mixtures thereof. The frequency of the abrasive granules on the sheet will also be conventional.
The abrasive granule may be oriented or may be applied to the backing without orientation, depending upon the requirements of the particular coated abrasive product.
The coated abrasive product of the invention may also include ~uch modifications as are known in this art.
For example, a back coating such as pressure-sensitive ~:5i3~(~3 .
adhe~ive may be applied to the nonabra~ive side oE the backing and various supersizes, such as zinc 3tearate, may be applied to the abrasive surace to prevent abra~ive loading, and other~.
The binders or the coated abrasive of this invention comprise copolymers formed by the copolymeriæation of comonomers selected from two classe~.
The reaction mixture must contain at lea~t one comonomer from each clas~. The fir.st class of monomer3 includes isocyanurate derivatives or i~ocyanate derivatives having at lea3t one terminal or pendant acrylate group. ~9 u.sed herein, "acrylate" includes hoth acrylate and rnethacrylate.
The Aecond class of aliphatic or cycloaliphatic monomers includes acrylic acid e~ters. These monomers must contain at lea~t ons terminal or pendant acrylate group.
The monomer~ of isocyanurate derivatives can be repre~ented by the following structure:
cao R--N ~N--R
O=C~ ~C=O
N
R
where each R can be the ~ame or different and represents a group containing at lea~t one terminal acrylate or methacrylate group.~ Preferably, R repre~ents 1l H
- Rl-0-C-C=C\ (Ia) -Rl-NH-C-o-R6C ~ R7-o-C-C=C 1 (Ib) Rc L R2 \ R3~a - Rl-0-C-NH~R6-C ~ R7-o-C-C-C \ ~ (Ic) S
where Rl repre~ent~ a divalent alkylene group having, for example, ~rom 1 to 20 carbon atoms, prefeeably from 1 to 10 carbon atoms, R2 repre.qent~ -~1 or -C~13, R3 repr-e~entA -ll or -Cl~3, R4 repre~qents hydrogen, an alkyl group having, for example, 1 to 20 carbon atoms, an arylalkyl group having, for example, 6 to 26 carbon atoms, R5 represents hydrogen, an alkyl group having, for example, 1 to 20 carbon atoms, an arylalkyl group having, for example, 6 to 26 carbon atoms, R6 represent~ a divalent alXylene group having, for example, from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, ~2~ R7 represents a covalent bond or a divalent alkylene group having, for example, ~rom 1 to 20 carbon atoms, preferably, 1 to 10 carbon atoms, a represent~ an integer from 1 to 3, inclusive, b represent~ 0 or 1, c repre~ent~ 0 or 1, and a t b + c = 3.
The ~oieties represented by Rl, R6, R7 can be straight chain, branched, or cyclic. If cyclic, the cyclic r;ng can con~ain 5 or 6 ring atoms.
I30cyanurate monomers 3uitable for the pre~ent invention can be prepared according to methods described in U.S. Patents 3,932,401, 4,145,544, 4,288,586, 4,324,879,
4,~5,226^
The monomer.s of acyclic isocyanate derivatives can be represented by the following structure:
~' 7~3~
.
o o R8-C-NH - A ~ NH-C-R8 II
where A represents a divalent alkylene group having, for example, from 1 to 20 carbon atoms, preferably 1 to 10 carbon atom~, R8 can be the ~arne or different and represents _o_R6_C__~7 -o-c-c-c\ a where a, b, c, R2, R3, R4, R5, R6, R7 are as defined above.
A can be straight chain, branched chain, or if sufficiently long, cyclic. -Because of availability of starting materials, A is preferably -cl~2-c(Cl~3)2-cll2-c~l(cH3)-c~l2 CH2 The monomers in the heterocyclic ring configuration are preferred because polymer~ formed from them are more durable, particularly under high temperature grinding conditions.
The preferred aliphatic or cycloaliphatic rnonomers having at least one terminal or pendant acrylate group can be represented by the following structure:
where each R9 can be the same or different~ and o / H
R9 represents H or _R13-o-c-i _ C
R12 Rll i3~
~7--R10 represent~ alkyl group having, for example, 1 to 10 carbon atoms, Rll represent3 ~l or -C~13, Rl~ repre~ents ~l or CH3, R13 represents a covalent bond or a divalent alkylene group having, Eor example, from 1 to 20 carbon atoms, provided that at least one R9 is not ll.
The moiety represented by R13 can be straight chain, branched, or cyclic. If cyclic, the cyclic ring can 0 contain 5 or ~ ring atoms.
Acrylate monomers of Formula III suitable for the present invention include the mono- or polyfunctional esters of acrylic, methacrylic, or crotonic acids, for example, methyl, ethyl, propyl, butyl, hexyl or hydroxyalkyl esters of these acids, and aromatic monomers ~uch a~ vinyl toluene, styrenes, divinylbenzene and allylesters. Acrylic ester monomers suitable for this invention are commercially available.
The ratio of monomer I or monomer II to monomer ZO III can range from about 1:3 to about 3:1, and preferably ranges from about 1.5:1 to about 1:1.5.
The copolymerizable monomers themselves can act as diluents to control the viscosity of the coating resin without imparting the pollution effects of non-reactive solventsO
In order to prepare the composition for preparing the binder, the monomers, along with any filler~, catalyst~, and other additives are first mixed together in a suitable vessel. The thus-formed mixture is then applied to the 3urface upon which the coating is to be formed, e.g.
the backing for the make coat, the layer of abra~ive mineral for the size coat.
The copolymers useful in forming the binder of this invention are preferably formed and cured by means of 3S electromagnetic radiation, more preferably ionizing radiation, e.g., electron beam radiation having an energy of 0.1 to 10 Mrad, preferably 1 to 10 Mrad. The amount of -8~ 3q~3 radiation u~ecl depencl~ upon the degree of cure de3ired o~
the monomers used to prepare the copolymer3. Typical electron radiation doses allow proce3sing speQd3 o~ up to 300 m/min. The rate of curing with a given level of radiation varie~ according to the thicknes3 a~ well as the den3ity and nature of composition. Other 30urces of ionizinq radiation suitable for curing the binders of this invention include gamma-radiation and X-ray. Ultraviolet radiation can also he u~ed to ~orm and cure the copolymers oE the binder oE this invention. In addition, after the binder i9 cured by me~n~ oP radiation, it can be post-cured by means of thermal energy in order to fully cure any copolymer that may be in grit shadow during radiation exposure. Alternatively, the copolymer~ can he formed and cured by means of thermal energy. If thermal energy i9 employed, either for post-curing or for primary curing, it is preferable to include a thermal curing catalyst in the compo3ition conta;ning the monomers. Conventional peroxide curing catalysts, e.g. benzoyl peroxide, can be employed when thermal curing i~ utilized.
The make coat and the 3ize coat can be cured simultaneou3ly or 3eparately. Cure can be performed in air, but is preferably performed in a nitrogen atmosphere.
When cured ~eparately, the make coat i5 cured in air because it i3 generally de3ired to have the ~urface of the make coat not fully cured at the time of the size coat application to allow the curing o~ the size coat to effect a bond between the two coat~. Either the make coat or size coat can be thermally cured, typically with the addition of a proper cataly~t. I~owever, it i~ preferred that both make coat and size coat be radiation curable to retain the de3ired proce~sing advantage~.
It is not necessary that hoth the make coat and 3ize coat be Pormed of the binder of the pre3ent invention.
If the ~ize coat is formed of the binder of this invention, the make coat can be formed of a conventional binder material, e.g. phenolic resins, hide glue, varni3h, epoxy _9_ resin~, urea-formaldehyde resins, polyurethane resins. If the make coat i8 formed o the binder o~ this invention, the ~ize coat can be ~ormed of a conventional blnder material. Of cour~, both the make coat and size coat can be formed ~rom a binder or binder~ of the~present invention.
It i~ also contemplated that a single binder coat can be employed, r~ther than a make coat and a ~ize coat.
I-lowever~ it i.s preferred that both a make coat and size coat be ~Iti]ized.
The propertieq and ~erformance of coated abra~ives according to the invention are equal to or ~uperior to tho~e of coated abrasives having binders comprising phenolic re~in. Propertie~ such as Barcol hardne~s, temperature ~tability, binding ~trength, and durability under grinding condition3 of the binders of this invention meet or exceed tho~e propertie~ exhibited by binders comprising phenolic resin. The cured re~in of the abrasive product~ of this invention result~ in ~uperior thermal resistance to binder degradation which i9 brought about by high speed grinding. Coated abrasive product~
employing the re~inou~ hinder of this invention are amenable to water cooling.
In additiQn, the binder of the present invention doe~ not requ~re a solvent, thereby eliminating the need ~or ~olvent removal and pollution abatement problem~.
In the example~ which eollow, the ~ollowin~
abbreviations are used:
AA - Acrylic acid TMP~A - Trimethylol propane triacrylate TATHEIC - Triacrylate of tristhydroxy ethyl) i~ocyanurate NVP - N-vinyl-2-pyrrolidone IIMDI - Tri~Hexamethylene dii~ocyanate~
HMnI-T7 - Tris(Hexamethylene diisocyanate) havinq 7 acrylate groups -lo--HMDI-T9 - Tris(Hexamqthylene diisocyanate) having 9 acrylate yroups N-BUMA - N-butyl urethane methacrylate TEGDMA - Triethyleneglycol dimethacrylate TMDI - 2,2,~-trimethyl hexamethylene diisocyanate TMDI-Ir2 - 2,2,4-trlmethyl hexamethylene r3iisocyanate having 2 acrylate groups TMDI-T4 - 2,2,4-trimethyl hexamethylene diisocyanate having 4 acrylate groups IBOA - isobornyl acrylate CaC03 - calcium carbonate.
The ~ollowing examples are offered to aid in understanding the present invention and are not to be construed as limiting the scope thereof. All amounts are in parts by weight unless indicated otherwiseO
EXAMPLE l This example demonstrates how the superior su~face hardness of the resins or copolymers used to prepare binders of thi~ invention compares with that property of re~ins used to prepare binders of the prior art.
In each sample, the binder was prepared by introducing the ingredients into a veqsel equipped with a mechanical stirrer and stirring the ingredients until the mixture was homogeneous. The radiation-curable binder compo~ltions were knife coated onto a polyethylene terephthalate (PET) film at a 4 mil wet thickneqq and then irradiated at 200 Kev Witt1 a dose of 5 Mrad in a nitrogen atmosphere with a Model 250 Electrocurtain electron beam from Energy Science, Inc., Woburn, MA. The phenolic control samples were prepared by casting the phenolic compositions in a glass tray, followed by a 90 minute cure at 90C and a subsequent 12 hour cure at 100C~
25;3~7~i7 The samples prepared as described above were measured for hardnes~ by the ~arcol method (ASl'M
D-2533-75). The method involves applying a force to a needle point, ob~erving the penetration weiyht, and recording said weigllt as a percent Oe the weight required to penetrate gla~s. The results are shown in Table I, wllerein samples 1 and 2 describe binders of the present invention and sample~ 3 through 8, inclusive, describe binders of the prior art. ..Sample~s 3~5 were thermally . 10 cured, and sampl.e~ 6-~ were cured by radiation.
:~ ~,5~
--~. 2--_ -a r~ n ~n o ~ 1n n r~ r~
¦ I Ln I ¦ Ln ¦ I o,) 1 8" r~) l l U
~1 ~
~ ~ I I I I j~; ~ I o~
~D
~1 u I I I I I ~ o o ~ ¦ u~I I I a' m ~ o n r~) ~
1 ~ C ~ ' ~ 3 r~ a ~
~5370~:3 The filled and unfilled TMPTA/TATHEIC rQsin systems display hardne~s exceeding that oE any of the other radiation-cured re~ins or of the thermally cured phenolic resins.
This example compares thermal ~tability of the radiation cured resinou~ binders of this invention with the thermally cured F)henolic binders of the prior art. Thermal stability was mea.sured by loss of weight, in percent, a5 a function of temperature.
Samples were prepared according to the procedure described in Example 1. The samples were removed from the PET film and glass tray and were analyzed by thermal gravimetric analysis (~GA)~ The TGA measurements were conducted in an air atmo.sphere at a flow rate of 100 cc/minute to a maximum temperature of 450C on a P~rkin-Elmer Model TGS-2 thermal analyzer. The starting temperature o~ 20C was increased at a rate of 20C/min.
The re~ults are shown in Table II, wherein samples 9 through 11, inclusive, describe tlle cured binder of the pre~ent invention, and ~samples 12 through 16, inclusive, de~cribe binders of the prior art. Samples 12-14 were thermally cured and Sample~ 15-16 were cured by radiation.
The monomer.s of acyclic isocyanate derivatives can be represented by the following structure:
~' 7~3~
.
o o R8-C-NH - A ~ NH-C-R8 II
where A represents a divalent alkylene group having, for example, from 1 to 20 carbon atoms, preferably 1 to 10 carbon atom~, R8 can be the ~arne or different and represents _o_R6_C__~7 -o-c-c-c\ a where a, b, c, R2, R3, R4, R5, R6, R7 are as defined above.
A can be straight chain, branched chain, or if sufficiently long, cyclic. -Because of availability of starting materials, A is preferably -cl~2-c(Cl~3)2-cll2-c~l(cH3)-c~l2 CH2 The monomers in the heterocyclic ring configuration are preferred because polymer~ formed from them are more durable, particularly under high temperature grinding conditions.
The preferred aliphatic or cycloaliphatic rnonomers having at least one terminal or pendant acrylate group can be represented by the following structure:
where each R9 can be the same or different~ and o / H
R9 represents H or _R13-o-c-i _ C
R12 Rll i3~
~7--R10 represent~ alkyl group having, for example, 1 to 10 carbon atoms, Rll represent3 ~l or -C~13, Rl~ repre~ents ~l or CH3, R13 represents a covalent bond or a divalent alkylene group having, Eor example, from 1 to 20 carbon atoms, provided that at least one R9 is not ll.
The moiety represented by R13 can be straight chain, branched, or cyclic. If cyclic, the cyclic ring can 0 contain 5 or ~ ring atoms.
Acrylate monomers of Formula III suitable for the present invention include the mono- or polyfunctional esters of acrylic, methacrylic, or crotonic acids, for example, methyl, ethyl, propyl, butyl, hexyl or hydroxyalkyl esters of these acids, and aromatic monomers ~uch a~ vinyl toluene, styrenes, divinylbenzene and allylesters. Acrylic ester monomers suitable for this invention are commercially available.
The ratio of monomer I or monomer II to monomer ZO III can range from about 1:3 to about 3:1, and preferably ranges from about 1.5:1 to about 1:1.5.
The copolymerizable monomers themselves can act as diluents to control the viscosity of the coating resin without imparting the pollution effects of non-reactive solventsO
In order to prepare the composition for preparing the binder, the monomers, along with any filler~, catalyst~, and other additives are first mixed together in a suitable vessel. The thus-formed mixture is then applied to the 3urface upon which the coating is to be formed, e.g.
the backing for the make coat, the layer of abra~ive mineral for the size coat.
The copolymers useful in forming the binder of this invention are preferably formed and cured by means of 3S electromagnetic radiation, more preferably ionizing radiation, e.g., electron beam radiation having an energy of 0.1 to 10 Mrad, preferably 1 to 10 Mrad. The amount of -8~ 3q~3 radiation u~ecl depencl~ upon the degree of cure de3ired o~
the monomers used to prepare the copolymer3. Typical electron radiation doses allow proce3sing speQd3 o~ up to 300 m/min. The rate of curing with a given level of radiation varie~ according to the thicknes3 a~ well as the den3ity and nature of composition. Other 30urces of ionizinq radiation suitable for curing the binders of this invention include gamma-radiation and X-ray. Ultraviolet radiation can also he u~ed to ~orm and cure the copolymers oE the binder oE this invention. In addition, after the binder i9 cured by me~n~ oP radiation, it can be post-cured by means of thermal energy in order to fully cure any copolymer that may be in grit shadow during radiation exposure. Alternatively, the copolymer~ can he formed and cured by means of thermal energy. If thermal energy i9 employed, either for post-curing or for primary curing, it is preferable to include a thermal curing catalyst in the compo3ition conta;ning the monomers. Conventional peroxide curing catalysts, e.g. benzoyl peroxide, can be employed when thermal curing i~ utilized.
The make coat and the 3ize coat can be cured simultaneou3ly or 3eparately. Cure can be performed in air, but is preferably performed in a nitrogen atmosphere.
When cured ~eparately, the make coat i5 cured in air because it i3 generally de3ired to have the ~urface of the make coat not fully cured at the time of the size coat application to allow the curing o~ the size coat to effect a bond between the two coat~. Either the make coat or size coat can be thermally cured, typically with the addition of a proper cataly~t. I~owever, it i~ preferred that both make coat and size coat be radiation curable to retain the de3ired proce~sing advantage~.
It is not necessary that hoth the make coat and 3ize coat be Pormed of the binder of the pre3ent invention.
If the ~ize coat is formed of the binder of this invention, the make coat can be formed of a conventional binder material, e.g. phenolic resins, hide glue, varni3h, epoxy _9_ resin~, urea-formaldehyde resins, polyurethane resins. If the make coat i8 formed o the binder o~ this invention, the ~ize coat can be ~ormed of a conventional blnder material. Of cour~, both the make coat and size coat can be formed ~rom a binder or binder~ of the~present invention.
It i~ also contemplated that a single binder coat can be employed, r~ther than a make coat and a ~ize coat.
I-lowever~ it i.s preferred that both a make coat and size coat be ~Iti]ized.
The propertieq and ~erformance of coated abra~ives according to the invention are equal to or ~uperior to tho~e of coated abrasives having binders comprising phenolic re~in. Propertie~ such as Barcol hardne~s, temperature ~tability, binding ~trength, and durability under grinding condition3 of the binders of this invention meet or exceed tho~e propertie~ exhibited by binders comprising phenolic resin. The cured re~in of the abrasive product~ of this invention result~ in ~uperior thermal resistance to binder degradation which i9 brought about by high speed grinding. Coated abrasive product~
employing the re~inou~ hinder of this invention are amenable to water cooling.
In additiQn, the binder of the present invention doe~ not requ~re a solvent, thereby eliminating the need ~or ~olvent removal and pollution abatement problem~.
In the example~ which eollow, the ~ollowin~
abbreviations are used:
AA - Acrylic acid TMP~A - Trimethylol propane triacrylate TATHEIC - Triacrylate of tristhydroxy ethyl) i~ocyanurate NVP - N-vinyl-2-pyrrolidone IIMDI - Tri~Hexamethylene dii~ocyanate~
HMnI-T7 - Tris(Hexamethylene diisocyanate) havinq 7 acrylate groups -lo--HMDI-T9 - Tris(Hexamqthylene diisocyanate) having 9 acrylate yroups N-BUMA - N-butyl urethane methacrylate TEGDMA - Triethyleneglycol dimethacrylate TMDI - 2,2,~-trimethyl hexamethylene diisocyanate TMDI-Ir2 - 2,2,4-trlmethyl hexamethylene r3iisocyanate having 2 acrylate groups TMDI-T4 - 2,2,4-trimethyl hexamethylene diisocyanate having 4 acrylate groups IBOA - isobornyl acrylate CaC03 - calcium carbonate.
The ~ollowing examples are offered to aid in understanding the present invention and are not to be construed as limiting the scope thereof. All amounts are in parts by weight unless indicated otherwiseO
EXAMPLE l This example demonstrates how the superior su~face hardness of the resins or copolymers used to prepare binders of thi~ invention compares with that property of re~ins used to prepare binders of the prior art.
In each sample, the binder was prepared by introducing the ingredients into a veqsel equipped with a mechanical stirrer and stirring the ingredients until the mixture was homogeneous. The radiation-curable binder compo~ltions were knife coated onto a polyethylene terephthalate (PET) film at a 4 mil wet thickneqq and then irradiated at 200 Kev Witt1 a dose of 5 Mrad in a nitrogen atmosphere with a Model 250 Electrocurtain electron beam from Energy Science, Inc., Woburn, MA. The phenolic control samples were prepared by casting the phenolic compositions in a glass tray, followed by a 90 minute cure at 90C and a subsequent 12 hour cure at 100C~
25;3~7~i7 The samples prepared as described above were measured for hardnes~ by the ~arcol method (ASl'M
D-2533-75). The method involves applying a force to a needle point, ob~erving the penetration weiyht, and recording said weigllt as a percent Oe the weight required to penetrate gla~s. The results are shown in Table I, wllerein samples 1 and 2 describe binders of the present invention and sample~ 3 through 8, inclusive, describe binders of the prior art. ..Sample~s 3~5 were thermally . 10 cured, and sampl.e~ 6-~ were cured by radiation.
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~5370~:3 The filled and unfilled TMPTA/TATHEIC rQsin systems display hardne~s exceeding that oE any of the other radiation-cured re~ins or of the thermally cured phenolic resins.
This example compares thermal ~tability of the radiation cured resinou~ binders of this invention with the thermally cured F)henolic binders of the prior art. Thermal stability was mea.sured by loss of weight, in percent, a5 a function of temperature.
Samples were prepared according to the procedure described in Example 1. The samples were removed from the PET film and glass tray and were analyzed by thermal gravimetric analysis (~GA)~ The TGA measurements were conducted in an air atmo.sphere at a flow rate of 100 cc/minute to a maximum temperature of 450C on a P~rkin-Elmer Model TGS-2 thermal analyzer. The starting temperature o~ 20C was increased at a rate of 20C/min.
The re~ults are shown in Table II, wherein samples 9 through 11, inclusive, describe tlle cured binder of the pre~ent invention, and ~samples 12 through 16, inclusive, de~cribe binders of the prior art. Samples 12-14 were thermally cured and Sample~ 15-16 were cured by radiation.
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~15-The filled and unfilled TMPTA/TATIIEIC resin systems of the present invention have thermal stability equivalent to or superior to the other resin ~y~tems.
This example demonstrates grinding performance results of the coated abrasives of tl1is lnvention.
A racliation curable resinous binder composition was prepared by mixing 50 g of TMPTA with 50 g of TATI~IC.
Then lO0 g of quartz (Imsil ~-lO) was hlended with the resinous mixture until a homogeneous mix was obtained~ The same composition was usec1 for the make coat and size coat.
The make coat composition was applied to a 3 in. by 132 in.
standard single cotton belt abrasive backing using a knife coater to give a uniform make coat. Abrasive mineral (grade 50 aluminum oxide) was then applied over the make coat of the belts via electrostatic coating to give uniform surface coverage. An electrostatic coater useful for this step i9 manufactured by Peter Swabe Co., West Germany. The abrasive loaded coating was passed thtough a 250 Kev electrocurtain electron beam (Energy Sciences, Inc.) operating at l-lO Mrad of radiation as indicated in Table IIt. The line speed and current were controlled to give uniform dose.
The size coat was applied over the layer of abrasive mineral using a roll coater. Curing was completed under the same conditions as were used to cure the make coat. Several combinations of make coat and size coat were prepared according to this procedure. The samples thus prepared are summarized in Table III.
~2~37~7 -16~
TABLE III
Radiation ~) dosa~e (Mrad) Make Size Make Size 5 ~ ~ coat Mineral coat coatl coat2 ~ _ _ 17Cotton 41 15~ 92 5 10 (Y weight) 18Cotton 50 166 76 10 10 (Y weight) 1O19 Cottotl ~6 1~6 96 5 10 (X weight) 20Cotkon 50 157 138 10 10 (X weight) 1 Make coat was irradiated on the top as well as through the backing of the belt.
2 Size coat was irradiated on the top only.
The samples were tested on a single belt rohot grinder manufactured by Divine ~rothers Co.~ Inc.~ Utica~
~ew York. Each 3 inch by 132 inch belt was mounted upon a 55A durometer 14 inch diameter contact wheel which was driven at 6400 square feet per minute (SFPM) while a 1 inch by 10 inch reciprocating mild steel work piece (1018) was positioned parallel to the axis of the contact wheel. The work piece was forced against the belt using a constant load of 25 lbs. As used in this example and in those following, "initial cut wt." means weight of work piece ground away in the first minute of grinding, and "total cut wt." means weight of work piece ground away during the indicated grinding time. Tl~e results are shown in Table IV.
~25;371~
Table IV
Initial Total cut wt. 1 cut wt. 2 Time Sam~le _ ~ (g) (min) 17 ~0 939 16.5 18 71 103g 21.5 ~a 1219 2 89 1294 2~
1 ~eight of metal ground during first minute of grinding.
2 Weight of metal ground for time indicated.
3 Samples were ground using constant load of 25 pounds.
The resinous binders of the present invention performed successfully as radiation-cured coated abrasive binders~
Example 4 This example, like Example 3, demonstrates grinding performance result~ of the coated abrasive of this invention, the major difference being that 220 grade abrasive mineral was used.
A radiation curable resinous binder composition was prepared by mixing 50 g of TMPT~ with 50 g of TATI~EIC
until a homogenous mix was obtained. The same compostion was u~ed for the make coat and size coat. The make coat composition was applied to a 3 in. by 132 in. standard single cotton belt abrasive backing using a knife coater to yive a uniform make coat. The weight of the make coat was 10 g. Abrasive mineral (grade 220 aluminum oxide) was then applied over the make coat of the belts via electrostatic coating to give uniform surface coverage. The weight of the abrasive mineral was 61 g. The abrasive loaded coating was passed through a 250 ~ev Electrocurtain~ electron beam (Energy Sciences, Inc~) operating at 10 Mrad of radiation as indicated in Table III. The line speed and current were controlled to give uniform dose~
-3~3i3 -lU-The sample, which was de3ignatecl Sample 21, was coated by means of a two-roll coater with a size coat of an amount just sufficient to cover the abrasive mineral.
Curing was completed using electron beam radiation (10 Mrad).
The sample was testec1 as in Example 3, the only difference being that the load of the work piece against the belt was 10 lbs. The initial cut weight (1 min.) was 25 g:
the total cut wei~ht (20 min.) wa~ 279 9. A control\
employing phenolic resin ha(l an initial cut weight of 12 g and a total cut weight of 212 g~ The coated abrasives of the present invention was superior in grinding performance to a coated abrasive employing a phenolic binder.
Example 5 This example demonstrates that an optional thermal cure can be used to insure cure of any resinous material not exposed to radiation on account of shielding by abrasive granules.
A thermal catalyst was added to the make coat compo~ition to insure complete cure of any resinous material shaded by the abrasive mineral. The desired amount of catalyst was dissolved in an aliquot of solvent. The ratio of monomers, filler, and catalyst as shown in Table V were mixed until a homogeneous mixture was obtained.
Table V
Sample Monomer A Amount Monomer B Amount Filler Amount 221 TMPTA 50 TATHEIC 50 Quartz 100 231 TMPTA 50 TATHEIC 50 Quartz 100 peroxide catalyst was used in Samples 22 and 23 at a level of 0.05 parts hy weight.
The mixture, i e. the make coat, was applied to the backing, X weight cotton in each case, by a knife coater.
~253 d~i3 The abrasive mineral, aluminum oxide, was then electrostatically coated over the make coat to give a uniform surface coating. The resulting coat was then irradiated by pas~ing under a 250 Kev electrocurtain electron-beam oper~ting 80 as to give the de~ired do3e of radiation. The samples were then thermally post cured in a forced air oven at 10()C for 4 hours.
After the thermal post-cure the sample~ were coate~ by means oC a two-roll coater with a size coat of an amount just sufficient to cover the abrasive mineral~ The size coat of each sample was the same composition as that used for the make coat. Curing was completed using only electron-beam irradiation. Table VI shows coat weight and cure conditions for the abrasive samples.
TABLE VI
Make coat Mineral Dose make Thermal Dose size wt wt Mineral coat cure coat Sample (g) (g) ~ (Mrad) (hrs) (Mrad) 2022 47 139 50(AY) 2 4 10 23 4805 139.5 50(AY) 2 4 10 The samples were te~ted on a single belt robot grinder o~ Example 3. The test procedure was the 3ame a~
that used in Example 3.
The results of the robot grinding test are shown in Table VII. The controls were standard 3M~ phenolic RBC-GG abrasive belts manufactured by the Minnesota Mining and Manufacturing Company.
TABLE VII
Initial cut wt Total cut wt Time Sample ~ _ (g) (min) 3523 9~ 1577 30 Controll 90 -1432 30 .
1 Grade 50 ~AY) aluminum oxide, phenolic re~in binder.
5;3~ 3 -20~
The com~ination of a thermal cure with a radiation cure in~ures that the acrylate monomer~ will be polymerized and fully cured, even though they may be in a grit shadow during radiation expo~ure. Without a complete cure, the individual abrasive particles may be lost during grinding, thereby reducin~J the cutting performance.
Example 6 .
This example demonstrates continuous coating techniques which are similar to actual manufacturing procedures for a radiation curable binder. The ma~e and size resin coating composition~ were prepared by methods described in Example 3, except that calcium carbonate was also used as a filler. A thermal catalyst was included in the composition as previously described in Example 5.
Table VIII shows the ingredients and amounts thereof used for the make and size coat compositions. A pilot plant continuous coating line was set up to operate at 25 feet per minute web speed. The backing to be coated was treated in a continuous manner by knife coatin~ the make coat, electrostatically coating the abrasive mineral, and then irradiation with an electron beam in an air atmosphere.
The semi-finished web was given a thermal cure. Continuous treatment continued with roll coating a re~in ~ize coat on to the mineral side of the w~!b and then irradiating with an electron beam in a nitrogen atmosphere.
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~15-The filled and unfilled TMPTA/TATIIEIC resin systems of the present invention have thermal stability equivalent to or superior to the other resin ~y~tems.
This example demonstrates grinding performance results of the coated abrasives of tl1is lnvention.
A racliation curable resinous binder composition was prepared by mixing 50 g of TMPTA with 50 g of TATI~IC.
Then lO0 g of quartz (Imsil ~-lO) was hlended with the resinous mixture until a homogeneous mix was obtained~ The same composition was usec1 for the make coat and size coat.
The make coat composition was applied to a 3 in. by 132 in.
standard single cotton belt abrasive backing using a knife coater to give a uniform make coat. Abrasive mineral (grade 50 aluminum oxide) was then applied over the make coat of the belts via electrostatic coating to give uniform surface coverage. An electrostatic coater useful for this step i9 manufactured by Peter Swabe Co., West Germany. The abrasive loaded coating was passed thtough a 250 Kev electrocurtain electron beam (Energy Sciences, Inc.) operating at l-lO Mrad of radiation as indicated in Table IIt. The line speed and current were controlled to give uniform dose.
The size coat was applied over the layer of abrasive mineral using a roll coater. Curing was completed under the same conditions as were used to cure the make coat. Several combinations of make coat and size coat were prepared according to this procedure. The samples thus prepared are summarized in Table III.
~2~37~7 -16~
TABLE III
Radiation ~) dosa~e (Mrad) Make Size Make Size 5 ~ ~ coat Mineral coat coatl coat2 ~ _ _ 17Cotton 41 15~ 92 5 10 (Y weight) 18Cotton 50 166 76 10 10 (Y weight) 1O19 Cottotl ~6 1~6 96 5 10 (X weight) 20Cotkon 50 157 138 10 10 (X weight) 1 Make coat was irradiated on the top as well as through the backing of the belt.
2 Size coat was irradiated on the top only.
The samples were tested on a single belt rohot grinder manufactured by Divine ~rothers Co.~ Inc.~ Utica~
~ew York. Each 3 inch by 132 inch belt was mounted upon a 55A durometer 14 inch diameter contact wheel which was driven at 6400 square feet per minute (SFPM) while a 1 inch by 10 inch reciprocating mild steel work piece (1018) was positioned parallel to the axis of the contact wheel. The work piece was forced against the belt using a constant load of 25 lbs. As used in this example and in those following, "initial cut wt." means weight of work piece ground away in the first minute of grinding, and "total cut wt." means weight of work piece ground away during the indicated grinding time. Tl~e results are shown in Table IV.
~25;371~
Table IV
Initial Total cut wt. 1 cut wt. 2 Time Sam~le _ ~ (g) (min) 17 ~0 939 16.5 18 71 103g 21.5 ~a 1219 2 89 1294 2~
1 ~eight of metal ground during first minute of grinding.
2 Weight of metal ground for time indicated.
3 Samples were ground using constant load of 25 pounds.
The resinous binders of the present invention performed successfully as radiation-cured coated abrasive binders~
Example 4 This example, like Example 3, demonstrates grinding performance result~ of the coated abrasive of this invention, the major difference being that 220 grade abrasive mineral was used.
A radiation curable resinous binder composition was prepared by mixing 50 g of TMPT~ with 50 g of TATI~EIC
until a homogenous mix was obtained. The same compostion was u~ed for the make coat and size coat. The make coat composition was applied to a 3 in. by 132 in. standard single cotton belt abrasive backing using a knife coater to yive a uniform make coat. The weight of the make coat was 10 g. Abrasive mineral (grade 220 aluminum oxide) was then applied over the make coat of the belts via electrostatic coating to give uniform surface coverage. The weight of the abrasive mineral was 61 g. The abrasive loaded coating was passed through a 250 ~ev Electrocurtain~ electron beam (Energy Sciences, Inc~) operating at 10 Mrad of radiation as indicated in Table III. The line speed and current were controlled to give uniform dose~
-3~3i3 -lU-The sample, which was de3ignatecl Sample 21, was coated by means of a two-roll coater with a size coat of an amount just sufficient to cover the abrasive mineral.
Curing was completed using electron beam radiation (10 Mrad).
The sample was testec1 as in Example 3, the only difference being that the load of the work piece against the belt was 10 lbs. The initial cut weight (1 min.) was 25 g:
the total cut wei~ht (20 min.) wa~ 279 9. A control\
employing phenolic resin ha(l an initial cut weight of 12 g and a total cut weight of 212 g~ The coated abrasives of the present invention was superior in grinding performance to a coated abrasive employing a phenolic binder.
Example 5 This example demonstrates that an optional thermal cure can be used to insure cure of any resinous material not exposed to radiation on account of shielding by abrasive granules.
A thermal catalyst was added to the make coat compo~ition to insure complete cure of any resinous material shaded by the abrasive mineral. The desired amount of catalyst was dissolved in an aliquot of solvent. The ratio of monomers, filler, and catalyst as shown in Table V were mixed until a homogeneous mixture was obtained.
Table V
Sample Monomer A Amount Monomer B Amount Filler Amount 221 TMPTA 50 TATHEIC 50 Quartz 100 231 TMPTA 50 TATHEIC 50 Quartz 100 peroxide catalyst was used in Samples 22 and 23 at a level of 0.05 parts hy weight.
The mixture, i e. the make coat, was applied to the backing, X weight cotton in each case, by a knife coater.
~253 d~i3 The abrasive mineral, aluminum oxide, was then electrostatically coated over the make coat to give a uniform surface coating. The resulting coat was then irradiated by pas~ing under a 250 Kev electrocurtain electron-beam oper~ting 80 as to give the de~ired do3e of radiation. The samples were then thermally post cured in a forced air oven at 10()C for 4 hours.
After the thermal post-cure the sample~ were coate~ by means oC a two-roll coater with a size coat of an amount just sufficient to cover the abrasive mineral~ The size coat of each sample was the same composition as that used for the make coat. Curing was completed using only electron-beam irradiation. Table VI shows coat weight and cure conditions for the abrasive samples.
TABLE VI
Make coat Mineral Dose make Thermal Dose size wt wt Mineral coat cure coat Sample (g) (g) ~ (Mrad) (hrs) (Mrad) 2022 47 139 50(AY) 2 4 10 23 4805 139.5 50(AY) 2 4 10 The samples were te~ted on a single belt robot grinder o~ Example 3. The test procedure was the 3ame a~
that used in Example 3.
The results of the robot grinding test are shown in Table VII. The controls were standard 3M~ phenolic RBC-GG abrasive belts manufactured by the Minnesota Mining and Manufacturing Company.
TABLE VII
Initial cut wt Total cut wt Time Sample ~ _ (g) (min) 3523 9~ 1577 30 Controll 90 -1432 30 .
1 Grade 50 ~AY) aluminum oxide, phenolic re~in binder.
5;3~ 3 -20~
The com~ination of a thermal cure with a radiation cure in~ures that the acrylate monomer~ will be polymerized and fully cured, even though they may be in a grit shadow during radiation expo~ure. Without a complete cure, the individual abrasive particles may be lost during grinding, thereby reducin~J the cutting performance.
Example 6 .
This example demonstrates continuous coating techniques which are similar to actual manufacturing procedures for a radiation curable binder. The ma~e and size resin coating composition~ were prepared by methods described in Example 3, except that calcium carbonate was also used as a filler. A thermal catalyst was included in the composition as previously described in Example 5.
Table VIII shows the ingredients and amounts thereof used for the make and size coat compositions. A pilot plant continuous coating line was set up to operate at 25 feet per minute web speed. The backing to be coated was treated in a continuous manner by knife coatin~ the make coat, electrostatically coating the abrasive mineral, and then irradiation with an electron beam in an air atmosphere.
The semi-finished web was given a thermal cure. Continuous treatment continued with roll coating a re~in ~ize coat on to the mineral side of the w~!b and then irradiating with an electron beam in a nitrogen atmosphere.
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C u~ ~ ~ E
~rl O r~ ~ Q) al o nJ E ~c,l a c~ u c~
o o C~ C~
Table IX shows which composition was used for the make coat and which was used for the size coat in each ~ample.
5 ~ TABLE IX
Mineral Grade Make resin Size resirl 24 ~1203 50 (AY) Asame as make A123 50 (~Y) B~ame as make 26 A123 ~30 (AY) Bsame as make 27 A123 ~0 (AY) C D
28 A123 100 (AY) B~ame a~ make 29 A123 100 (AY) Bsame as make The make resin was knife coated onto the backing, X weight cotton in each ca~e, at a 4 mil wet thickness.
The abrasive mineral was then electro-statically coated over the make coat to give the desired coating weight for a given grade of mineral as shown in Table X. The make coat was irradiated at 225 Kev with a do~e of 3 Mrad under 20 ambient air. Sample.~ 24-26 and 2~-29 received thermal cure in an oven at 100C for ~ hour~ before being size coated.
The size coat was applied with a roll coater at a coating weight in accordance with Table X.
TABLE X
Mineral weightSize coat wt.
(g/sq. in.) (g~. in.) o.~ 0.14 0.24 0.097 100 0.19 0.064 The 3ize coat was cured at 225 Kev with a do~e of 3 Mrad under a nitrogen blanket.
Performance testing was conducted with a robot grinder according to test conditions previou~ly de~cribed in Example 3, with the exceptions that the load for grade 80 mineral was 15 lbs., and the load for grade 100 mineral 53~7~
was 15 lbs. The results are shown in Table XI.
ABLE XI
Initial Total Time cut wt. cut wt.
Sample(g) _ (~) (min) ~ Control 24 ~0 1,248 30 92 ~5 82 1,341 30 9 Controll (phenolic) 70 1,361 30 100 26 41 ~3 30 100 27 3~ 628 30 75 Control2 (phenolic) 40 843 30 100 Control3 (phenolic) 30 507 30 100 _ _ 1 Grade 50 (~Y) A1203 on 3M~ RBC-GG abrasive belt having phenolic binder.
2 Grade 80 (AY) A1203 on 3M RBC-GG abrasive belt having phenolic binder.
3 Grade 100 (AY) A1203 on 3M~ RBC~GG abrasive belt having phenolic bind~r.
The abrasive ~heets of this invention exhibited grinding properties equivalent or superior to those of the phenolic controls and the prior art (sample 27).
- Example 7 This example demonstrates additional novel hinder resin ~ormulations. The radiation curable resinous compositions were prepared by mixing the monomers and fillers as shown in Table XII. A thermal cataly~t was included in two of the resinous compositions. The make ~2:53~
2aS-resin composition was coated onto the backing, X weight cotton in each case, by means oE a knife coater to a 4 mil wet thickness. The abrasive mineral, A1203 (grade 100 (AY) in each case), was applied over the`make coat by means of 5 electrostatic coating. The mineral coated resin was electron beam cured at 240 Kev with a dose of 3 Mrad in air. This was followed by application by roll coater of size resin composition (0.064 g/sq. in.) and cure thereof at 240 Kev with a dose of 3 Mrad. Samples 30 and 32 each 10 received a thermal post cure at 100C for 4 hours.
Table XII
SampleMonomer AAmountMonomer AAmount Filler Amount _ _ 301 E~DI-T7 25TMPTA 25 CaC0350 1531 HMDI-T7 25TMPTA 25 CaC0350 321 HMDI-T9 25l~PTA 25 CaC0350 33 HMDI-T9 25TMPTA 25 CaC0350 ,~, 1 Benzoyl peroxide catalyst was used in Samples 30 and 32 at a level of 0.02 parts by weight.
The robot grinder was employed to measure performance of these samples as in Example 3 with a constant load of 15 lbs. The performance results are shown 25in Table XIII.
TABLE XIII
Thermal post Initial cut wt Total cut wt Time 30 Sam~le cure (g) (g) __ (min) Controll (phenolic) 35 585 30 Yes 36 681 30 31 No 30 640 30 32 Yes 39 644 30 33 No 31 647 30 .
Grade lOO~AY) A1203 on 3M~ RBC-GG abrasive belt having - phenolic binder.
. .
~L~53~
The abrasive sheet of this invention exhibited grinding properties equivalent to or superior to those of the phenolic control.
Example 8 This example demonstrates the performance of the coated ahrasive on fiber discs. The radiation curable coating composition was prepared according to the conditions for composition B of Example 6. The make coat compositi-on was applied by paint brush to a 30 mil vulcanized rag pulp fiber disc (e.g. a 3M~ type C disc.) having a diameter of 7 inches. The total weight of the make coat was 4 g. The abrasive mineral, 15 g Grade 50 Cubitron~ abrasive (see U.S. Patent 4,314,827), was applied over the make coat by electrostatic coating. The coated sample was irradiated with electron beam at 250 Kev with a 5 Mrad dose in air.
The size coat composition was applied over the abrasive coat with a paint brush at a weight of 9 g. The size coat was cured with electron beam at 250 Kev with a 5 Mrad dose in nitrogen~ A subsequent thermal post cure (~
hours at 100C) was then conducted. Performance testing was conducted by a 3M~ standard disc sanding test which consisted of an edge and flat test. The edge test involved placing the work piece in proximity to the outer periphery of the disc at the prescribed angle at the prescribed load for the prescribed time. The flat test involved placing the work piece at a distance of about 1 inch inward from the outer periphery of the disc at the prescribed angle at the prescribed load for the prescribed time. The edge test was conducted at an angle of 18~ under a constant load (2896 g) for 8 minutes while the flat was conducted at an angle of 7 under a constant load (2670 g) for 8 minutes.
The work piece was mild steel. The results are shown in Table XIV.
i376~
, ~ ~
' TABLE XIV
-Total cut wt. (g) Sample Edge F _ Controll 48 61 1 3M~ type C disk having a phenolic binder.
The abrasive sheets of this invention exhibited grinding performance equivalent to or superior to those of the phenolic control.
Example 9 This example demonstrates abrasive construction usable under wet condition~ made from a radiation curable resinous binderO The radiation curable resin used for the make and size coâting compositions was prepared by stirring the ingredients with a mechanical mixer. The ingredients and amounts thereof are shown in Table XV.
TABLE XV
`
Sample ~ Make Resin Size Resin 36 A wt paper 70% HMDI-T7, 70% TMDI-T2, 30% N-BUMA 30% TMPTA
37 A wt paper 70% HMDI-T7, 70% TMDI-T2, 30% N-BUMA 30% TMPTA
33 A wt paper 70% HMDI-T7, 70% TMDI-T4, 30% N-BUMA 30% TEGDMA
39 A wt paper 70% HMDI-T7, 70% TMDI-T4, 30% N-BUMA 30% TEGDMA
A wt paper 70% TMDI-T2, 70% T~IDI-T2, 30% TMPTD 30% TMPTA
41 1.3 mil PET 70% HMDI-T7, 70% TMDI-T2, 30% N-BUMA 30% TMPTA
i37~
The make coat composition was applied by a knife coater to give a coating tllickness of 1 mil. ~brasive mineral, SiC, 220 grade, was applLod over the make coat by electrostatic coating at ~ coating density of 0.081 g/sq. in. The coat was cured hy irradiating with electron beam at 235 Kev with a 3 Mrad dose in an air environment~
The size coat cornposition was appliec3 by means of a roll coater to give a coating weight of 0.029 9/8~. in.
The coat was cured by irra~;liating with electron beam at 2()0 Kev with a 3 Mrad dose in a nitrogen environment.
The samples were tested using a modified ~Schieffer disc tester. Four-inch diameter discs were die cut and installed in a testin~ machine for evaluation o~
abrasiveness~ The testing machine consisted of a mechanically driven 4-inch diameter rotating steel backing plate upon which the abrasive coated samples were applied.
The rotating abrasive samples were forced with a constant load of 10 pounds against a stationary surface of a polymethylmethacrylate (PMMA) disc. The te~t consi~ted of a 500 revolution cycle per test with a continuous wetting of the PMMA disc. Reported results, set forth in Table XVI
consi~t of an average of four runs for each sample tested.
TABLE XVI
Average cut wt.
(9) % Control Controll 2.02 100 36 1.83 91 37 1.95 97 38 1.88 93 39 1.88 93 ~0 1.89 94 41 1.~7 93 ,........ _ 1 3M~ grade 220 WET or DRY~ Tri-M-ite paper A wt. W2.
a~2~i;370~
-2~-E~am~ 10 This example compare~ the binder formulation of the present invention with that oE binders described in the prior art. The make coat compo~ition in each sample was knife coate~l onto the backing at a 4 mil wet thickness.
The coatinq compositions i~ shown in Table XVII.
37~63 .
C ~ O o o E
~5 ~1 O C~ O O
~1 U C~ C,) C~
.,., a 0 ç~
EOi ~ I I .
~ ~ .
~J
Ei .¢
O ~
C
~ O O
O -1 ~ I I
E
~:
H U
X E~ ~
O ~':1 E-l I I
~4~ C : I I
~Q ~ H~1 ~: cl ~) OL~
E. ~ ~ ~I
:a ~ ~ .
O T~ E-C ~ Cl- E~
O
~: æ æ E-l E~
C U~ 'O ~ U~ ' O ~ ` ~I
~ ~ JJ ~ r-aJ ~ ~ fa s E~
Ej _I X ~ L) '~S I
O ~ O ~ aJ E
O t.~ a) t) ~ ~ 5' . Q~
f`~ ~ In ~a ~ ~ ~ ~
, ................................ .
-30~ 3P7~
In each sample the backing waR X weight cotton and th'e abra~ive mineral wa3 grade 100 (AY) aluminum oxide.
The abra~ive mineral was applied by electrostatic coating at a weight of 0,19 g/sq~ in. The ~amples were irradiated 5 at 240 ~ev with 5 Mrad in air with the abrasive mineral ~ide up.
The size coat composition in each sample wa~
applied Witil a roll coater at a coating weiyht of 0.064 g/s~. in. The .~ample.s were cured by irradiation with electron beam at 240 Kev with a dose of 5 Mrad in a nitrogen environment. The si~e coat compositons for sample 42 contained 31 parts Celrad~ 3600 acrylate epoxy, 9 part.s I~OA, 6 parts TMPT~, 9 parts NVP, ana 25 parts CaC03. The .~i7,e co~t compo.sition.~ Eor samples 43, 44, and 45 were the same a~ those of the make coat compositions of the~e samples, as shown in Tahle XVII.
After the ~iæe coat had been cured, the ~amples were irra-liate(l throu~h the back side at 240 ~ev wi~h a 5 Mrad dose. Per~ormance te~ting was done on single belt robot grinder a3 previously described in Example 3 with a load of 15 lbs. The results of the performance test are ~hown in Table XVIII.
, TABLE XVIII
2~
Initial cut Total cut Time , Sample wt. (g)wt. (~) (min) 4~ 35 659 30 Sample~ 44 and 45, the samples of the pre~ent invention, exhihit grinding properties superior to tho3e of the prior art ~samples 42 and 43).
~2~
-3.l-Various moclifications and alterations o~ this invention will become apparent to those skilled in the art wihout ~epartlng ~rom the ~cope and ~plrlt o~ this invention, and it ~llould he uncler~too(l that this inventlon i.~ not to he unduly limited to the illustrative emhodiments set ~orth herein.
O ~E~ ~ O ~ O o c.
C ~ Q.
o ~: ~ U ~ U
E~ ~: ~ O o ul o o C
~D ~n O
.
C ~ 3 .
,~ ~ ~
v a~ 1~ 0 C~ ~ ~ ~
C u~ ~ ~ E
~rl O r~ ~ Q) al o nJ E ~c,l a c~ u c~
o o C~ C~
Table IX shows which composition was used for the make coat and which was used for the size coat in each ~ample.
5 ~ TABLE IX
Mineral Grade Make resin Size resirl 24 ~1203 50 (AY) Asame as make A123 50 (~Y) B~ame as make 26 A123 ~30 (AY) Bsame as make 27 A123 ~0 (AY) C D
28 A123 100 (AY) B~ame a~ make 29 A123 100 (AY) Bsame as make The make resin was knife coated onto the backing, X weight cotton in each ca~e, at a 4 mil wet thickness.
The abrasive mineral was then electro-statically coated over the make coat to give the desired coating weight for a given grade of mineral as shown in Table X. The make coat was irradiated at 225 Kev with a do~e of 3 Mrad under 20 ambient air. Sample.~ 24-26 and 2~-29 received thermal cure in an oven at 100C for ~ hour~ before being size coated.
The size coat was applied with a roll coater at a coating weight in accordance with Table X.
TABLE X
Mineral weightSize coat wt.
(g/sq. in.) (g~. in.) o.~ 0.14 0.24 0.097 100 0.19 0.064 The 3ize coat was cured at 225 Kev with a do~e of 3 Mrad under a nitrogen blanket.
Performance testing was conducted with a robot grinder according to test conditions previou~ly de~cribed in Example 3, with the exceptions that the load for grade 80 mineral was 15 lbs., and the load for grade 100 mineral 53~7~
was 15 lbs. The results are shown in Table XI.
ABLE XI
Initial Total Time cut wt. cut wt.
Sample(g) _ (~) (min) ~ Control 24 ~0 1,248 30 92 ~5 82 1,341 30 9 Controll (phenolic) 70 1,361 30 100 26 41 ~3 30 100 27 3~ 628 30 75 Control2 (phenolic) 40 843 30 100 Control3 (phenolic) 30 507 30 100 _ _ 1 Grade 50 (~Y) A1203 on 3M~ RBC-GG abrasive belt having phenolic binder.
2 Grade 80 (AY) A1203 on 3M RBC-GG abrasive belt having phenolic binder.
3 Grade 100 (AY) A1203 on 3M~ RBC~GG abrasive belt having phenolic bind~r.
The abrasive ~heets of this invention exhibited grinding properties equivalent or superior to those of the phenolic controls and the prior art (sample 27).
- Example 7 This example demonstrates additional novel hinder resin ~ormulations. The radiation curable resinous compositions were prepared by mixing the monomers and fillers as shown in Table XII. A thermal cataly~t was included in two of the resinous compositions. The make ~2:53~
2aS-resin composition was coated onto the backing, X weight cotton in each case, by means oE a knife coater to a 4 mil wet thickness. The abrasive mineral, A1203 (grade 100 (AY) in each case), was applied over the`make coat by means of 5 electrostatic coating. The mineral coated resin was electron beam cured at 240 Kev with a dose of 3 Mrad in air. This was followed by application by roll coater of size resin composition (0.064 g/sq. in.) and cure thereof at 240 Kev with a dose of 3 Mrad. Samples 30 and 32 each 10 received a thermal post cure at 100C for 4 hours.
Table XII
SampleMonomer AAmountMonomer AAmount Filler Amount _ _ 301 E~DI-T7 25TMPTA 25 CaC0350 1531 HMDI-T7 25TMPTA 25 CaC0350 321 HMDI-T9 25l~PTA 25 CaC0350 33 HMDI-T9 25TMPTA 25 CaC0350 ,~, 1 Benzoyl peroxide catalyst was used in Samples 30 and 32 at a level of 0.02 parts by weight.
The robot grinder was employed to measure performance of these samples as in Example 3 with a constant load of 15 lbs. The performance results are shown 25in Table XIII.
TABLE XIII
Thermal post Initial cut wt Total cut wt Time 30 Sam~le cure (g) (g) __ (min) Controll (phenolic) 35 585 30 Yes 36 681 30 31 No 30 640 30 32 Yes 39 644 30 33 No 31 647 30 .
Grade lOO~AY) A1203 on 3M~ RBC-GG abrasive belt having - phenolic binder.
. .
~L~53~
The abrasive sheet of this invention exhibited grinding properties equivalent to or superior to those of the phenolic control.
Example 8 This example demonstrates the performance of the coated ahrasive on fiber discs. The radiation curable coating composition was prepared according to the conditions for composition B of Example 6. The make coat compositi-on was applied by paint brush to a 30 mil vulcanized rag pulp fiber disc (e.g. a 3M~ type C disc.) having a diameter of 7 inches. The total weight of the make coat was 4 g. The abrasive mineral, 15 g Grade 50 Cubitron~ abrasive (see U.S. Patent 4,314,827), was applied over the make coat by electrostatic coating. The coated sample was irradiated with electron beam at 250 Kev with a 5 Mrad dose in air.
The size coat composition was applied over the abrasive coat with a paint brush at a weight of 9 g. The size coat was cured with electron beam at 250 Kev with a 5 Mrad dose in nitrogen~ A subsequent thermal post cure (~
hours at 100C) was then conducted. Performance testing was conducted by a 3M~ standard disc sanding test which consisted of an edge and flat test. The edge test involved placing the work piece in proximity to the outer periphery of the disc at the prescribed angle at the prescribed load for the prescribed time. The flat test involved placing the work piece at a distance of about 1 inch inward from the outer periphery of the disc at the prescribed angle at the prescribed load for the prescribed time. The edge test was conducted at an angle of 18~ under a constant load (2896 g) for 8 minutes while the flat was conducted at an angle of 7 under a constant load (2670 g) for 8 minutes.
The work piece was mild steel. The results are shown in Table XIV.
i376~
, ~ ~
' TABLE XIV
-Total cut wt. (g) Sample Edge F _ Controll 48 61 1 3M~ type C disk having a phenolic binder.
The abrasive sheets of this invention exhibited grinding performance equivalent to or superior to those of the phenolic control.
Example 9 This example demonstrates abrasive construction usable under wet condition~ made from a radiation curable resinous binderO The radiation curable resin used for the make and size coâting compositions was prepared by stirring the ingredients with a mechanical mixer. The ingredients and amounts thereof are shown in Table XV.
TABLE XV
`
Sample ~ Make Resin Size Resin 36 A wt paper 70% HMDI-T7, 70% TMDI-T2, 30% N-BUMA 30% TMPTA
37 A wt paper 70% HMDI-T7, 70% TMDI-T2, 30% N-BUMA 30% TMPTA
33 A wt paper 70% HMDI-T7, 70% TMDI-T4, 30% N-BUMA 30% TEGDMA
39 A wt paper 70% HMDI-T7, 70% TMDI-T4, 30% N-BUMA 30% TEGDMA
A wt paper 70% TMDI-T2, 70% T~IDI-T2, 30% TMPTD 30% TMPTA
41 1.3 mil PET 70% HMDI-T7, 70% TMDI-T2, 30% N-BUMA 30% TMPTA
i37~
The make coat composition was applied by a knife coater to give a coating tllickness of 1 mil. ~brasive mineral, SiC, 220 grade, was applLod over the make coat by electrostatic coating at ~ coating density of 0.081 g/sq. in. The coat was cured hy irradiating with electron beam at 235 Kev with a 3 Mrad dose in an air environment~
The size coat cornposition was appliec3 by means of a roll coater to give a coating weight of 0.029 9/8~. in.
The coat was cured by irra~;liating with electron beam at 2()0 Kev with a 3 Mrad dose in a nitrogen environment.
The samples were tested using a modified ~Schieffer disc tester. Four-inch diameter discs were die cut and installed in a testin~ machine for evaluation o~
abrasiveness~ The testing machine consisted of a mechanically driven 4-inch diameter rotating steel backing plate upon which the abrasive coated samples were applied.
The rotating abrasive samples were forced with a constant load of 10 pounds against a stationary surface of a polymethylmethacrylate (PMMA) disc. The te~t consi~ted of a 500 revolution cycle per test with a continuous wetting of the PMMA disc. Reported results, set forth in Table XVI
consi~t of an average of four runs for each sample tested.
TABLE XVI
Average cut wt.
(9) % Control Controll 2.02 100 36 1.83 91 37 1.95 97 38 1.88 93 39 1.88 93 ~0 1.89 94 41 1.~7 93 ,........ _ 1 3M~ grade 220 WET or DRY~ Tri-M-ite paper A wt. W2.
a~2~i;370~
-2~-E~am~ 10 This example compare~ the binder formulation of the present invention with that oE binders described in the prior art. The make coat compo~ition in each sample was knife coate~l onto the backing at a 4 mil wet thickness.
The coatinq compositions i~ shown in Table XVII.
37~63 .
C ~ O o o E
~5 ~1 O C~ O O
~1 U C~ C,) C~
.,., a 0 ç~
EOi ~ I I .
~ ~ .
~J
Ei .¢
O ~
C
~ O O
O -1 ~ I I
E
~:
H U
X E~ ~
O ~':1 E-l I I
~4~ C : I I
~Q ~ H~1 ~: cl ~) OL~
E. ~ ~ ~I
:a ~ ~ .
O T~ E-C ~ Cl- E~
O
~: æ æ E-l E~
C U~ 'O ~ U~ ' O ~ ` ~I
~ ~ JJ ~ r-aJ ~ ~ fa s E~
Ej _I X ~ L) '~S I
O ~ O ~ aJ E
O t.~ a) t) ~ ~ 5' . Q~
f`~ ~ In ~a ~ ~ ~ ~
, ................................ .
-30~ 3P7~
In each sample the backing waR X weight cotton and th'e abra~ive mineral wa3 grade 100 (AY) aluminum oxide.
The abra~ive mineral was applied by electrostatic coating at a weight of 0,19 g/sq~ in. The ~amples were irradiated 5 at 240 ~ev with 5 Mrad in air with the abrasive mineral ~ide up.
The size coat composition in each sample wa~
applied Witil a roll coater at a coating weiyht of 0.064 g/s~. in. The .~ample.s were cured by irradiation with electron beam at 240 Kev with a dose of 5 Mrad in a nitrogen environment. The si~e coat compositons for sample 42 contained 31 parts Celrad~ 3600 acrylate epoxy, 9 part.s I~OA, 6 parts TMPT~, 9 parts NVP, ana 25 parts CaC03. The .~i7,e co~t compo.sition.~ Eor samples 43, 44, and 45 were the same a~ those of the make coat compositions of the~e samples, as shown in Tahle XVII.
After the ~iæe coat had been cured, the ~amples were irra-liate(l throu~h the back side at 240 ~ev wi~h a 5 Mrad dose. Per~ormance te~ting was done on single belt robot grinder a3 previously described in Example 3 with a load of 15 lbs. The results of the performance test are ~hown in Table XVIII.
, TABLE XVIII
2~
Initial cut Total cut Time , Sample wt. (g)wt. (~) (min) 4~ 35 659 30 Sample~ 44 and 45, the samples of the pre~ent invention, exhihit grinding properties superior to tho3e of the prior art ~samples 42 and 43).
~2~
-3.l-Various moclifications and alterations o~ this invention will become apparent to those skilled in the art wihout ~epartlng ~rom the ~cope and ~plrlt o~ this invention, and it ~llould he uncler~too(l that this inventlon i.~ not to he unduly limited to the illustrative emhodiments set ~orth herein.
Claims (19)
1. A coated abrasive product comprising abrasive granules which are supported on and adherently bonded to at least one major surface of a backing sheet by a make coat of a first resinous hinder material and a size coat of a second resinous binder material, at least one of said first resinous binder material or said second resinous binder material comprising a copolymer formed from a mixture comprising (1) at least one monomer selected from the group consisting of isocyanurate derivatives having at least one terminal or pendant acrylate group and isocyanate derivatives having at least one terminal or pendant acrylate group, and (2) at least one aliphatic or cycloaliphatic monomer having at least one terminal or pendant acrylate group.
2. The abrasive product of claim 1 wherein the ratio of isocyanurate or isocyanurate derivative monomer to the aliphatic or cycloaliphatic monomer having at least one terminal or pendant acrylate group ranges from about 1:3 to 3:1.
3. The abrasive product of claim 1 wherein the ratio of isocyanurate or isocyanate derivative monomer to the aliphatic or cycloaliphatic monomer having at least one terminal or pendant acrylate group ranges from about 1:1.5 to about 1.5:1.
4. The abrasive product of claim 1 wherein said isocyanurate derivative monomer is represented by the formula:
where each R can be the same or different and represents a group containing at least one terminal or pendant acrylate or methacrylate group.
where each R can be the same or different and represents a group containing at least one terminal or pendant acrylate or methacrylate group.
5. The abrasive product of claim 4 where R is selected from the group consisting of R1 represents a divalent alkylene group, R2 represents -H or -CH3, R3 represents -H or -CH3, R4 represents -H, an alkyl group, or an arylalkyl group, R5 represents -H, an alkyl group, or an arylalkyl group, R6 represents -H divalent alkylene group, R7 represents a covalent bond or a divalent alkylene group, a represents an integer from 1 to 3, inclusive, b represents 0 or 1, c represents 0 or 1, and a + b + c = 3.
6. The abrasive product of claim 1 wherein said isocyanate derivative monomer is represented by the formula:
where A represent a divalent alkylene group, each R8 can be the same or different and represents R2 represents -H or -CH3, R3 represents -H or -CH3, R4 represents -H, an alkyl group, or an arylalkyl group, R5 represents -H, an alkyl group, or an arylalkyl group, R6 represents a divalent alkylene group, R7 represents a covalent bond or a divalent alkylene group, a represents an integer from 1 to 3, inclusive, b represents 0 or 1, c represents 0 or 1; and a + b + c = 3.
where A represent a divalent alkylene group, each R8 can be the same or different and represents R2 represents -H or -CH3, R3 represents -H or -CH3, R4 represents -H, an alkyl group, or an arylalkyl group, R5 represents -H, an alkyl group, or an arylalkyl group, R6 represents a divalent alkylene group, R7 represents a covalent bond or a divalent alkylene group, a represents an integer from 1 to 3, inclusive, b represents 0 or 1, c represents 0 or 1; and a + b + c = 3.
7. The abrasive product of claim 1 wherein said aliphatic or cycloaliphatic monomer having at least one acrylic group is represented by the formula:
where each R9 can be the same or different, and R9 represents -H or , R10 represents an alkyl group, R11 represents -H or -CH3, R12 represents -H or -CH3, and R13 represents a covalent bond or a divalent alkylene group, at one of said R9 not being -H.
where each R9 can be the same or different, and R9 represents -H or , R10 represents an alkyl group, R11 represents -H or -CH3, R12 represents -H or -CH3, and R13 represents a covalent bond or a divalent alkylene group, at one of said R9 not being -H.
8. The abrasive product of claim 1 wherein said abrasive granules are selected from the group consisting of flint, garnet, aluminum oxide, alumina:zirconia, diamond, and silicon carbide.
9. The abrasive product of claim 1 wherein said first resinous binder is said copolymer and said second resinous binder is selected from the group consisting of glue, varnish, epoxy resin, phenolic resin and polyurethane.
10. The abrasive product of claim 1 wherein said first resinous binder is selected from the group consisting of glue, varnish, epoxy resin, phenolic resin and polyurethane and said second resinous binder is said copolymer.
11. The abrasive product of claim 1 wherein said hacking sheet is formed of paper, film, fiber, or woven cloth.
12. The abrasive product of claim 1 wherein said mixture further comprises a thermal curing catalyst.
13. Method of preparing the coated abrasive product of claim 1 comprising the steps of:
(1) providing a backing sheet, (2) applying said make coat to said backing sheet, (3) applying abrasive granules over said make coat, (4) at least partially curing said make coat, (5) applying said size coat over said make coat and said abrasive granules, and (6) completely curing said make and said size coat.
(1) providing a backing sheet, (2) applying said make coat to said backing sheet, (3) applying abrasive granules over said make coat, (4) at least partially curing said make coat, (5) applying said size coat over said make coat and said abrasive granules, and (6) completely curing said make and said size coat.
14. The method of claim 13 wherein at least one of said curing steps is conducted by means of electromagnetic radiation.
15. The method of claim 14 wherein said electromagnetic radiation is ultraviolet radiation.
16. The method of claim 14 wherein said electromagnetic radiation is ionizing radiation.
17. The method of claim 16 wherein said ionizing radiation is electron beam radiation.
18. The method of claim 13 further including the step of post-curing said cured coated abrasive product by means of thermal energy.
19. A coated abrasive product comprising abrasive granules which are supported on and adherently bonded to at least one major surface of a backing sheet by a resinous binder material, said resinous binder material comprising a copolymer formed from a mixture comprising (1) at least one monomer selected from the group consisting of isocyanurate derivatives having at least one terminal or pendant acrylate group and isocyanate derivatives having at least one terminal or pendant acrylate group, and (2) at least one aliphatic or cycloaliphatic monomer having at least one terminal or pendant acrylate qroup.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/763,331 US4652274A (en) | 1985-08-07 | 1985-08-07 | Coated abrasive product having radiation curable binder |
| US763,331 | 1991-09-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1253700A true CA1253700A (en) | 1989-05-09 |
Family
ID=25067524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000510630A Expired CA1253700A (en) | 1985-08-07 | 1986-06-02 | Coated abrasive product having radiation curable binder |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4652274A (en) |
| EP (1) | EP0213738B1 (en) |
| JP (1) | JPH0796624B2 (en) |
| KR (1) | KR940003574B1 (en) |
| AT (1) | ATE53525T1 (en) |
| CA (1) | CA1253700A (en) |
| DE (1) | DE3671852D1 (en) |
| FI (1) | FI80895C (en) |
Families Citing this family (415)
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| US4889792A (en) * | 1987-12-09 | 1989-12-26 | Minnesota Mining And Manufacturing Company | Ternary photoinitiator system for addition polymerization |
| US4927431A (en) * | 1988-09-08 | 1990-05-22 | Minnesota Mining And Manufacturing Company | Binder for coated abrasives |
| US5055113A (en) * | 1988-11-23 | 1991-10-08 | Minnesota Mining And Manufacturing Company | Abrasive product having binder comprising an aminoplast resin |
| US4903440A (en) * | 1988-11-23 | 1990-02-27 | Minnesota Mining And Manufacturing Company | Abrasive product having binder comprising an aminoplast resin |
| US4992082A (en) * | 1989-01-12 | 1991-02-12 | Ford Motor Company | Method of toughening diamond coated tools |
| US4933373A (en) * | 1989-04-06 | 1990-06-12 | Minnesota Mining And Manufacturing Company | Abrasive wheels |
| US5103598A (en) * | 1989-04-28 | 1992-04-14 | Norton Company | Coated abrasive material containing abrasive filaments |
| US5007943A (en) * | 1989-11-03 | 1991-04-16 | Norton Company | Sol-gel process alumina abrasive grain blends in coated abrasive material |
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| CA2083868A1 (en) * | 1990-11-14 | 1993-06-12 | Chong Soo Lee | Coated abrasive having a coating of an epoxy resin coatable from water |
| CA2054554A1 (en) * | 1990-11-14 | 1992-05-15 | Chong Soo Lee | Coated abrasive having an overcoating of an epoxy resin coatable from water and a grinding aid |
| CA2058700C (en) * | 1991-01-08 | 2000-04-04 | David E. Williams | Polymer backed material with non-slip surface |
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| DE4133191A1 (en) * | 1991-10-07 | 1993-04-08 | Basf Ag | ABRASIVE |
| US5183479A (en) * | 1991-11-01 | 1993-02-02 | Gemtex Company Limited | Abrasive disks and method of making |
| US5316812A (en) * | 1991-12-20 | 1994-05-31 | Minnesota Mining And Manufacturing Company | Coated abrasive backing |
| US6406577B1 (en) | 1991-12-20 | 2002-06-18 | 3M Innovative Properties Company | Method of making abrasive belt with an endless, seamless backing |
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| DE69326774T2 (en) * | 1993-06-02 | 2000-06-21 | Dainippon Printing Co Ltd | GRINDING BELT AND METHOD FOR THE PRODUCTION THEREOF |
| US5744557A (en) * | 1993-06-16 | 1998-04-28 | Minnesota Mining And Manufacturing Company | Energy-curable cyanate/ethylenically unsaturated compositions |
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| AU683688B2 (en) * | 1993-10-19 | 1997-11-20 | Minnesota Mining And Manufacturing Company | Abrasive articles comprising a make coat transferred by lamination |
| US5632668A (en) * | 1993-10-29 | 1997-05-27 | Minnesota Mining And Manufacturing Company | Method for the polishing and finishing of optical lenses |
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| CA2134156A1 (en) * | 1993-11-22 | 1995-05-23 | Thomas P. Klun | Coatable compositions, abrasive articles made therefrom, and methods of making and using same |
| US5391210A (en) * | 1993-12-16 | 1995-02-21 | Minnesota Mining And Manufacturing Company | Abrasive article |
| JPH07179622A (en) * | 1993-12-22 | 1995-07-18 | Tipton Mfg Corp | Barrel-polishing stone containing compound and its production |
| US5785784A (en) * | 1994-01-13 | 1998-07-28 | Minnesota Mining And Manufacturing Company | Abrasive articles method of making same and abrading apparatus |
| DE69511068T2 (en) * | 1994-02-22 | 2000-04-06 | Minnesota Mining & Mfg | ABRASIVE ARTICLE, METHOD FOR PRODUCING THE SAME, AND METHOD FOR APPLYING THE SAME IN FINISHING |
| AU1735295A (en) * | 1994-02-22 | 1995-09-04 | Minnesota Mining And Manufacturing Company | Method for making an endless coated abrasive article and the product thereof |
| US5591527A (en) * | 1994-11-02 | 1997-01-07 | Minnesota Mining And Manufacturing Company | Optical security articles and methods for making same |
| US5571297A (en) * | 1995-06-06 | 1996-11-05 | Norton Company | Dual-cure binder system |
| US5578096A (en) * | 1995-08-10 | 1996-11-26 | Minnesota Mining And Manufacturing Company | Method for making a spliceless coated abrasive belt and the product thereof |
| US5958794A (en) * | 1995-09-22 | 1999-09-28 | Minnesota Mining And Manufacturing Company | Method of modifying an exposed surface of a semiconductor wafer |
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| USH1678H (en) * | 1995-11-03 | 1997-09-02 | Minnesota Mining And Manufacturing Company | Abrasive article including a polyvinyl carbamate coating, and methods for making and using the same |
| US5624303A (en) * | 1996-01-22 | 1997-04-29 | Micron Technology, Inc. | Polishing pad and a method for making a polishing pad with covalently bonded particles |
| KR19990087232A (en) * | 1996-02-26 | 1999-12-15 | 볼스트 스테판 엘. | Radiation curable supersize |
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| US5882796A (en) * | 1996-04-01 | 1999-03-16 | Minnesota Mining And Manufacturing Company | Bonded structured retroreflective sheeting |
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| CH507781A (en) * | 1966-09-01 | 1971-05-31 | Esterol Ag | Grinding wheels contng polyester binder and opt glass - fibres |
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| US3932401A (en) * | 1974-01-31 | 1976-01-13 | Minnesota Mining And Manufacturing Company | Mixed acrylic acid/methacrylic acid esters of tris (hydroxyalkyl) isocyanurates |
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| US4126428A (en) * | 1976-01-14 | 1978-11-21 | Minnesota Mining And Manufacturing Company | Coated abrasive containing isocyanurate binder and method of producing same |
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| CA1112243A (en) * | 1978-09-08 | 1981-11-10 | Manfred Bock | Process for the preparation of polyisocyanates containing isocyanurate groups and the use thereof |
| DE2853761B1 (en) * | 1978-12-13 | 1980-03-27 | Hoechst Ag | Process for the production of abrasives |
| US4345545A (en) * | 1980-07-28 | 1982-08-24 | The Carborundum Company | Apparatus for electron curing of resin coated webs |
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| DD160038A1 (en) * | 1981-06-30 | 1983-04-27 | Amlong Uwe Jens | PROCESS FOR GENERATING INTERSIVE REACTION BY ELECTROMAGNETIC ENERGY |
| DE3318147A1 (en) * | 1983-05-18 | 1984-11-22 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF COMPOUNDS HAVING ISOCYANURATE GROUPS AND OLEFINIC DOUBLE BINDINGS, THE COMPOUNDS AVAILABLE ACCORDING TO THIS METHOD AND THEIR USE AS BINDERS OR. BINDING COMPONENT IN COATING AGENTS |
-
1985
- 1985-08-07 US US06/763,331 patent/US4652274A/en not_active Expired - Lifetime
-
1986
- 1986-06-02 CA CA000510630A patent/CA1253700A/en not_active Expired
- 1986-06-16 FI FI862556A patent/FI80895C/en not_active IP Right Cessation
- 1986-07-28 DE DE8686305788T patent/DE3671852D1/en not_active Expired - Fee Related
- 1986-07-28 EP EP86305788A patent/EP0213738B1/en not_active Expired - Lifetime
- 1986-07-28 AT AT86305788T patent/ATE53525T1/en not_active IP Right Cessation
- 1986-07-30 JP JP61179808A patent/JPH0796624B2/en not_active Expired - Lifetime
- 1986-08-06 KR KR1019860006480A patent/KR940003574B1/en not_active IP Right Cessation
Also Published As
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|---|---|
| EP0213738A1 (en) | 1987-03-11 |
| JPH0796624B2 (en) | 1995-10-18 |
| JPS6234781A (en) | 1987-02-14 |
| FI80895C (en) | 1990-08-10 |
| FI80895B (en) | 1990-04-30 |
| FI862556A (en) | 1987-02-08 |
| FI862556A0 (en) | 1986-06-16 |
| KR940003574B1 (en) | 1994-04-25 |
| DE3671852D1 (en) | 1990-07-19 |
| KR870002228A (en) | 1987-03-30 |
| ATE53525T1 (en) | 1990-06-15 |
| EP0213738B1 (en) | 1990-06-13 |
| US4652274A (en) | 1987-03-24 |
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