# US 5,703,137 A · Initiators for the cationic crosslinking of polymers containing organofunctional groups

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- Number: US 5,703,137 A
- Document ID: US5703137A
- Status: Granted
- Kind: A
- Application number: 08/616,170
- Filed: 1996-03-14
- Granted: 1997-12-30
- Earliest claimed: 1996-03-14
- Assignees: Rhone-Poulenc Chimie
- Inventors: Christian Priou; Stuart Kerr, III
- Web page: https://patentgrep.com/patent/US5703137A

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- C08G 59/3254: {containing atoms other than carbon, hydrogen, oxygen or nitrogen}
- C08G 59/68: characterised by the catalysts used
- C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators}
- C09D 183/06: containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence)
- D21H 27/001: {Release paper}
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- D21H: PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR

## Abstract

The present invention relates to initiators for the polymerization and/or crosslinking, cationically and under photochemical and/or thermal activation and/or activation by a beam of electrons, of monomers and/or polymers containing organofunctional groups. The said initiators are of the type comprising an onium salt of an element from groups 15 to 17 of the Periodic Table (Chem & Eng News, Vol 63, N5, 26, of 4 Feb. 1985) and they are characterized in that they contain at least one polymerization and/or crosslinking accelerator chosen from .alpha.-hydroxylated carboxylic acid esters such as, for example, lactic acid esters. Another subject of the invention is compositions based on at least one cationically crosslinkable polyorganosiloxane and on at least one initiator.

## Claims

### Claim 1

A composition useful for polymerizing or cationically crosslinking one or more monomers containing epoxide or vinyl ether organofunctional groups as a result of exposure to photochemical activation, thermal activation or electron beam radiation comprising:
(a) a catalytically effective amount of either an onium borate salt of an element selected from the group consisting of I, S, Se, P and N, or an oxoisothiochromanium salt; and
(b) an accelerator comprising a compound of formula (I) ##STR11## wherein R.sup.1 is selected from the group consisting of: a linear or branched C.sub.1 -C.sub.10 alkyl radical, optionally substituted with a linear or branched C.sub.1 -C.sub.4 alkoxy group;
a C.sub.4 -C.sub.10 cycloalkyl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
a C.sub.5 -C.sub.12 aryl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
an aralkyl or aroxyalkyl radical in which the aryl part of the radical is a C.sub.5 -C.sub.12 group optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups, wherein the alkyl part of the radical is a linear or branched C.sub.1 -C.sub.4 group;
a linear or branched C.sub.1 -C.sub.15 alkoxy radical; and
a C.sub.4 -C.sub.10 cycloalkyloxy radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups; and
wherein R.sup.2 is selected from the group consisting of:
a linear or branched C.sub.1 -C.sub.10 alkyl radical, optionally substituted with a linear or branched C.sub.1 -C.sub.4 alkoxy group;
a C.sub.4 -C.sub.10 cycloalkyl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
a C.sub.5 -C.sub.12 aryl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups; and
an aralkyl or aroxyalkyl radical in which the aryl part is a C.sub.5 -C.sub.12 group optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups, wherein the alkyl part or the radical is a linear or branched C.sub.1 -C.sub.4 group.

### Claim 2 (depends on 1)

The composition according to claim 1, wherein R.sup.1 represents a linear C.sub.1 -C.sub.3 alkyl radical, and R.sup.2 represents a linear or branched C.sub.2 -C.sub.6 alkyl radical.

### Claim 3 (depends on 2)

The composition according to claim 2, wherein R.sup.1 represents a methyl radical and R.sup.2 represents a linear C.sub.3 -C.sub.5 alkyl radical.

### Claim 4 (depends on 1)

The composition according to claim 1 wherein
(a) comprises a catalytically effective amount of an onium borate salt wherein the cationic species of said salt is selected from the group consisting of:
(1) onium salts of formula (II)
›(R.sup.3).sub.n --A--(R.sup.4).sub.m !.sup.+ (II)
in which:
A represents an element selected from the group consisting of I, S, Se, P and N;
R.sup.3 represents a C.sub.6 -C.sub.20 carbocyclic or heterocyclic aryl radical, when R.sup.3 represents a heterocyclic aryl radical, said heterocyclic radical may contain nitrogen or sulphur as hetero elements,
R.sup.4 represents the same moiety as R.sup.3 or a linear or branched C.sub.1 -C.sub.30 alkyl or alkenyl radical;
said radicals R.sup.3 and R.sup.4 optionally being substituted with a C.sub.1 -C.sub.25 alkoxy, C.sub.1 -C.sub.25 alkyl, nitro, chloro, bromo, cyano, carboxyl or mercapto group;
n is an integer ranging from 1 to (v+1), v being the valence of the element A,
m is an integer ranging from 0 to (v-1) wherein n+m=v+1; or
(2) an oxoisothiochromanium salt;
and wherein said anionic borate species is of formula (III):
›BX.sub.a R.sub.b !.sup.- (III)
in which:
a is an integer ranging from 0 to 3, and b is an integer ranging from 0 to 4, wherein a+b=4;
X represents either a halogen atom with the proviso that a is an integer from 0 to 3, or an OH function with the proviso that a is an integer from 0 to 2,
R is identical or different and represents a member selected from the group consisting of:
a phenyl radical substituted with at least one electron-withdrawing group; and
an aryl radical containing at least two aromatic rings optionally substituted with at least one element or an electron-withdrawing group selected from the group consisting of a halogen atom, CF.sub.3, OCF.sub.3, NO.sub.2 or CN.

### Claim 5 (depends on 4)

The composition according to claim 4, wherein the anionic borate species is selected from the group consisting of: ##STR12##

### Claim 6 (depends on 4)

The composition according to claim 4, wherein the cationic species of said salt is selected from the group consisting of: ##STR13## wherein .phi. represents a phenyl group.

### Claim 7 (depends on 4)

The composition according to claim 4, wherein said onium borate is selected from the group consisting of: ##STR14## wherein .phi. represents a phenyl group.

### Claim 8

A composition comprising:
(a) a catalytically effective amount of either an onium salt of an element selected from the group consisting of I, S, Se, P and N, or an oxioisothiochromanium salt;
(b) an accelerator comprising a compound of formula (I) ##STR15## wherein R.sup.1 is selected from the group consisting of: a linear or branched C.sub.1 -C.sub.10 alkyl radical, optionally substituted with a linear or branched C.sub.1 -C.sub.4 alkoxy group;
a C.sub.4 -C.sub.10 cycloalkyl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
a C.sub.5 -C.sub.12 aryl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
an aralkyl or aroxyalkyl radical in which the aryl part of the radical is a C.sub.5 -C.sub.12 group optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups, wherein the alkyl part of the radical is a linear or branched C.sub.1 -C.sub.4 group;
a linear or branched C.sub.1 -C.sub.15 alkoxy radical; and
a C.sub.4 -C.sub.10 cycloalkyloxy radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups; and
wherein R.sup.2 is selected from the group consisting of:
a linear or branched C.sub.1 -C.sub.10 alkyl radical, optionally substituted with a linear or branched C.sub.1 -C.sub.4 alkoxy group;
a C.sub.4 -C.sub.10 cycloalkyl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
a C.sub.5 -C.sub.12 aryl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups; and
an aralkyl or aroxyalkyl radical in which the aryl part is a C.sub.5 -C.sub.12 group optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups, wherein the alkyl part or the radical is a linear or branched C.sub.1 -C.sub.4 group; and
(c) at least one cationically crosslinkable polyorganosiloxane containing epoxide or vinyl ether functional groups.

### Claim 9 (depends on 8)

The composition according to claim 8, wherein the polyorganosiloxane is selected from the group consisting of:
either linear or substantially linear compounds consisting of units of formula (IV), ending with units of formula (V);
or cyclic and consisting of units of formula (IV): ##STR16## in which formalae: the symbols R.sup.6 are identical or different and represent:
either a linear or branched C.sub.1 -C.sub.6 alkyl radical, optionally substituted with one or more halogens;
an optionally substituted C.sub.5 -C.sub.8 cycloalkyl radical; or
a C.sub.5 -C.sub.12 aryl radical or aralkyl radical having a C.sub.5 -C.sub.12 aryl part and a C.sub.1 -C.sub.4 alkyl part, optionally substituted on the aryl part with halogens, C.sub.1 -C.sub.3 alkyl or alkoxy groups;
Y is identical or different and represents:
either the radical R.sup.6 ; or
a cationically crosslinkable organofunctional group connected to the silicon by a divalent radical containing from 2 to 20 carbon atoms optionally containing a hetero atom;
wherein at least one of the symbols Y is a cationically crosslinkable epoxide or vinyl ether organofunctional group.

### Claim 10 (depends on 9)

The compositions according to claim 9, wherein the polyorganosiloxane contains from 1 to 10 organofunctional groups per mole.

### Claim 11 (depends on 9)

The composition according to claim 9 wherein the polyorganosiloxane has a structure in which:
at least 60 mole % of the radicals R.sup.6 are methyl radicals.

### Claim 12 (depends on 9)

The compositions according to claim 9 wherein said polyorganosiloxane is linear and has a viscosity at 25.degree. C. of about 10 to 10,000 mPa s.

### Claim 13

A process for rendering articles non-adhesive to surfaces to which they would normally adhere, comprising the steps of:
(a) applying a composition comprising:
(1) a catalytically effective amount of either an onium salt of an element selected from the group consisting of I, S, Se, P and N, or an oxoisothiochromanium salt;
(2) an accelerator comprising a compound of formula (I) ##STR17## wherein R.sup.1 is selected from the group consisting of: a linear or branched C.sub.1 -C.sub.10 alkyl radical, optionally substituted with a linear or branched C.sub.1 -C.sub.4 alkoxy group;
a C.sub.4 -C.sub.10 cycloalkyl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
a C.sub.5 -C.sub.12 aryl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
an aralkyl or aroxyalkyl radical in which the aryl part is a C.sub.5 -C.sub.12 group optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups, wherein the alkyl part or the radical is a linear or branched C.sub.1 -C.sub.4 group;
a linear or branched C.sub.1 -C.sub.15 alkoxy radical; and
a C.sub.4 -C.sub.10 cycloalkyloxy radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups; and
wherein R.sup.2 is selected from the group consisting of:
a linear or branched C.sub.1 -C.sub.10 alkyl radical, optionally substituted with a linear or branched C.sub.1 -C.sub.4 alkoxy group;
a C.sub.4 -C.sub.10 cycloalkyl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
a C.sub.5 -C.sub.12 aryl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups; and
an aralkyl or aroxyalkyl radical in which the aryl part is a C.sub.5 -C.sub.12 group optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups, wherein the alkyl part or the radical is a linear or branched C.sub.1 -C.sub.4 group; and
(3) at least one cationically crosslinkable polyorganosiloxane having epoxide or vinyl ether functional groups;
in an amount of between 0.1 and 500 g per m.sup.2 of a surface of the said article to be coated; and
(b) exposing said surface to photochemical activation, thermal activation or electron beam radiation to cure said polyorganosiloxane onto said surface.

### Claim 14 (depends on 13)

The process according to claim 13, wherein step (b) comprises exposing said surface to ultraviolet radiation at a of wavelength of about 200 to 400 nanometers.

### Claim 15 (depends on 14)

The process according to claim 14 wherein step (b) further comprises exposing said surface to thermal activation.

### Claim 16

An article of manufacture having coated and cured on one or more of its surfaces a film of a composition comprising:
(1) a catalytically effective amount of either an onium salt of an element selected from the group consisting of I, S, Se, P and N, or an oxoisothiochromanium salt; and
(2) an accelerator comprising a compound of formula (I) ##STR18## wherein R.sup.1 is selected from the group consisting of: a linear or branched C.sub.1 -C.sub.10 alkyl radical, optionally substituted with a linear or branched C.sub.1 -C.sub.4 alkoxy group;
a C.sub.4 -C.sub.10 cycloalkyl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
a C.sub.5 -C.sub.12 aryl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
an aralkyl or aroxyalkyl radical in which the aryl part is a C.sub.5 -C.sub.12 group optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups,
wherein the alkyl part or the radical is a linear or branched C.sub.1 -C.sub.4 group;
a linear or branched C.sub.1 -C.sub.15 alkoxy radical; and
a C.sub.4 -C.sub.10 cycloalkyloxy radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups; and
wherein R.sup.2 is selected from the group consisting of:
a linear or branched C.sub.1 -C.sub.10 alkyl radical, optionally substituted with a linear or branched C.sub.1 -C.sub.4 alkoxy group;
a C.sub.4 -C.sub.10 cycloalkyl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups;
a C.sub.5 -C.sub.12 aryl radical, optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups; and
an aralkyl or aroxyalkyl radical in which the aryl part is a C.sub.5 -C.sub.12 group optionally substituted with one or more linear or branched C.sub.1 -C.sub.4 alkyl or alkoxy groups, wherein the alkyl part or the radical is a linear or branched C.sub.1 -C.sub.4 group; and
(3) at least one cationically crosslinkable polyorganosiloxane containing epoxide or vinyl ether functional groups.