CA1216816A - Process for curing acid-curable abrasive compositions - Google Patents
Process for curing acid-curable abrasive compositionsInfo
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- CA1216816A CA1216816A CA000428111A CA428111A CA1216816A CA 1216816 A CA1216816 A CA 1216816A CA 000428111 A CA000428111 A CA 000428111A CA 428111 A CA428111 A CA 428111A CA 1216816 A CA1216816 A CA 1216816A
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- Prior art keywords
- alkyl
- phenyl
- substituted
- unsubstituted
- curing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
-
- 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
- B24D3/285—Reaction products obtained from aldehydes or ketones
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A process for curing acid-curable abrasive compositions Abstract A process for curing abrasive compositions containing an acid-curable binder and, as curing catalyst, an organic sulfonic acid releasable by the action of light, and also additives customarily used in abrasives technology, in which process the abrasive compositions after drying are exposed to the action of light rays and thus cured.
Of particular interest as masked curing catalysts are organic compounds of the formulae I and II
Of particular interest as masked curing catalysts are organic compounds of the formulae I and II
Description
8~
Case 3-13918/~
A process for curing acid-curable abrasive compositions The present invention relates to a process for curing acid-curable abrasive compositions based on an acid-curable resin containing a masked curing catalyst.
By a grinding tool is meant in general the combination of a hard granular abrasive, optionally also of a carrier element or reinforcement, with a binder to form a closed composite material.
Grinding tools can be classified, according to typical structural features, under two main groups, namely, grinding wheels or disks, such as abrasive wheels, rings or points, and flexible abrasives on flat or sheetlike carrier materials.
In the case of flexible abrasives on flat carrier materials, there are used as binders the most varied synthetic resins, including however to the greater extent the pheno- and aminoplasts, and also the alkyd-melamine resins.
To produce these abrasives, the carrier material is coated with a thin film of a liquid base binder and the abrasive grain; the binder is then dried, and subsequently cured by heat treatment to such a degree that the abrasive grain is sufficiently anchored so as not to become r/, ~2~16 displaced or turned over during further treatment. A
final covering binder layer, which is usuall~ filled with calcium carbonate, is afterwards applied, and is likewise cured by ~eing subjected to a a heat ~reatment, the two operations taking several hours to perform. '['he reason for this considerable amount of drying and curlng time being required is in particular the fact that the binders used are in most cases in the form of aqueous dispersions, so that firstly the dispersion water has to be removed in the drying operation, and that, especially with the use of phenol-formaldehyde reslns as binders, a further amount of water is released on curing, and consequently this also has to be removed. Furthermore, high temperatures are necessary for curing.
The use of acid curing catalysts to accelerate the curing of acid-curable resins is indeed known, including for example organic acids such as p-toluenesulfonic acid (cp. in this connection Houben-Weyl, ~ethoden der organischen Chemie (Methods in organic Chemistry), Vol.
20 14/2, 4th Edition (1963), p. 238, or German Patent Specifi-cation No. 2,406,992). For the production of abrasive compositions based on acid-curable binders, the use of such acids as catalysts to accelerate the curing stage is however not possible, since acids of this type effect already 25 during the drying phase premature curing of the resin.
This leads to undesirable bubble formation which is caused by the water or condensation product entrapped by the resin.
To accelerate the drying and curing process, there has also been suggested, in the German Offenlegungsschrift 30 No. 2,444,525, a process for producing abrasive compo-sitions, in which phenol-resol binders in polar organlc solvents are used in place of the customary aqueous binders.
This process does not however satisfy in all respPcts the 3 1~8~6 demands made.
It has now been found that with speci~ic, so-called masked catalysts, which as a result oE exposure to liyht rays during the curing stage are rapidly degraded with the formation of free sulonic acids, the curiny p~ocess can be considerably accelerated and shortened. Curing can moreover be carried out at a lower temperature.
The essential advantage of curi~g catalysts of the said type is that, as inactive compounds during the drying stage, they effect no undesirable premature curing of the binder. By virtue of this factor, the use of acid catalysis for the curing of abrasive compositions is for the first time rendered possible.
Subject matter of the present invention is accordingly a process ~or curing abrasive compositions containing an acid-curable binder and, as curing catalyst, an organic sulfonic acid releasable by the action of light, in which process the abrasive compositions after drying are exposed to the action of light rays and thus cured.
Of particular interest as masked curing catalysts are organic compounds of the formulae I and II
o R20 1 ~ R ,R6~8 L 3 ~D L 7 (I) (II) wherein n is 1 or 2, Rl is phenyl or naphthyl which is unsubstituted or sub-stituted by 1, 2 or 3 radicals : -Cl, - Br, -CN, -N02, Cl-C12-alkyl, Cl-C4-alkoxy, phenyloxy, tolyloxy, phenylthio, tolylthio, Cl-C8-alkylthio, -SCH2CH20H, Cl-c4-alkylsulfonyl~ phenylsulfonyl, ~r ~Z~L68~ 6i C2-C4-alkoxycarbonyl, Cl-C4-alkylamino, C2-C~-dialkylamino, phenyl-CONH- or Cl-C~-alkyl-CONH-, or by benzoyl, or Rl is anthryl., phenanthryl, thienyl, pyridy.~, ~uryl, indolyl o~ tetrahydronaphthyl, and R2 and R3 independently o~ one another are each hydrogen, or Cl-C8-alkyl which is unsubstituted or substituted by -OH. -Cl, Cl-C4~alkoxy, -CN, C2-C5-alkoxycarbonyl, phenyl, chlorophenyl, C7-C10-alkylphenyl or C7-C10-alkoxyphenyl, or they are benzoyl, in addition R3 is phenyl which is unsubstituted or substituted by -Cl, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-alkylthio, or it is C2-C8-alkoxycarbonyl, -CN, Cl-C4-alkyl-NH-CO-, phenyl-NH-CO- or -CONH2, or R2 and R3 together with the carbon atom to which they are bound form a C4-C6-cycloalkyl ring, R4 is, when n = 1, Cl-C18-alkyl, phenyl which is unsub-stituted or substituted by halogen, Cl-C12-alkyl, Cl-C4-alkoxy, Cl-C4-alkyl-CONH-, phenyl-CONH-, -N02 or benzoyl, or it is naphthyl which is unsubstituted or substituted by halogen, Cl-C12-alkyl or Cl-C4-alkoxy, or it is C5-C6-cycloalkyl, C7-Cg-aralkyl, campheryl, -CF3, -CC13, -F or -NH2, and R4 is, when n = 2, a -(CH2) group, wherein m is 2 to 8, or phenylene or naphthylene each unsubstituted or substituted by Cl-C12-alkyl, is phenyl or naphthyl which are each unsubstituted or substituted by 1,
Case 3-13918/~
A process for curing acid-curable abrasive compositions The present invention relates to a process for curing acid-curable abrasive compositions based on an acid-curable resin containing a masked curing catalyst.
By a grinding tool is meant in general the combination of a hard granular abrasive, optionally also of a carrier element or reinforcement, with a binder to form a closed composite material.
Grinding tools can be classified, according to typical structural features, under two main groups, namely, grinding wheels or disks, such as abrasive wheels, rings or points, and flexible abrasives on flat or sheetlike carrier materials.
In the case of flexible abrasives on flat carrier materials, there are used as binders the most varied synthetic resins, including however to the greater extent the pheno- and aminoplasts, and also the alkyd-melamine resins.
To produce these abrasives, the carrier material is coated with a thin film of a liquid base binder and the abrasive grain; the binder is then dried, and subsequently cured by heat treatment to such a degree that the abrasive grain is sufficiently anchored so as not to become r/, ~2~16 displaced or turned over during further treatment. A
final covering binder layer, which is usuall~ filled with calcium carbonate, is afterwards applied, and is likewise cured by ~eing subjected to a a heat ~reatment, the two operations taking several hours to perform. '['he reason for this considerable amount of drying and curlng time being required is in particular the fact that the binders used are in most cases in the form of aqueous dispersions, so that firstly the dispersion water has to be removed in the drying operation, and that, especially with the use of phenol-formaldehyde reslns as binders, a further amount of water is released on curing, and consequently this also has to be removed. Furthermore, high temperatures are necessary for curing.
The use of acid curing catalysts to accelerate the curing of acid-curable resins is indeed known, including for example organic acids such as p-toluenesulfonic acid (cp. in this connection Houben-Weyl, ~ethoden der organischen Chemie (Methods in organic Chemistry), Vol.
20 14/2, 4th Edition (1963), p. 238, or German Patent Specifi-cation No. 2,406,992). For the production of abrasive compositions based on acid-curable binders, the use of such acids as catalysts to accelerate the curing stage is however not possible, since acids of this type effect already 25 during the drying phase premature curing of the resin.
This leads to undesirable bubble formation which is caused by the water or condensation product entrapped by the resin.
To accelerate the drying and curing process, there has also been suggested, in the German Offenlegungsschrift 30 No. 2,444,525, a process for producing abrasive compo-sitions, in which phenol-resol binders in polar organlc solvents are used in place of the customary aqueous binders.
This process does not however satisfy in all respPcts the 3 1~8~6 demands made.
It has now been found that with speci~ic, so-called masked catalysts, which as a result oE exposure to liyht rays during the curing stage are rapidly degraded with the formation of free sulonic acids, the curiny p~ocess can be considerably accelerated and shortened. Curing can moreover be carried out at a lower temperature.
The essential advantage of curi~g catalysts of the said type is that, as inactive compounds during the drying stage, they effect no undesirable premature curing of the binder. By virtue of this factor, the use of acid catalysis for the curing of abrasive compositions is for the first time rendered possible.
Subject matter of the present invention is accordingly a process ~or curing abrasive compositions containing an acid-curable binder and, as curing catalyst, an organic sulfonic acid releasable by the action of light, in which process the abrasive compositions after drying are exposed to the action of light rays and thus cured.
Of particular interest as masked curing catalysts are organic compounds of the formulae I and II
o R20 1 ~ R ,R6~8 L 3 ~D L 7 (I) (II) wherein n is 1 or 2, Rl is phenyl or naphthyl which is unsubstituted or sub-stituted by 1, 2 or 3 radicals : -Cl, - Br, -CN, -N02, Cl-C12-alkyl, Cl-C4-alkoxy, phenyloxy, tolyloxy, phenylthio, tolylthio, Cl-C8-alkylthio, -SCH2CH20H, Cl-c4-alkylsulfonyl~ phenylsulfonyl, ~r ~Z~L68~ 6i C2-C4-alkoxycarbonyl, Cl-C4-alkylamino, C2-C~-dialkylamino, phenyl-CONH- or Cl-C~-alkyl-CONH-, or by benzoyl, or Rl is anthryl., phenanthryl, thienyl, pyridy.~, ~uryl, indolyl o~ tetrahydronaphthyl, and R2 and R3 independently o~ one another are each hydrogen, or Cl-C8-alkyl which is unsubstituted or substituted by -OH. -Cl, Cl-C4~alkoxy, -CN, C2-C5-alkoxycarbonyl, phenyl, chlorophenyl, C7-C10-alkylphenyl or C7-C10-alkoxyphenyl, or they are benzoyl, in addition R3 is phenyl which is unsubstituted or substituted by -Cl, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-alkylthio, or it is C2-C8-alkoxycarbonyl, -CN, Cl-C4-alkyl-NH-CO-, phenyl-NH-CO- or -CONH2, or R2 and R3 together with the carbon atom to which they are bound form a C4-C6-cycloalkyl ring, R4 is, when n = 1, Cl-C18-alkyl, phenyl which is unsub-stituted or substituted by halogen, Cl-C12-alkyl, Cl-C4-alkoxy, Cl-C4-alkyl-CONH-, phenyl-CONH-, -N02 or benzoyl, or it is naphthyl which is unsubstituted or substituted by halogen, Cl-C12-alkyl or Cl-C4-alkoxy, or it is C5-C6-cycloalkyl, C7-Cg-aralkyl, campheryl, -CF3, -CC13, -F or -NH2, and R4 is, when n = 2, a -(CH2) group, wherein m is 2 to 8, or phenylene or naphthylene each unsubstituted or substituted by Cl-C12-alkyl, is phenyl or naphthyl which are each unsubstituted or substituted by 1,
2 or 3 radicals: -Cl, -Br, Cl-C12-alkyl, ~henyl, Cl-C4-alkoxy, phenyloxy, benzyloxy, Cl-C8-alkylthio, phenylthio, -SCH2CH20H, Cl-C4-alkyl-CONH-, benzoyl-amino or demethylamino, ,.... ...
~Zl~
or by benzoyl, or R5 is ~nthryl or phenanthryl, R6 is hydrogen, ~OH, Cl-C~-alkoxy,-OSi(CH3)3~ -OCOCH3, or Cl-C8-alkyl which is unsubstituted or substi-tuted by phenyl, R7 is hydrogen, or Cl-C8-alkyl which is unsubsti~uted or substituted by phenyl, or R7 is -CN, henzoyl, Cl-C4-alkylcarbonyl, C2-C5-alkoxycarbonyl or phenyl, R8 is hydrogen, Cl-C8-alkyl which is unsubstituted or substituted by -0~1, -Cl or phenyl, or it is phenyl which is unsubstituted or substituted by -OH, -Cl, Cl-C4-alkyl or Cl-C4-alkoxy, or R8 is c2-C6-alkenyl, C8-Cg-phenylalkenyl, furyl, thienyl or -CC13, or saturated or unsaturated C5-C6-cycloalkyl, and moreover Rs with ~7, R7 with R8 or R6 with R7, together with the carbon structure to which they are bound, ~orm a 5- or 6-membered ring which contains 1 to 5: -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO-, -S02-, -CO-, -N(CO-Cl-C4-alkyl)- or -N(COC6H5)- groups.
When phenyl and naphthyl, as Rl and R5, are substituted by Cl-C12-alkyl, they are straight-chain or branched-chain substituents, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl, especially however methyl~ If phenyl and naphthyl, as Rl and R5, are sub-stituted by Cl-C4-alkoxy, they are for example methoxy, ethoxy, propoxy or tert-butoxy.
When phenyl and naphthyl, as Rl and R5, are substiti-tuted by Cl-C8-alkylthio, they are straight chain or branched-chain substituents, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl 3 particularly methylthio.
If Rl is a phenyl or naphthyl substituted by Cl-C4-alkylamino or C2-C~-dialkylamino, it is for example - 6- lZ~8~6 a methy~, ethy~, propyl- or n butylamino group, or a dimethyl- or diethylamino substitution group.
When phenyl or naphthyl as Rl is substituted by Cl-C~-alkylsulfonyl, it is for example methyl-, ethyl-, 5 propyl-, butyl~ or tert-butylsulonyl.
When phenyl or n~phthyl denoted by Rl is substituted by Cl-C4-alkyl-CONH-, the substituents are for example methyl-, ethyl-, propyl- or n-butyl-CONH-. If phenyl as R4 contains Cl-C4-alkyl-CONH-, the substituents are for example methyl-, ethyl-, propyl- or n-butyl-CONH-.
Where Rl is thienyl, pyridyl, furyl, indolyl or tetrahydronaphthyl, all position isomers come into consideration. Preferred position isomers are however:
2-thienyl, 3-pyridyl, 2-furyl, 3-indolyl or 1,2,3,4-tetrahydro-6-naphthyl.
1 8 yl~ R2, R3, R6 and R8 are straight-chain or branched-chain alkyl groups, preferably however straight-chain Cl-C4-alkyl groups, for example methyl, ethyl, n-propyl or n-butyl.
When Cl-C8-alkyl in the case of R2 and R3, and phenyl or naphthyl in the case of R4, are substituted by Cl-C4-alkoxy, and if R6 is Cl-C4-alkoxy, they are for example methoxy, ethoxy, propoxy or tert-butoxy substituents.
When Gl-C8-alkyl, as R2 and R3, is substituted by C7-C10-alkylphenyl or C7-C10-alkoxyphenyl, the substituents are for example methyl-, methoxy-, ethyl-, ethoxy , tert-butyl- or tert-butoxyphenyl.
If alkyl as R3 is substituted by Cl-C4-alkylthio, the substituents are for example methyl-, ethyl-, propyl-and tert-butylthio.
When R2 and R3 together with the C atom to which they _ 7 _ ~2~16 are bound form a C4-C6-cycloalkyl ring, it is ~or exa~ple a cyclopentane, cyclohexane or cycloheptane ring, in particular however a cyclohexane ring.
When R4, i~ n = 1, is Cl-C18-alkyl, it is a straight-5 chain or branched-chain group, such as: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 2-ethylhexyl, undecyl, dodecyl, tert-dodecyl, tridecyl, tetradecyl, hexadecyl or octadecyl.
When phenyl or naphthyl as R4 is substituted by Cl-C12-alkyl, it is a straight-chain or branched-chain alkyl group.
Where R4 is C5-C6-cycloalkyl, it is cyclopentyl and cyclohexyl.
If R4 is C7-C9-aralkyl, it is for example l-phenylethyl, 2-phenylethyl or benzyl.
Where R4 is campheryl, it is 10-campheryl.
When R4, if n = 2, is a -(CH2)m- group, it is for example ethylene, propylene, butylene, pentylene or 20 hexamethylene.
When phenylene and naphthalene are substituted by Cl-C12-alkyl, they are straight-chain or branched-chain alkyl groups.
I~ the various phenyl groups in the radicals Rl, R3-R4, 25 R5 and R8 are substituted by radicals other than hydrogen atomsg this substitution occurs in the ortho-, meta- or para-position, especially in the para-position.
When R6, R7 and R8 are Cl-C8-alkyl substituted by phenyl, they are for example benzyl or phenylethyl groups.
If R7 is Cl-C4-alkylcarbonyl, the substituents are ~ZlÇ~6 for example methyl-, ethyl-, propyl- or tert-butyl-carbonyl.
I~ R7 is C2-C5-alkoxycarbonyl, substituents are e.g methoxy-, ethoxy-, isopropoxy-, butoxy- or tert-butoxy-carbonyl.
When phenyl as R8 is substituted by Cl-C4-alkyl or Cl-C4-alkoxy, the substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, or methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.
When R8 is C2-C6-alkenyl, it is for example vinyl, l-propenyl, 2-propenyl, isopropenyl, 2-butenyl, isobutenyl, 2-pentenyl, 2-hexenyl or 5-hexenyl, particularly however vinyl, isobutenyl or l-propenyl.
When R8 is C8-Cg-phPnylalkenyl, substituents are styryl or 3-phenylpropenyl, especially however styryl.
If R8 is furyl or thienyl, all position isomers come into consideration. Preferred position isomers are however 2-furyl and 2-thienyl.
If R8 is unsaturated C5-C6-cycloalkyl, it is for example 2-cyclopenten-1-yl, l-cyclohexen-l-yl or 3~cyclo-hexen-l-yl.
Particularly preferred curing catalysts of the formulae I and II are those wherein n = 1, and Rl is phenyl which is unsubstituted or substituted for example by: chlorine, methyl, methoxy, methylthio, phenylthio, -SCH2CH20H or benzoyl, R2 is hydrogen or Cl-C4-alkyl, R3 is hydrogen or Cl-C4-alkyl, or R2 and R3 together with the carbon atom to which they are bound form a cyclohexane ring, -R4 is Cl-C18-alkyl, phenyl or ~aphthyl each unsubstituted or substituted by Cl-C12-alkyl, or it is campheryl, R5 is phenyl which is ~msubstituted or substituted by: -Cl, Cl-C4-alkyl, Cl-C4-alkoxy, -SC~3 or phenyl, R6 is -OH
or Cl-C4-alkyl, R7 is Cl-C~-alkyl or phenyl, and R8 is -H, cl-c4-alkyl, furyl or -CC13, or R7 with R8 together wi~h ~he carbon atom to which they are bound form a cyclohexane ring.
More especially preferred are cwring catalysts of the formulae I and II wherein n = 1, Rl and R5 are each phenyl, p-tolyl or p-methylthiophenyl, R2 is hydrogen, R3 is methyl, isopropyl, n-decyl or benzyl, R~ is phenyl, p-tolyl or p-n~dodecylphenyl, R6 is -OH, R7 is -CH3 or phenyl, and R8 is -~.
The compounds of the formula I are known and can be produced by known processes, for example by reaction of the corresponding hydro~yl compounds of the formula tA) Rl c - c - OH (A) I
with one or half an equivalent of the corresponding mono-or di-sulfonic acid chlorides of the formula (B) R4-(S02Cl)n (B), in the presence of a base (cp. in this connection: Journal of the Chemical Society Perkin I, 1981, p. 263), or by reaction of the corresponding bromine derivatives of the formula (C) o Rl - C - C/R2 ~C) Br with one or half an equivalent of the silver salts of the corresponding mono- or disulfonic acid derivatives of the formula (D) - lo- 1~16~
( g 3 ~ 4 (D) 7 as for example according to the process given in the Journal of Organic Chemistry of the UdSSR, Vol. 8, p. 2166 (1972). In the formulae (A), (B3, (C) and (D)~
the symbols Rl to R4 and n have the meanings defined in the foregoing.
The intermediates of the formulae (A), (B), (C) and (D) are known compounds which can be produced by known processes, for example by those which are described in 10 Houben-Weyl, Methoden der Organischen Chemie: Vol. V/4, pp. 171-189, for the compounds of the formula (C);
Vol. IX, p. 411 or 563, for the compounds of the formula (B); and for the compounds of the formula (A): the references A. 526, 143, 164 (1936)~ Am.Soc. 76, 4402 (1954) or Z. obsc. Chim. 34, 3165 (1964).
The compounds of the formula (II) are known and can be produced by known processes, for example by reaction of the corresponding epoxy compound of the formula (E) 11 1 7 ~R
R5-C-C~C 8 (E) 20 with one equivalent of the corresponding monosulfonic acid derivative of the formula (F), or with half an equivalent of the disulfonic acid derivative of the formula (G) R4 - S03H (F) 3 4 S03M (G), for example by the processes described in Ber. Deutsch.
25 Chem. Ges. 69, 2753 (1936), and in J. Chem. Soc. 1949, 315;
or by reaction of a corresponding hydroxyl compound of the formula 1~ 0 R6 R8 R - C C - CH
. 5 I t z~
with a mono- or disulfonic acid chloride of the formulae R4 - S02Cl and C102S-R4-So2cl, respectively, according to the process given in the German Of~enlegwngssehrift 1,919,678.
In the formulae (E), (F) and (G), the symbols R5, R6, R7, R8 and R4 have the mea~in.gs defined in the ~oregoing.
The required epoxy compounds of the formula (E) can be produced by known processes, for example by chlorination of the corresponding compound of the formula (H) .
' R - C - CH - R (H) to the corresponding chlorine derivative of the formula (K) o Il R - C - CH - R (K) Cl which is reacted by subsequent condensation with the corresponding aldehyde of the formula (L) I' o R8 ~ c -El (L) to the corresponding epoxy compound of the formula (E) [cp. in this respect: Chem. Soc. 75, 2042 (1953)];
or by an aldol condensation of the corresponding compound of the formula (H) with the corresponding aldehyde of the formula (L) to give the corresponding compound of the formula (M) O R
Il _ 17 ~R8 C (M), ~1 which is subsequently reacted for example by means of hydrogen peroxide to the corresponding epoxy compound - 12 - ~Z~8~6 of the for~ula (E) [cp. in this connection: J Ch~m. Soc., 79, 928 (1901)] and Org. Syntheses 60, 88 (1981) 7 or the aldol condensation, and J. Org. Chem~ 28, 250 (1963) or Org. Syntheses 55, (1967), ~or the ormation of the epoxy derivatives].
In the ~ormulae (H), (K), (L) and (M), the symbols R5, R7 and R8 are as defined in the foregoing.
The compounds of the formulae (F) and (G) can be produced by known processes, for example by those which lo are described in Houben-Weyl, Methoden der Organischen Chemie, Vol. IX, p.p. 347 and 435.
Further masked curing catalysts can be used in the present process. Examples of these are a-methylol-benzoinsulfonic acid esters, which are described in the German Offenlegungsschrift No. 1,919,678; 4-benzoyl-4-phenyl-2-oxo-1,3,2-dioxathiolane (according to German Offenlegungsschrift No. 2,842,002); and N-sulfonyloxy-imides, which are described for example in the European Patent Application ~o. 58638.
The curing catalysts which are usable according to the invention are added to the resins in an amount sufficient for curing. The required amount depends not only on the type of resin, but also on the intended curing temperature and curing time. The amount used in general is 0.1 to 10 % by weight, preferably 0.5 to 5 % by weight, of curing catalyst, relative to the solvent-free resin. Also mixtures of such curing catalysts can be used.
Suitable as acid-curable binders for abrasives are the resins of which the curing can be accelerated by acid catalysts. They are in particular pheno-and aminoplasts, for example the condensation products of formaldehyde with phenol, resorcin, cresol, xylenol, and - 13 ~ ~ ~ ~ 6 ~ ~ ~
mixtures thereof, urea, anilines or melamine. Other aldehydes, such as acetaldehyde, ~urfurol and acrole~
can be wsed in place of formaldehyde.
The acid-curable phenol resins and aminoplasts are described in detail in "Methoden der Organischen Chemie", Houben-Weyl, Vol. 14/2~ 4th Edition (1963), p.p. 193-302 and 319-400.
Further acid-curable resins can be modified melamine resins, including etherified, esterified and otherwise modified melamine resins, for example alkydmelamine resins, as well as acrylic esters or polyesters, or alkyd resins.
The binders can moreover consist of several identical or different acid-curable resins. Mixtures of various phenol resins, which are described for example in the European Patent Applicat;on No. 12409, can also be used.
The phenol-formaldehyde resins are particularly preferred, especially the aqueous-liquid, weakly alkaline to neutral phenol-formaldehyde condensation products of the resol type, which have greatly gained in importance.
It is advantageous with the use of aqueous-liquid alkaline resins to neutralise resins of this type before the addition of the curing catalyst.
More especially of interest are aqueous phenol-formaldehyde resins (the so-called resol types) which have been made neutral to weakly acid (pH 4-6).
The binders can be solutions or dispersions of the resin in an organic solvent, preferably in aliphatic alcohols, or in water. They can contain, in addition to the abrasive and the curing catalyst, also fillers and additives, such as those customarily used in the abrasives industry, for example: agents improving the viscosity index~
thickeners, dispersing agents~ additives for improving the - 14 - lLZ~G~8~6 mechanical and thermal properties of the abrasives, and also adhesion promoters.
As abrasives or abrasive grain, there are used substances having a very great hardness and diferent particle sizes, the actual chipping or cutting work being done by these substances. Corundum and silicon carbide are mainly used. Further known abrasive grains are zirconium oxide, boron carbide, boron nitride, quartz, granate, or glass, and various metal powders, such as Si, Cu, Ag or Ni, as well as metal alloys.
Examples of fillers and additives are: graphite, molybdenum disulfide, iron pyrite, potassium sulfate, barium sulfate, cryolite, iron sulfide, sodium chloride3 magnesia, calcium oxide, calcium fluoride, calcium lS carbonate, kaolin, glass fibres and also various plastics, for example vinyl chloride/vinylidene chloride copolymers, polyvinylidene chloride and PVC, or various halides, sulfates or sulfites, or mixtures thereof, or other fillers known in the abrasives industry.
The binders can also contain smallish amounts of special additives, for example co-initiators, as well as spectroscopic sensitisers. Examples of these are benzoln and derivatives thereof, benzil and derivatives thereof, and a-di- and trisubstituted acetophenones, derivatives of anthracene or thioxanthone, and also organic dyes.
The mentioned resins and binders, abrasives, fillers and additives constitute no limitation of scope: they are given merely by way of example of an embodiment of the invention.
Preferred abrasive compositions ar~ as follows:-for the covering binder:
A) 30 - 70 % by weight of a filler, - 15 - ~ 2 ~ 6 70 - 30 % by weight of resol (80 % by weight in water), 1 - 5 % by weight of water, and 0.2 - 2% by weight of a curing catalys~;
and for the base binder:
~) 2 20 % by weight of filler(.s), 80 - 98 % by weight of resol (80 % by weight in water), 1 - 5 % by weight of water, and 1 - 4 % by weight of catalyst:
with the proviso that the sum of the four components of the composition amounts always to 100 % by weight.
As already mentioned, the process for producing flexible abrasives passes through two phases, namely, the drying phase for the abrasive composition and the subsequent curing phase.
In the drying phase, the employed solvent or water is partially to completely evaporated off.
In the subsequent curing phase, the binder is cross-linked to the extent that the abrasive grain is adequately anchored during further treatment and can thus be no longer moved. This anchoring is of decisive importance for the quality of the finished product. The preliminary curing is usually performed at relatively high temperature, for example at 130C and above, and for one to several hours.
With the use of the masked catalysts which are applicable according to the present invention, the curing process can however be performed at relatively low temperatures and with short~ned curing times~ thus for example at temperatures of below 100C, preferably at between 60 and 90C, and within 1 to Z00 min~ttes.
These relatively low curing temperatures and shortened curing times in the process according to the invention - 16 - ~ Z ~ 6 ~ ~ ~
are of considerable technical importarlce; ~hus for e~ample in the case where water-containing substrates are used a subsequent tempering in a humiclity chamber in order to recover flexibility is renclered unnecessary by virtue of these advantages. ~ further factor is the resulting saving in energy costs.
A further advantage of the process according to the invention is that the storage stability of the abrasive compositions is not impaired, even though they contain a curing catalyst. Furthermore, the curing catalyst becomes active not in the drying phase but subsequently in the irradiation phase, effecting not until then the curing of the binder with formation of free sulfonic acid.
The exposure of the resin to light rays is performed pre~erably with W light, for which purpose there is available today a variety of suitable commercial devices.
These incorporate medium pressure, high pressure or low pressure mercury vapour lamps, as well as fluorescent tubes, the emission maxima of which are at 250 to 400 nm.
The exposure times necessary depend on the layer thickness of the resin, on the ~illing of the abrasive composition, on the light intensity of the lamps and on the distance between the lamps and the material being exposed. An abrasive composition at the customary layer thickness requires in the usual W radiation aparatus an exposure time of several seconds to minutes. In this time, the latent catalyst has become photochemically transformed with the formation of free sulfonic acid.
When photosensitisers are added to the resin, the irradiation can be carried o~t also with daylight lamps.
Examples of known photosensitisers are condensed aromatic compounds, for example perylene, aromatic amines (such as are described for example in the U.S. Patent Specification 1 Z~L~81~
No, ~,069,054)9 or cationic and basic dyes ~s~lch as are rlescribed for example in the U.S. Patent Speciication No.
4,026,705), The curing catalysts which are applicable according to the invention can be used also in the sub-sequent treatment, in which a covering binder layer, usually filled with fillers such as calcium carbonate, is applied, and then cured by exposure to light and heat treatment, in consequence of which the curing of the covering binder is accelerated and the curing time shortened.
A tempering treatment in a humidity chamber can if required be performed following the curing operation.
The further processing steps in the production of the abrasives are carried out in the manner customary in practice.
The process according to the invention is suitable in particular for producing flexible abrasives on flat (sheetlike) carrier material, for example on fibres, such as vulcanised fibres, abrasive fabrics or abrasive paper, as well as on combinations of paper and textile fabrics.
The process is suitable moreover for the production of abrasive disks, such as abrasive elements, rings, points~
segments, cylinders or heads.
The following ~xamples further illustrate the process of the invention on the basis of specific compositions acccrding to the invention. The term 'parts' denotes parts by weight, and percentages are per cent by weight.
~Z~L~i8~6 Example 1: Testing of -the anchoring of the abrasive grain, and also of the curing of the base binder in the presence of cwring catalysts applicable accor-:ling to the invention ....
30 % by weight (relative to the solid content o the 5 phenol-formaldehyde resin) of a 10 % (by weight) catalyst solution (in methylpentyl ketone) is mixed up in an aqueous phenol-formaldehyde resin MS 7215(*). The phenol-formaldehyde resin solution thus obtained is applied with a 200 ~u coating knife to an aluminium sheet (dry-film 10 thickness about 40-50 ~), and subsequen~ly coated with corundum. For this purpose, the corundum is placed into a longish V-shaped funnel, the slit-shaped opening of which is covered with a metal sieve~ and the funnel is secured to a vibrator. For applying the corundum coating, the ; 15 vibrator is switched on, whereupon the aluminium sheet coated with resin is passed at a uniform rate under the funnel (amount applied per m2: 400-600 g of corundum).
For removal of the water, the aluminium sheet thus coated - is afterwards transferred for 35 minutes to a circulating-20 air chamber at 90C, and is then exposed at a distance of l$ cm to light rays from fluorescent tubes (Philips TLK ~ 40/09) for 5, lQ and 15 minutes, in the course of which there is liberated from the catalyst applicable according to the invention an organic acid which catalyses 25 the curing of the binder. The specimens are tested after ; subsequent curing for 20 minutes at 90C.
The anchoring of the abrasive grain (corundum) in the preliminarily cured phenol-formaldehyde resin is quali-tatively tested by the surface of the specimens being 30 touched, and assessed according to the following system of classification:
A = can be moved with the finger B = is firmly anchored, and can no longer be moved with the finger.
- 19 - ~21~ii8~6 The degree of curing of the binder is measured on a binder film without corundum according to the Knoop-measuring method (ASTM D 1474). The results are shcwn in Table 1.
(*) phenol-formaldehyde resin MS 7215 (Ciba-Geigy):
77 % by weight of solid substance; aqueous solution;
pH = 4.5; viscosity = 2.5 - 3 Pas at 25C; molar ratio phenol:formaldehyde = 1:1.2.
- 20 ~ 12~68~i _ _ _ _ . _ 4~s~
C ¢ F4 F4 F4 ¢ F4 F4 F4 ¢ F4 F4 F4 ¢ F4 F4 F4
~Zl~
or by benzoyl, or R5 is ~nthryl or phenanthryl, R6 is hydrogen, ~OH, Cl-C~-alkoxy,-OSi(CH3)3~ -OCOCH3, or Cl-C8-alkyl which is unsubstituted or substi-tuted by phenyl, R7 is hydrogen, or Cl-C8-alkyl which is unsubsti~uted or substituted by phenyl, or R7 is -CN, henzoyl, Cl-C4-alkylcarbonyl, C2-C5-alkoxycarbonyl or phenyl, R8 is hydrogen, Cl-C8-alkyl which is unsubstituted or substituted by -0~1, -Cl or phenyl, or it is phenyl which is unsubstituted or substituted by -OH, -Cl, Cl-C4-alkyl or Cl-C4-alkoxy, or R8 is c2-C6-alkenyl, C8-Cg-phenylalkenyl, furyl, thienyl or -CC13, or saturated or unsaturated C5-C6-cycloalkyl, and moreover Rs with ~7, R7 with R8 or R6 with R7, together with the carbon structure to which they are bound, ~orm a 5- or 6-membered ring which contains 1 to 5: -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO-, -S02-, -CO-, -N(CO-Cl-C4-alkyl)- or -N(COC6H5)- groups.
When phenyl and naphthyl, as Rl and R5, are substituted by Cl-C12-alkyl, they are straight-chain or branched-chain substituents, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl, especially however methyl~ If phenyl and naphthyl, as Rl and R5, are sub-stituted by Cl-C4-alkoxy, they are for example methoxy, ethoxy, propoxy or tert-butoxy.
When phenyl and naphthyl, as Rl and R5, are substiti-tuted by Cl-C8-alkylthio, they are straight chain or branched-chain substituents, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl 3 particularly methylthio.
If Rl is a phenyl or naphthyl substituted by Cl-C4-alkylamino or C2-C~-dialkylamino, it is for example - 6- lZ~8~6 a methy~, ethy~, propyl- or n butylamino group, or a dimethyl- or diethylamino substitution group.
When phenyl or naphthyl as Rl is substituted by Cl-C~-alkylsulfonyl, it is for example methyl-, ethyl-, 5 propyl-, butyl~ or tert-butylsulonyl.
When phenyl or n~phthyl denoted by Rl is substituted by Cl-C4-alkyl-CONH-, the substituents are for example methyl-, ethyl-, propyl- or n-butyl-CONH-. If phenyl as R4 contains Cl-C4-alkyl-CONH-, the substituents are for example methyl-, ethyl-, propyl- or n-butyl-CONH-.
Where Rl is thienyl, pyridyl, furyl, indolyl or tetrahydronaphthyl, all position isomers come into consideration. Preferred position isomers are however:
2-thienyl, 3-pyridyl, 2-furyl, 3-indolyl or 1,2,3,4-tetrahydro-6-naphthyl.
1 8 yl~ R2, R3, R6 and R8 are straight-chain or branched-chain alkyl groups, preferably however straight-chain Cl-C4-alkyl groups, for example methyl, ethyl, n-propyl or n-butyl.
When Cl-C8-alkyl in the case of R2 and R3, and phenyl or naphthyl in the case of R4, are substituted by Cl-C4-alkoxy, and if R6 is Cl-C4-alkoxy, they are for example methoxy, ethoxy, propoxy or tert-butoxy substituents.
When Gl-C8-alkyl, as R2 and R3, is substituted by C7-C10-alkylphenyl or C7-C10-alkoxyphenyl, the substituents are for example methyl-, methoxy-, ethyl-, ethoxy , tert-butyl- or tert-butoxyphenyl.
If alkyl as R3 is substituted by Cl-C4-alkylthio, the substituents are for example methyl-, ethyl-, propyl-and tert-butylthio.
When R2 and R3 together with the C atom to which they _ 7 _ ~2~16 are bound form a C4-C6-cycloalkyl ring, it is ~or exa~ple a cyclopentane, cyclohexane or cycloheptane ring, in particular however a cyclohexane ring.
When R4, i~ n = 1, is Cl-C18-alkyl, it is a straight-5 chain or branched-chain group, such as: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 2-ethylhexyl, undecyl, dodecyl, tert-dodecyl, tridecyl, tetradecyl, hexadecyl or octadecyl.
When phenyl or naphthyl as R4 is substituted by Cl-C12-alkyl, it is a straight-chain or branched-chain alkyl group.
Where R4 is C5-C6-cycloalkyl, it is cyclopentyl and cyclohexyl.
If R4 is C7-C9-aralkyl, it is for example l-phenylethyl, 2-phenylethyl or benzyl.
Where R4 is campheryl, it is 10-campheryl.
When R4, if n = 2, is a -(CH2)m- group, it is for example ethylene, propylene, butylene, pentylene or 20 hexamethylene.
When phenylene and naphthalene are substituted by Cl-C12-alkyl, they are straight-chain or branched-chain alkyl groups.
I~ the various phenyl groups in the radicals Rl, R3-R4, 25 R5 and R8 are substituted by radicals other than hydrogen atomsg this substitution occurs in the ortho-, meta- or para-position, especially in the para-position.
When R6, R7 and R8 are Cl-C8-alkyl substituted by phenyl, they are for example benzyl or phenylethyl groups.
If R7 is Cl-C4-alkylcarbonyl, the substituents are ~ZlÇ~6 for example methyl-, ethyl-, propyl- or tert-butyl-carbonyl.
I~ R7 is C2-C5-alkoxycarbonyl, substituents are e.g methoxy-, ethoxy-, isopropoxy-, butoxy- or tert-butoxy-carbonyl.
When phenyl as R8 is substituted by Cl-C4-alkyl or Cl-C4-alkoxy, the substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, or methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.
When R8 is C2-C6-alkenyl, it is for example vinyl, l-propenyl, 2-propenyl, isopropenyl, 2-butenyl, isobutenyl, 2-pentenyl, 2-hexenyl or 5-hexenyl, particularly however vinyl, isobutenyl or l-propenyl.
When R8 is C8-Cg-phPnylalkenyl, substituents are styryl or 3-phenylpropenyl, especially however styryl.
If R8 is furyl or thienyl, all position isomers come into consideration. Preferred position isomers are however 2-furyl and 2-thienyl.
If R8 is unsaturated C5-C6-cycloalkyl, it is for example 2-cyclopenten-1-yl, l-cyclohexen-l-yl or 3~cyclo-hexen-l-yl.
Particularly preferred curing catalysts of the formulae I and II are those wherein n = 1, and Rl is phenyl which is unsubstituted or substituted for example by: chlorine, methyl, methoxy, methylthio, phenylthio, -SCH2CH20H or benzoyl, R2 is hydrogen or Cl-C4-alkyl, R3 is hydrogen or Cl-C4-alkyl, or R2 and R3 together with the carbon atom to which they are bound form a cyclohexane ring, -R4 is Cl-C18-alkyl, phenyl or ~aphthyl each unsubstituted or substituted by Cl-C12-alkyl, or it is campheryl, R5 is phenyl which is ~msubstituted or substituted by: -Cl, Cl-C4-alkyl, Cl-C4-alkoxy, -SC~3 or phenyl, R6 is -OH
or Cl-C4-alkyl, R7 is Cl-C~-alkyl or phenyl, and R8 is -H, cl-c4-alkyl, furyl or -CC13, or R7 with R8 together wi~h ~he carbon atom to which they are bound form a cyclohexane ring.
More especially preferred are cwring catalysts of the formulae I and II wherein n = 1, Rl and R5 are each phenyl, p-tolyl or p-methylthiophenyl, R2 is hydrogen, R3 is methyl, isopropyl, n-decyl or benzyl, R~ is phenyl, p-tolyl or p-n~dodecylphenyl, R6 is -OH, R7 is -CH3 or phenyl, and R8 is -~.
The compounds of the formula I are known and can be produced by known processes, for example by reaction of the corresponding hydro~yl compounds of the formula tA) Rl c - c - OH (A) I
with one or half an equivalent of the corresponding mono-or di-sulfonic acid chlorides of the formula (B) R4-(S02Cl)n (B), in the presence of a base (cp. in this connection: Journal of the Chemical Society Perkin I, 1981, p. 263), or by reaction of the corresponding bromine derivatives of the formula (C) o Rl - C - C/R2 ~C) Br with one or half an equivalent of the silver salts of the corresponding mono- or disulfonic acid derivatives of the formula (D) - lo- 1~16~
( g 3 ~ 4 (D) 7 as for example according to the process given in the Journal of Organic Chemistry of the UdSSR, Vol. 8, p. 2166 (1972). In the formulae (A), (B3, (C) and (D)~
the symbols Rl to R4 and n have the meanings defined in the foregoing.
The intermediates of the formulae (A), (B), (C) and (D) are known compounds which can be produced by known processes, for example by those which are described in 10 Houben-Weyl, Methoden der Organischen Chemie: Vol. V/4, pp. 171-189, for the compounds of the formula (C);
Vol. IX, p. 411 or 563, for the compounds of the formula (B); and for the compounds of the formula (A): the references A. 526, 143, 164 (1936)~ Am.Soc. 76, 4402 (1954) or Z. obsc. Chim. 34, 3165 (1964).
The compounds of the formula (II) are known and can be produced by known processes, for example by reaction of the corresponding epoxy compound of the formula (E) 11 1 7 ~R
R5-C-C~C 8 (E) 20 with one equivalent of the corresponding monosulfonic acid derivative of the formula (F), or with half an equivalent of the disulfonic acid derivative of the formula (G) R4 - S03H (F) 3 4 S03M (G), for example by the processes described in Ber. Deutsch.
25 Chem. Ges. 69, 2753 (1936), and in J. Chem. Soc. 1949, 315;
or by reaction of a corresponding hydroxyl compound of the formula 1~ 0 R6 R8 R - C C - CH
. 5 I t z~
with a mono- or disulfonic acid chloride of the formulae R4 - S02Cl and C102S-R4-So2cl, respectively, according to the process given in the German Of~enlegwngssehrift 1,919,678.
In the formulae (E), (F) and (G), the symbols R5, R6, R7, R8 and R4 have the mea~in.gs defined in the ~oregoing.
The required epoxy compounds of the formula (E) can be produced by known processes, for example by chlorination of the corresponding compound of the formula (H) .
' R - C - CH - R (H) to the corresponding chlorine derivative of the formula (K) o Il R - C - CH - R (K) Cl which is reacted by subsequent condensation with the corresponding aldehyde of the formula (L) I' o R8 ~ c -El (L) to the corresponding epoxy compound of the formula (E) [cp. in this respect: Chem. Soc. 75, 2042 (1953)];
or by an aldol condensation of the corresponding compound of the formula (H) with the corresponding aldehyde of the formula (L) to give the corresponding compound of the formula (M) O R
Il _ 17 ~R8 C (M), ~1 which is subsequently reacted for example by means of hydrogen peroxide to the corresponding epoxy compound - 12 - ~Z~8~6 of the for~ula (E) [cp. in this connection: J Ch~m. Soc., 79, 928 (1901)] and Org. Syntheses 60, 88 (1981) 7 or the aldol condensation, and J. Org. Chem~ 28, 250 (1963) or Org. Syntheses 55, (1967), ~or the ormation of the epoxy derivatives].
In the ~ormulae (H), (K), (L) and (M), the symbols R5, R7 and R8 are as defined in the foregoing.
The compounds of the formulae (F) and (G) can be produced by known processes, for example by those which lo are described in Houben-Weyl, Methoden der Organischen Chemie, Vol. IX, p.p. 347 and 435.
Further masked curing catalysts can be used in the present process. Examples of these are a-methylol-benzoinsulfonic acid esters, which are described in the German Offenlegungsschrift No. 1,919,678; 4-benzoyl-4-phenyl-2-oxo-1,3,2-dioxathiolane (according to German Offenlegungsschrift No. 2,842,002); and N-sulfonyloxy-imides, which are described for example in the European Patent Application ~o. 58638.
The curing catalysts which are usable according to the invention are added to the resins in an amount sufficient for curing. The required amount depends not only on the type of resin, but also on the intended curing temperature and curing time. The amount used in general is 0.1 to 10 % by weight, preferably 0.5 to 5 % by weight, of curing catalyst, relative to the solvent-free resin. Also mixtures of such curing catalysts can be used.
Suitable as acid-curable binders for abrasives are the resins of which the curing can be accelerated by acid catalysts. They are in particular pheno-and aminoplasts, for example the condensation products of formaldehyde with phenol, resorcin, cresol, xylenol, and - 13 ~ ~ ~ ~ 6 ~ ~ ~
mixtures thereof, urea, anilines or melamine. Other aldehydes, such as acetaldehyde, ~urfurol and acrole~
can be wsed in place of formaldehyde.
The acid-curable phenol resins and aminoplasts are described in detail in "Methoden der Organischen Chemie", Houben-Weyl, Vol. 14/2~ 4th Edition (1963), p.p. 193-302 and 319-400.
Further acid-curable resins can be modified melamine resins, including etherified, esterified and otherwise modified melamine resins, for example alkydmelamine resins, as well as acrylic esters or polyesters, or alkyd resins.
The binders can moreover consist of several identical or different acid-curable resins. Mixtures of various phenol resins, which are described for example in the European Patent Applicat;on No. 12409, can also be used.
The phenol-formaldehyde resins are particularly preferred, especially the aqueous-liquid, weakly alkaline to neutral phenol-formaldehyde condensation products of the resol type, which have greatly gained in importance.
It is advantageous with the use of aqueous-liquid alkaline resins to neutralise resins of this type before the addition of the curing catalyst.
More especially of interest are aqueous phenol-formaldehyde resins (the so-called resol types) which have been made neutral to weakly acid (pH 4-6).
The binders can be solutions or dispersions of the resin in an organic solvent, preferably in aliphatic alcohols, or in water. They can contain, in addition to the abrasive and the curing catalyst, also fillers and additives, such as those customarily used in the abrasives industry, for example: agents improving the viscosity index~
thickeners, dispersing agents~ additives for improving the - 14 - lLZ~G~8~6 mechanical and thermal properties of the abrasives, and also adhesion promoters.
As abrasives or abrasive grain, there are used substances having a very great hardness and diferent particle sizes, the actual chipping or cutting work being done by these substances. Corundum and silicon carbide are mainly used. Further known abrasive grains are zirconium oxide, boron carbide, boron nitride, quartz, granate, or glass, and various metal powders, such as Si, Cu, Ag or Ni, as well as metal alloys.
Examples of fillers and additives are: graphite, molybdenum disulfide, iron pyrite, potassium sulfate, barium sulfate, cryolite, iron sulfide, sodium chloride3 magnesia, calcium oxide, calcium fluoride, calcium lS carbonate, kaolin, glass fibres and also various plastics, for example vinyl chloride/vinylidene chloride copolymers, polyvinylidene chloride and PVC, or various halides, sulfates or sulfites, or mixtures thereof, or other fillers known in the abrasives industry.
The binders can also contain smallish amounts of special additives, for example co-initiators, as well as spectroscopic sensitisers. Examples of these are benzoln and derivatives thereof, benzil and derivatives thereof, and a-di- and trisubstituted acetophenones, derivatives of anthracene or thioxanthone, and also organic dyes.
The mentioned resins and binders, abrasives, fillers and additives constitute no limitation of scope: they are given merely by way of example of an embodiment of the invention.
Preferred abrasive compositions ar~ as follows:-for the covering binder:
A) 30 - 70 % by weight of a filler, - 15 - ~ 2 ~ 6 70 - 30 % by weight of resol (80 % by weight in water), 1 - 5 % by weight of water, and 0.2 - 2% by weight of a curing catalys~;
and for the base binder:
~) 2 20 % by weight of filler(.s), 80 - 98 % by weight of resol (80 % by weight in water), 1 - 5 % by weight of water, and 1 - 4 % by weight of catalyst:
with the proviso that the sum of the four components of the composition amounts always to 100 % by weight.
As already mentioned, the process for producing flexible abrasives passes through two phases, namely, the drying phase for the abrasive composition and the subsequent curing phase.
In the drying phase, the employed solvent or water is partially to completely evaporated off.
In the subsequent curing phase, the binder is cross-linked to the extent that the abrasive grain is adequately anchored during further treatment and can thus be no longer moved. This anchoring is of decisive importance for the quality of the finished product. The preliminary curing is usually performed at relatively high temperature, for example at 130C and above, and for one to several hours.
With the use of the masked catalysts which are applicable according to the present invention, the curing process can however be performed at relatively low temperatures and with short~ned curing times~ thus for example at temperatures of below 100C, preferably at between 60 and 90C, and within 1 to Z00 min~ttes.
These relatively low curing temperatures and shortened curing times in the process according to the invention - 16 - ~ Z ~ 6 ~ ~ ~
are of considerable technical importarlce; ~hus for e~ample in the case where water-containing substrates are used a subsequent tempering in a humiclity chamber in order to recover flexibility is renclered unnecessary by virtue of these advantages. ~ further factor is the resulting saving in energy costs.
A further advantage of the process according to the invention is that the storage stability of the abrasive compositions is not impaired, even though they contain a curing catalyst. Furthermore, the curing catalyst becomes active not in the drying phase but subsequently in the irradiation phase, effecting not until then the curing of the binder with formation of free sulfonic acid.
The exposure of the resin to light rays is performed pre~erably with W light, for which purpose there is available today a variety of suitable commercial devices.
These incorporate medium pressure, high pressure or low pressure mercury vapour lamps, as well as fluorescent tubes, the emission maxima of which are at 250 to 400 nm.
The exposure times necessary depend on the layer thickness of the resin, on the ~illing of the abrasive composition, on the light intensity of the lamps and on the distance between the lamps and the material being exposed. An abrasive composition at the customary layer thickness requires in the usual W radiation aparatus an exposure time of several seconds to minutes. In this time, the latent catalyst has become photochemically transformed with the formation of free sulfonic acid.
When photosensitisers are added to the resin, the irradiation can be carried o~t also with daylight lamps.
Examples of known photosensitisers are condensed aromatic compounds, for example perylene, aromatic amines (such as are described for example in the U.S. Patent Specification 1 Z~L~81~
No, ~,069,054)9 or cationic and basic dyes ~s~lch as are rlescribed for example in the U.S. Patent Speciication No.
4,026,705), The curing catalysts which are applicable according to the invention can be used also in the sub-sequent treatment, in which a covering binder layer, usually filled with fillers such as calcium carbonate, is applied, and then cured by exposure to light and heat treatment, in consequence of which the curing of the covering binder is accelerated and the curing time shortened.
A tempering treatment in a humidity chamber can if required be performed following the curing operation.
The further processing steps in the production of the abrasives are carried out in the manner customary in practice.
The process according to the invention is suitable in particular for producing flexible abrasives on flat (sheetlike) carrier material, for example on fibres, such as vulcanised fibres, abrasive fabrics or abrasive paper, as well as on combinations of paper and textile fabrics.
The process is suitable moreover for the production of abrasive disks, such as abrasive elements, rings, points~
segments, cylinders or heads.
The following ~xamples further illustrate the process of the invention on the basis of specific compositions acccrding to the invention. The term 'parts' denotes parts by weight, and percentages are per cent by weight.
~Z~L~i8~6 Example 1: Testing of -the anchoring of the abrasive grain, and also of the curing of the base binder in the presence of cwring catalysts applicable accor-:ling to the invention ....
30 % by weight (relative to the solid content o the 5 phenol-formaldehyde resin) of a 10 % (by weight) catalyst solution (in methylpentyl ketone) is mixed up in an aqueous phenol-formaldehyde resin MS 7215(*). The phenol-formaldehyde resin solution thus obtained is applied with a 200 ~u coating knife to an aluminium sheet (dry-film 10 thickness about 40-50 ~), and subsequen~ly coated with corundum. For this purpose, the corundum is placed into a longish V-shaped funnel, the slit-shaped opening of which is covered with a metal sieve~ and the funnel is secured to a vibrator. For applying the corundum coating, the ; 15 vibrator is switched on, whereupon the aluminium sheet coated with resin is passed at a uniform rate under the funnel (amount applied per m2: 400-600 g of corundum).
For removal of the water, the aluminium sheet thus coated - is afterwards transferred for 35 minutes to a circulating-20 air chamber at 90C, and is then exposed at a distance of l$ cm to light rays from fluorescent tubes (Philips TLK ~ 40/09) for 5, lQ and 15 minutes, in the course of which there is liberated from the catalyst applicable according to the invention an organic acid which catalyses 25 the curing of the binder. The specimens are tested after ; subsequent curing for 20 minutes at 90C.
The anchoring of the abrasive grain (corundum) in the preliminarily cured phenol-formaldehyde resin is quali-tatively tested by the surface of the specimens being 30 touched, and assessed according to the following system of classification:
A = can be moved with the finger B = is firmly anchored, and can no longer be moved with the finger.
- 19 - ~21~ii8~6 The degree of curing of the binder is measured on a binder film without corundum according to the Knoop-measuring method (ASTM D 1474). The results are shcwn in Table 1.
(*) phenol-formaldehyde resin MS 7215 (Ciba-Geigy):
77 % by weight of solid substance; aqueous solution;
pH = 4.5; viscosity = 2.5 - 3 Pas at 25C; molar ratio phenol:formaldehyde = 1:1.2.
- 20 ~ 12~68~i _ _ _ _ . _ 4~s~
C ¢ F4 F4 F4 ¢ F4 F4 F4 ¢ F4 F4 F4 ¢ F4 F4 F4
3~
~t__ . , ._ . __ _ * ~ ~X ~ `J ~ -X ~
~3' ~ ~ ~ 1 ¢ . . ____ ___ E
5~ ~ O n o u~ O u) O u~ o ~ o ~n o U~ o ~
o 3~ ~ ~ ~ ~ ~ ,/ ~
F~l ~
_ ._. . __ . .
Y . Il i il C~ ,//-\. ~/ '~,/
o W ~/- o~ ~-o~
o~ //o o~ ,//Y\. .//Y\.
i i l l I ~1 l ll .~ ."~fi~. "~ . \~, ~, ~ ~.,"~., ~., ~o/ ~ ~
~1 z . . . . . ~
F-l X F4 _ F~
- 21 - ~L2~
~,~ . ..... .....
C ~ ¢ a~ 4 ¢ ~ ~q ~q ¢ ¢ ¢ ¢
~ _ ,.
~' ~X ~t Ll~ ~ # ~ ~ ~ X -X -X ~X
--¢ _ _._ .~
~.~ o U~o U~ o U) ~ U~
X"~
[~ . ~ .
,o '~d o .//\ 1,~, ~ ,~
~d t) 5: 1 ~ ~ t o~ o- ~ ~) .~ a) .~ .~ O=C~ O=t~ ~ r ~ ~ /i ~ ~, ZO; _ _ ~
E-l ~ ~ _ ~ . J,~
.
~LZ~ti816 The results show that the catalysts applicable according to the invention effect no prelirninar~ curing during the drying phase (the unexposed coatings are still sot an~
sticky, the corundum is not firml~ anchored), Not until exposure to light rays does the catalyst becorne de~raded with the ~ormation of active sulfonic acids, which render possible a rapid preliminary curing of the binder at low temperatures, in consequence of which the curing process is simultaneously shortened. An adequate preliminary curing of the binder has occurred after 20 minutes at 90C, whereas the corresponding specimen without catalyst is still soft and sticky after the same curing time. The abrasive is already well anchored after an exposure time of 5 minutes, in comparison to which the unexposed specimens are freely movable.
Example 2: Testin~ of the curin~ of the coverin~ binder The phenol-formaldehyde resin MS 7215 described in Example 1 is mixed with 30 % by weight (relative to the solid content of the phenol resin) of a 10 % (by weight) 20 catalyst solution (in methylpentyl ketone), and then filled with chalk [ratio of resin (100% solid substance? to chalk is 2 to 11. The mixture obtained is applied, by the ~rocess given in Example 1, to an aluminium sheet. For removal of the water, the coa~ed aluminium sheet is placed for 35 minutes into the oven at 90C; it is then exposed for 5, 10 and 15 minutes, at a distance of 15 cm, to the light from fluorescent tubes (Philips TLK ~ 40/09). After subsequent curing of these test specimens for 20 minutes at 90C, the degree of curing of these specimens is determined according to the Knoop measuring method (ASTM D 1474).
The results are summarised in Table 2.
Table 2 . Catalyst of the formula IExposure time -j ~s,~
in minutes 1 1~74 C-C-C~l2OSO2~ --n-C H ~ 5 1 14 CH ~.=./ 12 25 1 17 ¦
* measurement not possible; specimen sticky and soft.
The results show that the exposed specimens have a sufficient hardness already after 5 minutes' exposure time and a curing time of 20 minutes at 90C, whereas the unexposed specimen is still soft and sticky after a curing time of 20 minutes.
Example 3- 30 % by weight (relative to the solid content of the phenol-formaldehyde resin) of a 10 % (by weight) catalyst solution (in methylpentyl ketone) is mixed up in an aqueous phenol-formaldehyde resin MS 7216 (*). The solution thus obtained is applied onto an aluminium sheet by the method described in Example 1, and thereupon coated with corundum; it is afterwards placed into an air-circu-lating oven at 90C for 35 minutes, and then exposed for 5, 10 and 15 minutes under fluorescent tubes. After subsequent curing for 20 minutes at 90C, the specimens are tested as in Example 1. The results are summarised in Table III.
.
~ 24 - ~ 2 Table III
Exposure Hardness ,Anchoring o Catalyst of the formulal tlme in AS'~M D Ithe abraslve ,' minutes ;147~ ' grain ~ C-C-~ ~. 5 3L ¦ ~
,\.=./ ¦ \.=./ ~---~ 10 i 35 B
CH2-OSO2--\ / C 3l 15 ' 29 ¦ B
...... -- ~
* measurement not possible; specimen sticky and soft;
A. B: see classification in Example 1.
(*) phenol-formaldehyde resin MS 7216 (Ciba-Geigy):
79 % by weight of solid substance; aqueous solution;
pH = 4.5; viscosity: 2.5 - 3.0 Pas at 25C; molar ratio phenol:formaldehyde = 1 : 1.8.
Note In the preceding disclosure reference is made to various patent publications. Fuller details for these are as follows:
Page 2: West German Patent Specification 2,406,992;
published April, 1982 assigned to Dynamit Nobel.
West German OLS 2,444,525; published April, 1976 assigned to Feldmuhle Dusseldorf.
Page 11: West German OLS 1,919,673; published November~
1970 assigned to Bayer; see also U.S. Patent 3,732,273.
- 2~a -Page 12: West German OLS 1,919,678; published November, 1970 asslgned to Bayer; see also U.S. Patent 3,732,273.
West German OLS 2,842,002; published April, 1980 assigned to Bayer.
European Application 58,638; published Augus-t, 1982 assigned to Ciba Geigy.
Page 13: European Application 12,409; published June, 1980 assigned to Hoechst.
~t__ . , ._ . __ _ * ~ ~X ~ `J ~ -X ~
~3' ~ ~ ~ 1 ¢ . . ____ ___ E
5~ ~ O n o u~ O u) O u~ o ~ o ~n o U~ o ~
o 3~ ~ ~ ~ ~ ~ ,/ ~
F~l ~
_ ._. . __ . .
Y . Il i il C~ ,//-\. ~/ '~,/
o W ~/- o~ ~-o~
o~ //o o~ ,//Y\. .//Y\.
i i l l I ~1 l ll .~ ."~fi~. "~ . \~, ~, ~ ~.,"~., ~., ~o/ ~ ~
~1 z . . . . . ~
F-l X F4 _ F~
- 21 - ~L2~
~,~ . ..... .....
C ~ ¢ a~ 4 ¢ ~ ~q ~q ¢ ¢ ¢ ¢
~ _ ,.
~' ~X ~t Ll~ ~ # ~ ~ ~ X -X -X ~X
--¢ _ _._ .~
~.~ o U~o U~ o U) ~ U~
X"~
[~ . ~ .
,o '~d o .//\ 1,~, ~ ,~
~d t) 5: 1 ~ ~ t o~ o- ~ ~) .~ a) .~ .~ O=C~ O=t~ ~ r ~ ~ /i ~ ~, ZO; _ _ ~
E-l ~ ~ _ ~ . J,~
.
~LZ~ti816 The results show that the catalysts applicable according to the invention effect no prelirninar~ curing during the drying phase (the unexposed coatings are still sot an~
sticky, the corundum is not firml~ anchored), Not until exposure to light rays does the catalyst becorne de~raded with the ~ormation of active sulfonic acids, which render possible a rapid preliminary curing of the binder at low temperatures, in consequence of which the curing process is simultaneously shortened. An adequate preliminary curing of the binder has occurred after 20 minutes at 90C, whereas the corresponding specimen without catalyst is still soft and sticky after the same curing time. The abrasive is already well anchored after an exposure time of 5 minutes, in comparison to which the unexposed specimens are freely movable.
Example 2: Testin~ of the curin~ of the coverin~ binder The phenol-formaldehyde resin MS 7215 described in Example 1 is mixed with 30 % by weight (relative to the solid content of the phenol resin) of a 10 % (by weight) 20 catalyst solution (in methylpentyl ketone), and then filled with chalk [ratio of resin (100% solid substance? to chalk is 2 to 11. The mixture obtained is applied, by the ~rocess given in Example 1, to an aluminium sheet. For removal of the water, the coa~ed aluminium sheet is placed for 35 minutes into the oven at 90C; it is then exposed for 5, 10 and 15 minutes, at a distance of 15 cm, to the light from fluorescent tubes (Philips TLK ~ 40/09). After subsequent curing of these test specimens for 20 minutes at 90C, the degree of curing of these specimens is determined according to the Knoop measuring method (ASTM D 1474).
The results are summarised in Table 2.
Table 2 . Catalyst of the formula IExposure time -j ~s,~
in minutes 1 1~74 C-C-C~l2OSO2~ --n-C H ~ 5 1 14 CH ~.=./ 12 25 1 17 ¦
* measurement not possible; specimen sticky and soft.
The results show that the exposed specimens have a sufficient hardness already after 5 minutes' exposure time and a curing time of 20 minutes at 90C, whereas the unexposed specimen is still soft and sticky after a curing time of 20 minutes.
Example 3- 30 % by weight (relative to the solid content of the phenol-formaldehyde resin) of a 10 % (by weight) catalyst solution (in methylpentyl ketone) is mixed up in an aqueous phenol-formaldehyde resin MS 7216 (*). The solution thus obtained is applied onto an aluminium sheet by the method described in Example 1, and thereupon coated with corundum; it is afterwards placed into an air-circu-lating oven at 90C for 35 minutes, and then exposed for 5, 10 and 15 minutes under fluorescent tubes. After subsequent curing for 20 minutes at 90C, the specimens are tested as in Example 1. The results are summarised in Table III.
.
~ 24 - ~ 2 Table III
Exposure Hardness ,Anchoring o Catalyst of the formulal tlme in AS'~M D Ithe abraslve ,' minutes ;147~ ' grain ~ C-C-~ ~. 5 3L ¦ ~
,\.=./ ¦ \.=./ ~---~ 10 i 35 B
CH2-OSO2--\ / C 3l 15 ' 29 ¦ B
...... -- ~
* measurement not possible; specimen sticky and soft;
A. B: see classification in Example 1.
(*) phenol-formaldehyde resin MS 7216 (Ciba-Geigy):
79 % by weight of solid substance; aqueous solution;
pH = 4.5; viscosity: 2.5 - 3.0 Pas at 25C; molar ratio phenol:formaldehyde = 1 : 1.8.
Note In the preceding disclosure reference is made to various patent publications. Fuller details for these are as follows:
Page 2: West German Patent Specification 2,406,992;
published April, 1982 assigned to Dynamit Nobel.
West German OLS 2,444,525; published April, 1976 assigned to Feldmuhle Dusseldorf.
Page 11: West German OLS 1,919,673; published November~
1970 assigned to Bayer; see also U.S. Patent 3,732,273.
- 2~a -Page 12: West German OLS 1,919,678; published November, 1970 asslgned to Bayer; see also U.S. Patent 3,732,273.
West German OLS 2,842,002; published April, 1980 assigned to Bayer.
European Application 58,638; published Augus-t, 1982 assigned to Ciba Geigy.
Page 13: European Application 12,409; published June, 1980 assigned to Hoechst.
Claims (12)
1. A process for curing abrasive compositions containing an acid-curable binder and, as curing catalyst, an organic sulfonic acid releasable by the action of light, in which process the abrasive compositions after drying are exposed to the action of light rays and thus cured.
2. A process according to Claim 1, wherein the curing is performed at temperatures of between 60° and 100°C.
3. A process according to Claim 1, wherein the exposure is performed with UV light.
4. A process according to Claim 1, wherein there are used as curing catalysts, organic compounds of the formulae I and II
(I) (II) wherein n is 1 or 2, R1 is phenyl or naphthyl which is unsubstituted or sub-stituted by 1, 2 or 3 radicals : -Cl, -Br, -CN, -NO2, C1-C12-alkyl, C1-C4-alkoxy, phenyloxy, tolyl-oxy, phenylthio, tolylthio, C1-C8-alkylthio, -SCH2CH2OH, C1-C4-alkylsulfonyl, phenylsulfonyl, C2-C4-alkoxycarbonyl, C1-C4-alkylamino, C2-C4-dialkylamino, phenyl-CONH- or C1-C4-alkyl-CONH-or by benzoyl, or R1 is anthryl, phenanthryl, thienyl, pyridyl, furyl, indolyl or tetrahydronaphthyl, and R2 and R3 independently of one another are each hydrogen,or C1-C8-alkyl which is unsubstituted or substituted by -OH, -Cl, C1-C4-alkoxy, -CN, C2-C5-alkoxycarbonyl, phenyl, chlorophenyl, C7-C10-alkylphenyl or C7-C10-alkoxyphenyl, or they are benzoyl, in addition R3 is phenyl which is unsubstituted or substituted by -Cl, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio, or it is C2-C8-alkoxycarbonyl, -CN, C1-C4-alkyl-NH-CO-, phenyl-NH-CO- or -CONH2, or R2 and R3 together with the carbon atom to which they are bound form a C4-C6-cycloalkyl ring, R4 is, when n = 1, C1-C18-alkyl, phenyl which is unsub-stituted or substituted by halogen, C1-C12-alkyl, C1-C4-alkoxy, C1-C4-alkyl-CONH-, phenyl-CONH, -NO2 or benzoyl, or it is naphthyl which is unsubstituted or substituted by halogen, C1-C12-alkyl or C1-C4-alkoxy, or it is C5-C6-cycloalkyl, C7-C9-aralkyl, campheryl, -CF3, -CCl3, -F or -NH2, and R4 is, when n = 2, a -(CH2)m group, wherein m is 2 to 8, or phenylene or naphthylene each unsubstituted or substituted by C1-C12-alkyl, R5 is phenyl or naphthyl which are each unsubstituted or substituted by 1, 2 or 3 radicals: -Cl, -Br, C1-C12-alkyl, phenyl, C1-C4-alkoxy, phenyloxy, benzyl-oxy, C1-C3-alkylthio, phenylthio, -SCH2CH2OH, C1-C4-alkyl-CONH-, benzoylamino or dimethylamino, or by benzoyl, or R5 is anthryl or phenanthryl, R6 is hydrogen, -OH, C1-C4-alkoxy, -OSi(CH3)3, -OCOCH3 or C1-C8-alkyl which is unsubstituted or substituted by phenyl, R7 is hydrogen, or C1-C8-alkyl which is unsubstituted or substituted by phenyl, or R7 is -CN, benzoyl, C1-C4-alkylcarbonyl, C2-C5-alkoxycarbonyl or phenyl, R8 is hydrogen, C1-C8-alkyl which is unsubstituted or substituted by -OH, -Cl or phenyl, or it is phenyl which is unsubstituted or substituted by -OH, -Cl, C1-C4-alkyl or C1-C4-alkoxy, or R8 is C2-C6-alkenyl, C8-C9-phenylalkenyl, furyl, thienyl or -CCl3, or saturated or unsaturated C5-C6-cycloalkyl, and moreover R5 with R7, R7 with R8 or R6 with R7, together with the carbon structure to which they are bound, form a 5- or 6-membered ring which contains 1 to 5: -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO-, -SO2-, -CO-, -N(CO-C1-C4-alkyl)- or -N(COC6H5)- groups.
(I) (II) wherein n is 1 or 2, R1 is phenyl or naphthyl which is unsubstituted or sub-stituted by 1, 2 or 3 radicals : -Cl, -Br, -CN, -NO2, C1-C12-alkyl, C1-C4-alkoxy, phenyloxy, tolyl-oxy, phenylthio, tolylthio, C1-C8-alkylthio, -SCH2CH2OH, C1-C4-alkylsulfonyl, phenylsulfonyl, C2-C4-alkoxycarbonyl, C1-C4-alkylamino, C2-C4-dialkylamino, phenyl-CONH- or C1-C4-alkyl-CONH-or by benzoyl, or R1 is anthryl, phenanthryl, thienyl, pyridyl, furyl, indolyl or tetrahydronaphthyl, and R2 and R3 independently of one another are each hydrogen,or C1-C8-alkyl which is unsubstituted or substituted by -OH, -Cl, C1-C4-alkoxy, -CN, C2-C5-alkoxycarbonyl, phenyl, chlorophenyl, C7-C10-alkylphenyl or C7-C10-alkoxyphenyl, or they are benzoyl, in addition R3 is phenyl which is unsubstituted or substituted by -Cl, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio, or it is C2-C8-alkoxycarbonyl, -CN, C1-C4-alkyl-NH-CO-, phenyl-NH-CO- or -CONH2, or R2 and R3 together with the carbon atom to which they are bound form a C4-C6-cycloalkyl ring, R4 is, when n = 1, C1-C18-alkyl, phenyl which is unsub-stituted or substituted by halogen, C1-C12-alkyl, C1-C4-alkoxy, C1-C4-alkyl-CONH-, phenyl-CONH, -NO2 or benzoyl, or it is naphthyl which is unsubstituted or substituted by halogen, C1-C12-alkyl or C1-C4-alkoxy, or it is C5-C6-cycloalkyl, C7-C9-aralkyl, campheryl, -CF3, -CCl3, -F or -NH2, and R4 is, when n = 2, a -(CH2)m group, wherein m is 2 to 8, or phenylene or naphthylene each unsubstituted or substituted by C1-C12-alkyl, R5 is phenyl or naphthyl which are each unsubstituted or substituted by 1, 2 or 3 radicals: -Cl, -Br, C1-C12-alkyl, phenyl, C1-C4-alkoxy, phenyloxy, benzyl-oxy, C1-C3-alkylthio, phenylthio, -SCH2CH2OH, C1-C4-alkyl-CONH-, benzoylamino or dimethylamino, or by benzoyl, or R5 is anthryl or phenanthryl, R6 is hydrogen, -OH, C1-C4-alkoxy, -OSi(CH3)3, -OCOCH3 or C1-C8-alkyl which is unsubstituted or substituted by phenyl, R7 is hydrogen, or C1-C8-alkyl which is unsubstituted or substituted by phenyl, or R7 is -CN, benzoyl, C1-C4-alkylcarbonyl, C2-C5-alkoxycarbonyl or phenyl, R8 is hydrogen, C1-C8-alkyl which is unsubstituted or substituted by -OH, -Cl or phenyl, or it is phenyl which is unsubstituted or substituted by -OH, -Cl, C1-C4-alkyl or C1-C4-alkoxy, or R8 is C2-C6-alkenyl, C8-C9-phenylalkenyl, furyl, thienyl or -CCl3, or saturated or unsaturated C5-C6-cycloalkyl, and moreover R5 with R7, R7 with R8 or R6 with R7, together with the carbon structure to which they are bound, form a 5- or 6-membered ring which contains 1 to 5: -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -S-, -SO-, -SO2-, -CO-, -N(CO-C1-C4-alkyl)- or -N(COC6H5)- groups.
5. A process according to Claim 4, wherein in the formulae I and II
n is 1, R1 is phenyl which is unsubstituted or substituted by chlorine, methyl, methoxy, methylthio, phenylthio, -SCH2CH2OH or benzoyl, R2 is hydrogen or C1-C4-alkyl, R3 is hydrogen or C1-C4-alkyl, or R2 and R3 together with the carbon atom to which they are bound form a cyclohexane ring, R4 is C1-C18-alkyl, phenyl or naphthyl each unsubstituted or substituted by C1-C12-alkyl, or it is campheryl, R5 is phenyl which is unsubstituted or substituted by:
-Cl, C1-C4-alkyl, C1-C4-alkoxy, -SCH3 or phenyl, R6 is -OH or C1-C4-alkyl, R7 is C1-C4-alkyl or phenyl, and R8 is -H, C1-C4-alkyl, furyl or -CCl3, or R7 with R8 together with the carbon atom to which they are bound form a cyclohexane ring.
n is 1, R1 is phenyl which is unsubstituted or substituted by chlorine, methyl, methoxy, methylthio, phenylthio, -SCH2CH2OH or benzoyl, R2 is hydrogen or C1-C4-alkyl, R3 is hydrogen or C1-C4-alkyl, or R2 and R3 together with the carbon atom to which they are bound form a cyclohexane ring, R4 is C1-C18-alkyl, phenyl or naphthyl each unsubstituted or substituted by C1-C12-alkyl, or it is campheryl, R5 is phenyl which is unsubstituted or substituted by:
-Cl, C1-C4-alkyl, C1-C4-alkoxy, -SCH3 or phenyl, R6 is -OH or C1-C4-alkyl, R7 is C1-C4-alkyl or phenyl, and R8 is -H, C1-C4-alkyl, furyl or -CCl3, or R7 with R8 together with the carbon atom to which they are bound form a cyclohexane ring.
6. A process according to Claim 4, wherein in the formulae I and II n is 1, R1 and R5 are each phenyl, p-tolyl or p-methylthiophenyl, R2 is hydrogen, R3 is methyl, isopropyl, n-decyl or benzyl, R4 is phenyl, p-tolyl or p-n-dodecylphenyl, R6 is -OH, R7 is -CH3 or phenyl, and R8 is -H.
7. A process according to Claim 1, wherein the acid-curable binder is a pheno- or aminoplast, or a mixture thereof.
8. A process according to Claim 7, wherein the acid-curable binder is a phenol-formaldehyde resin.
9. A process according to Claim 7, wherein the acid-curable binder is a resol.
10. A process according to Claim 1, wherein the acid-curable binder contains 0.1 to 10 % by weight, relative to the solvent-free binder, of the curing catalyst.
11. A process according to Claim 1, wherein the binder is the base binder.
12. A process according to Claim 1, wherein the binder is the covering binder.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH305182 | 1982-05-17 | ||
| CH3051/82-7 | 1982-05-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1216816A true CA1216816A (en) | 1987-01-20 |
Family
ID=4247509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000428111A Expired CA1216816A (en) | 1982-05-17 | 1983-05-13 | Process for curing acid-curable abrasive compositions |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS58213079A (en) |
| CA (1) | CA1216816A (en) |
| DE (1) | DE3317570A1 (en) |
| FR (1) | FR2526801B1 (en) |
| GB (1) | GB2120263B (en) |
| NO (1) | NO831755L (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3418477A1 (en) * | 1984-05-18 | 1985-11-21 | Rütgerswerke AG, 6000 Frankfurt | RADIATION-HARDENING BINDING AGENT AND METHOD FOR THE PRODUCTION OF FLAT AREAS |
| GB8413395D0 (en) * | 1984-05-25 | 1984-07-04 | Ciba Geigy Ag | Production of images |
| US4737426A (en) * | 1985-05-15 | 1988-04-12 | Ciba-Geigy Corporation | Cyclic acetals or ketals of beta-keto esters or amides |
| GB8512998D0 (en) * | 1985-05-22 | 1985-06-26 | Ciba Geigy Ag | Production of images |
| US4997717A (en) * | 1987-03-27 | 1991-03-05 | Ciba-Geigy Corporation | Photocurable abrasives |
| US4828583A (en) * | 1987-04-02 | 1989-05-09 | Minnesota Mining And Manufacturing Company | Coated abrasive binder containing ternary photoinitiator system |
| JPS63295680A (en) * | 1987-05-27 | 1988-12-02 | Nippon Paint Co Ltd | Thermosetting water-based coating composition |
| US4802896A (en) * | 1987-12-08 | 1989-02-07 | Minnesota Mining And Manufacturing Company | Modified resins and abrasive articles made with the same as a bond system |
| EP0599779A1 (en) * | 1992-10-29 | 1994-06-01 | OCG Microelectronic Materials AG | High-resolution negative photoresist having extended processing latitude |
| TW288112B (en) * | 1993-06-02 | 1996-10-11 | Sumitomo Chemical Co | |
| US5378252A (en) * | 1993-09-03 | 1995-01-03 | Minnesota Mining And Manufacturing Company | Abrasive articles |
| EP0709410A3 (en) | 1994-10-26 | 1997-03-26 | Ocg Microelectronic Materials | Polymers |
| AU2745797A (en) * | 1996-11-26 | 1998-06-22 | Eugene Keith Haisten Jr. | Waterless and solvent hand and skin cleaner |
| KR100905829B1 (en) | 2001-09-28 | 2009-07-02 | 다이셀 가가꾸 고교 가부시끼가이샤 | Catalysts Comprised of N-Substituted Cyclic Imides and Processes for Preparing Organic Compounds with The Catalysts |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR37152E (en) * | 1928-11-07 | 1930-10-25 | Method for collecting fruit falling from a tree, in particular for collecting apples or cider fruit and nuts | |
| GB572986A (en) * | 1941-05-17 | 1945-11-01 | Bakelite Ltd | Improvements in or relating to phenol-aldehyde resins |
| US2983593A (en) * | 1959-03-02 | 1961-05-09 | Norton Co | Adhesive compositions and products |
| GB964806A (en) * | 1960-08-24 | 1964-07-22 | Norton Co | Method of making a grinding wheel |
| US3560176A (en) * | 1968-12-19 | 1971-02-02 | Avco Corp | Epoxy resin bonded grinding wheel |
| CH543547A (en) * | 1969-03-14 | 1973-10-31 | Minnesota Mining & Mfg | Process for the production of latently curable molding compositions based on olefinically unsaturated monomers |
| DE1919678A1 (en) * | 1969-04-18 | 1970-11-05 | Bayer Ag | Alpha-methylol-benzoin-sulfonic acid ester |
| US3876579A (en) * | 1972-03-27 | 1975-04-08 | Rexnord Inc | Composition to be applied to a surface to increase its wear resistance |
| DE2557789C3 (en) * | 1975-12-22 | 1979-02-01 | Hoechst Ag, 6000 Frankfurt | Aqueous binders containing polyvinyl alcohol for abrasives |
| US4108747A (en) * | 1976-07-14 | 1978-08-22 | General Electric Company | Curable compositions and method for curing such compositions |
| DE2713797C3 (en) * | 1977-03-29 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | Photopolymerizable coating agents |
| DE2842002A1 (en) * | 1978-09-27 | 1980-04-10 | Bayer Ag | Benzoyl phenyl oxo-dioxathiolane cpds. useful as photoinitiators - for acid-hardenable resins and their prodn. from alpha:hydroxy-alkyl-benzoic cpds. |
| EP0009519B1 (en) * | 1978-10-09 | 1984-12-12 | Hoechst Aktiengesellschaft | Application of resin binders to the manufacture of abrasive articles, and the manufactured abrasive articles |
| JPS55118030A (en) * | 1979-03-06 | 1980-09-10 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| NL8001885A (en) * | 1980-03-31 | 1981-11-02 | Akzo Nv | INTIATOR SYSTEM FOR RADIATION-HARD COMPOSITIONS. |
| DE3265701D1 (en) * | 1981-02-13 | 1985-10-03 | Ciba Geigy Ag | Curable compositions containing an acid-curable resin, and process for curing them |
| US4510290A (en) * | 1982-01-11 | 1985-04-09 | Ciba Geigy Corporation | Acid-curable composition containing a masked curing catalyst, and a process for the curing thereof |
| EP0899822A3 (en) * | 1997-08-11 | 1999-11-03 | Framatome Connectors International | Plug-in connector arrangement |
-
1983
- 1983-05-12 GB GB08313057A patent/GB2120263B/en not_active Expired
- 1983-05-13 CA CA000428111A patent/CA1216816A/en not_active Expired
- 1983-05-13 DE DE19833317570 patent/DE3317570A1/en not_active Withdrawn
- 1983-05-16 NO NO831755A patent/NO831755L/en unknown
- 1983-05-16 FR FR8308043A patent/FR2526801B1/en not_active Expired
- 1983-05-17 JP JP58086488A patent/JPS58213079A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2526801B1 (en) | 1987-01-30 |
| GB2120263B (en) | 1985-07-31 |
| FR2526801A1 (en) | 1983-11-18 |
| GB2120263A (en) | 1983-11-30 |
| NO831755L (en) | 1983-11-18 |
| GB8313057D0 (en) | 1983-06-15 |
| DE3317570A1 (en) | 1983-11-17 |
| JPS58213079A (en) | 1983-12-10 |
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