AU735628B2 - Dental impression material with cure-indicating dye - Google Patents

Description

Our Ref: 718295 P/00/011 Regulation 3:2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Address for Service: Minnesota Mining and Manufacturing Company 3M Center PO Box 33427 Saint Paul Minnesota 55133-3427 UNITED STATES OF AMERICA DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Dental impression material with cure-indicating dye Invention Title: The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 Dental Impression Material with Cure-Indicating Dye Field of the Invention The invention relates to compositions and methods for indicating visually a cure point of a hydrosilation-curable silicone composition via a color change useful for preparing dental impression materials.

*5.5.5 ft...

SS

S S S. 5* *5 0

S..

S

S

*SSS

S

0*S* ft

S

5555 555555

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55 S S

S.

0 WO 96/00560 WO 9600560PCrIUS9SIO983 Background of the Invention Many materials undergo a change in state as a result of a "curing reaction."i For example, as a result of a curing reaction a liquid resin composition can be changed into a solid or elastomeric material. The curing reaction can be initiated in a number of diferent ways, including for example, heating the uncured sample, mixing two or more reactive components together, or exposing the uncured material to an activating radiation source or electron beam energy. Depending on the method of curing employed the transition time between states can vary in length. For some materials the change in state may be observed by simply probing the material and observing a change in viscosity. This technique, however, is subject to error and misiterretation in many cases. In addition, manually probing samples may damage the sample, and may not indicate small but important changes in the extent of cure. Other techniques of observing a material's change in state include monitoring the rheological properties of the material or analytically monitoring the 15 material using an instrument such as an NMR probe to observe directly a change in the functional groups of the material). Unfortunately, these direct techniques are often not practical for the routine monitoring of a cure reaction or may be invasive or destructive of the sample being monitored.

.One example of a material that undergoes a curing reaction is a silicone material. "Silicones" are synthetic polymeric materials that possess an extraordinarily wide range of physical properties. They can be low- or highviscosity liquids, solid resins, or vulcanizable gums. They display an unusual combination of organic and inorganic chemical properties that are due to their unique molecular structure of alternating silicon and oxygen atoms. One typical 25 polysiloxane polymer is depicted below in formula Fl1.

F H3 F 3 FF3(F 1)

CH

3

CH

3 CH- 3 These silicone polymers may be made by an equilibrium process from other siloxanes and typically range in viscosity from about 0.01I Pa s to 2500 Pa s.

-2- SUBSTTUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 Silicone polymers can be mixed with other chemicals and fillers into an enormous variety of products that serve in a multitude of applications.

Vulcanizing silicones are a special class of silicones that have as a common attribute the development of a "crosslinked" elastomer from relatively low molecular weight polymers by means of a chemical reaction that forms these crosslinks and effectively extends chain length simultaneously. Vulcanizing silicones addition-cure silicones) have many applications in industry including use as sealants, caulks, adhesives, coatings, potting materials, release liners, otologic impression materials, molding materials, dental impression materials and medical and dental implants. An essential ingredient in a vulcanizing silicone is a crosslinking component (hereinafter the "crosslinker") that reacts with the "functional group" or groups R' and R 2 of figure Fl) of the polymer chains to i simultaneously lengthen them and connect them laterally to form the crosslinked network characteristic of a silicone elastomer. Usually a catalytic agent is included 15 to facilitate the reaction of the crosslinker with the polymer's functional groups.

There are many types of vulcanizing silicones and likewise many types of crosslinking components and catalysts. Two such systems include condensationcured silicones and (ii) addition-cured, hydrosilylation cured (alternatively spelled "hydrosilation") silicones. Condensation-cured silicones characteristically, 20 and in many instances detrimentally, release water (or alcohol) as a by-product of the crosslinking reaction. The crosslinking reaction in these systems is triggered typically by combining the silicone polymer, the crosslinker and the catalyst. A variety of catalysts initiate and accelerate condensation curing such as amines and carboxylic acid salts of tin. At low temperatures the condensation-cured silicone typically requires long times to fully cure (hours or even days). Higher catalyst concentrations and/or higher temperatures can shorten the cure time.

Addition-cured silicones hydrosilylation cured silicones) are generally considered to be of higher quality and are dimensionally more accurate than condensation-cured silicones. Unlike condensation-cured silicones, addition-cured silicones, hydrosilation-cured silicones, do not produce detrimental by- -3- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/0O383 products during curing. Such silicones differ from condensation-cured silicones in that the hydrosilation-cured composition typically contains: a polymer which contains two or more vinyl functional groups; a "hydrosilane" crosslinker component containing two or more SiH bonds; and a precious metal catalyst such as a platinum catalyst.

A particularly preferred addition-cured silicone is formed by reacting a multiplyvinyl-containing organopolysiloxane with an organopolysiloxane containing a multiplicity of SiH bond per molecule (hereinafter "organohydropolysiloxane"). This reaction is typically facilitated by the presence of(3) a platinum catalyst of the Karstedt type. Platinum catalysts of the Karstedt type are described in U.S. Patent Nos. 3,715,334, 3,775,452 and 3,814,730 which are herein incorporated by reference.

g *o When vulcanizing silicones are used as modeling compounds dental S 15 impression materials) it is customary to provide the compound to the user as two separate mixtures the hydrosilation catalyst is stored separately from the hydrosilane crosslinker). When the user is ready to prepare an impression or model, the two parts will be mixed together, the silicone will be placed against the surface or object to be modeled and then the user will wait until the silicone completely cures. The cured silicone is then removed from the surface or object and retains a negative impression of that surface. A positive model may then be formed by filling the impression cavity with a material such as wax or plaster of Paris. In many instances it may not be feasible to form the positive model immediately. Therefore, it is also important that the impression retains its dimensional accuracy over a long period of time (often weeks or months).

The setting reaction of a vulcanizing silicone is triggered, in general, by the mixing together of the catalyst, crosslinker and polymer. By varying the amount of catalyst and crosslinker, the rate of setting may be adjusted. The rate of setting may be further adjusted by the incorporation of well known inhibitors and/or retarders.

One such inhibitor is 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasloxane. These retarders often operate by reacting competitively with the catalyst thereby slowing -4- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTAUS95/08383 the crosslinking reaction. In general, with the slowing of the reaction both the working time and the setting time (as defined below) are affected.

As the material begins to set, its viscosity increases. Eventually, the mixture becomes "gelled" and is changed irreversibly into a crosslinked polymer or an "elastomer. At the gel-point the material no longer easily flows or adapts to new shapes. Therefore, in applications such as the taking of a dental impression this period of time defines the extent of the "working time" period.

When the reaction is complete (or "practically" complete) the material is said to be "set." This "setting time" is likewise an important parameter for a silicone impression material, as it is crucial that the material remain in contact with the surface it is to replicate until it has completely set. For dental impressions it is desirable to have a relatively short setting time less than 10 minutes).

**.:Premature removal from the surface being replicated may result in a distorted .*..impression which will continue to crosslink, in the distorted position, outside of the 15 mouth. Unfortunately, this situation is often unnoticed by the dentist initially and is discovered only after an expensive, but worthless, dental appliance has been fabricated. The dentist and patient must then go through the entire lengthy imression making and appliance fabrication process again. This is a great expense and inconvenience.

For applications requiring detailed reproduction, such as dental impression materials, the setting time and the working time parameters are very important and must be carefully controlled. As previously mentioned, the working time measures the time period over which the reacting silicone material remains fluid enough to flow and change shape. After the reaction has reached the "gel point" the material's properties change drastically and resist further fluid flow. It is desirable to have sufficient working time so that the dentist may easily, and prior to gelation, mix the materials and place them in the mouth.

One major factor which affects both the working time and the setting time (in addition to the aforementioned use of an inhibitor or retarder) is the catalyst's "activity." Unfortunately, platinum catalysts of the Karstedt variety are somewhat sensitive to degradation and therefore are of variable activity. While the exact SUSTTUT SHEET (RULE 26) WO 96/00560 PCT/US95/08383 mechanism is presently unknown, this degradation may be advanced at high temperatures (such as might be encountered in a hot warehouse or in a trucktrailer). Over time the catalyst composition is believed to degrade and the setting time of the mixed composition becomes longer and longer. As previously mentioned even small changes in the setting time can have a detrimental effect on the accuracy of an impression if the user removes the material prior to its complete cure. Such early removal becomes more likely if the catalyst activity unexpectedly decreases upon storage. Another major factor which affects both the working time and the setting time is the ratio of catalyst to crosslinker. This ratio may be adjusted (purposely or inadvertently) by varying the amounts of each paste in the mix.

Various approaches have been attempted to provide an indication of a material's extent of cure. For example, U.S. patents 5,047,444; 5,118,559; and 1. 5,182,316 describe curable compositions that can be monitored for extent of cure via detection of a UV fluorophore which is generated during the curing process.

15 These compositions require the use of both a UV irradiation source and a UV fluorescence detector to monitor the extent of cure effectively and cannot be visualized by the naked eye. U.S. Patent 3,509,081 describes the use, in a so 0 condensation silicone composition, of a dye that exhibits a visible color change at the desired degree of cure. This system is apparently limited and unpredictable, 20 since, as the inventors state, it is "believed there is no technical relationship between the desired cure and the ultimate color change." In addition, as previously mentioned condensation silicones are limited by their dimensional instability.

European Patent Application 0 492 830 A2 describes a method, for ultraviolet radiation curing compositions, of indicating a cure point by color change.

Compositions of this invention comprise free-radical-curable materials, LTV activated free-radical initiators, and a dye that changes color upon exposure to ultraviolet radiation in the presence of free-radical-generating photoinitiators.

Preferred dyes of this invention include anthraquinone and bis-azo dyes. U.S.

Patent 4,788,240 discloses compositions comprising a polyorganosiloxane having two or more alkenyl radicals, a polyorganohydrogensiloxane, a platinum or platinum compound catalyst, and an anthraquinone or azo dye. The compositions -6- SUBSTTUTE SHEET (RULE 26) P:\WPDOCS\CRN\SPECI\718295.spe.doc-2613/O are described as being useful as a molding or dental impression material. Materials exemplified in this patent require extended curing times which are undesirable for many dental procedures.

Summary of the Invention This invention relates to compositions and methods for indicating visually a cure point of a hydrosilation-curable silicone composition via a color change useful for preparing dental impression materials.

The present invention provides a dental impression material in the form of a single-part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst; a crosslinker compound containing at least two SiH groups; a hydrosilation catalyst comprising a complex of platinum and an unsaturated organosilicon material; and one or more cure-indicating dyes, wherein 15 said dye exhibits a color change within about 10 minutes at 250 C when 500 ul of said dye, 500 pl of dichloromethane, 100 pl of pentamethyldisiloxane and 10 pl of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together and wherein said impression material exhibits a color change upon curing.

S 20 The present invention also provides a dental impression material in the form of a single-part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst; a crosslinker compound containing at least two SiH groups; a hydrosilation catalyst comprising a complex of platinum and a complexing material in the form of an unsaturated organosilicon material selected from the group consisting of: unsaturated silanes having the empirical formula, RaR'bSicXz where R is free of aliphatic unsaturation and selected from monovalent hydrocarbon radicals, R is selected from monovalent aliphatically unsaturated hydrocarbon radicals, X is a hydrolyzable radical, c is an integer having a value of at least 1, b is WO 96/00560 PC1'1US95/0933 an integer having a value greater than .or equal to 2 and the sum- of a. b and z equals the sumn of 2 and two ti mes c for a linear or branched silane and wherein c is an integer having a value from 4 to 1S and the sum ofha b and z equals two times c for a cyclic silane; unsaturated linear or branched siloxanes; of the empirical fornula.

where R and IV are as defined above, f is an integer having a value of between 2 and 10,000, e is an integer having a value greater than or equal to 2 and the sum of d and e equals the sum of 2 and two times g~ and unsaturated cyclic siloxanes of the empirical formula, RdR.Siajr w here R and TV are as defined above, e is an integer having a value greater than or eual to 2, fis an integet having a valuefoi3t18adhd d V two times C aund wherein said'catalyst complex is' formed using a platinum halide selected from the group consisting of H 2 PtC]6,nHzO, NaW'tCl 6 *nH 2

O,

KHItCl.-.H 2 0, Na 2 tCIenH 2 O, I2PtCljniH20 PtClinH 2 O, PtCI 2 Na 2 PtCL 1 -nHzO,

H

2 PtCI 4

H

2 O, NAH1ftCI4nH 2 O, KHNtCL nH 2

OK

2 PtBr 4 (H=H)tb (PtCliC3H", and the reaction product of chloroplatinic acid hexahydrate and octyl alcohol; and one or more cure-indicatin dyes. wherein said impression material exhibits a color change upon curing, wherein said dye exhibits a color change within about at 25*C when 500 pg of said dye, 500 jl ofdi oromethane, I0 WP1 of pexmtyl aiurne and 10 p1 of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together, and wherein said ctureindicating Oiye is present "m an amount between 0.0003 and 0.03 weight percent The present invention further provides a dental impression material in the form of a single-part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst; -7 a- SUBSTUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCT1US95/08383 a crosslinker compound containing at least two.Sill groups; a hydrosilation catalyst comprising a complex of platinum and a complexing material in the form of an unsaturated organosiicon material selected from the group consisting of~ ~unsaturated silanes having the empirical formnula, R.RbSi.Xz where R is fr-ee of aliphatic unsaturation and selected from monovalent hydrocarbon radicals R! is selected from monovalent aliphatically unsaturated hydrocarbon radicals X is a hydrolyzable radical, c is an integer having a value of at least 1, b is an integer having a value greater than or equal to 2 and the sum of a, b and z equals the sum of 2 and two times c for a linear or branched silane and wherein c is an integer having a value from 4 to 18 and the sum of a, b and z equals two times c for a cyclic silane; unsaturated linear or branched siloxanes of the empirical formula, RXR.SiEO(frz) *where R and R' are as defined above, f is an integer having a value of between 2 and *010,000, e is an integer having a value greater than or equal to 2 and the sum of d 20 and eequals the sum of 2and two times fand frua unsaturated cyclic siloxanes of the empirical frua RdR.SilOf where R. and R! are as defined above, e is an integer having a value greater than or equalto 2, fis aninteger having avalue from 3to18, and the sum of dande quals two times ftand wherein said catalyst complex is formed using a platinum halide 25 selected from the group consisting ofH 2 PtC 6 nH 2 O, NaHPtC] 6 -nH 2

O,

KHftCI 6 -nH 2 O, Na 2 PtCI6nH 2 O, K 2 PtCInH 2 O, PtCl4,nH 2 O, PtC 2 Na 2 PtClI7nH 2

O,

*H

2 PtCI 4 nH 2 O, NaHPtCl 4 nH 2 O, KHIPtCL nH 2 O, K 2 PtBr 4

((CH

2

=CH

2 PtCl 2 )2, (PtCliC 3 and the reaction product of chloroplatinic acid hexahydrate and octyl alcohol, and wherein said catalyst is a Karstedt catalyst and has available inorganic -7b- SUBSTTUT SHEET (RULE 26) \WV)POC~CSP11PlI\7Iudqr.d6c6dnfllu halogen of less than about 0.1 gram atoms of halogen per gram atom of platinum and one or more cure-indicating dyes having a molar extinction coefficient of at least 10,000 'cmt', wherein said impression material exhibits a color change upon curing of at least 10 AE* units.

The present invention still further provides a dental impression material in the form of a single-part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a catalyst; 101 a crossnker compound containing at least two SiH groups; a hydrosilation catalyst; and one or more cure-indicating dyes selected from the group consisting of Sneutral dyes represented by the following general formula:

R'

20 wherein: 2 each R 2

R

3 and R group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein R' and R 2 or R and R 4 may be connected to form a saturated or unsaturated ring; A is O, S, or NR 2 wherein R is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group; and B is any group capable of providing extended conjugation thereby rendering the dye capable of absorbing visible, near-UV, or near-infrared radiation and includes groups of formula D, E, F, H, or J, wherein D is represented by formula: -7c- P.\WPDOCS\CRN\SPECF\718293.Tc.doc-2(,/IOAX)

S

0 0 0S 0* SS 0 S 0 0S

S

101

S.

SSS

0

*SSSO@

wherein: each RW, Re, R 7 and R! group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two adjacent R 6

R

7 and R! groups may be connected to form a ring; E is represented by formula:

OOSS

*SS@

S

SOS.

S

S

S

@5 S

SO

wherein: X, is C(RI 2 2 S. NR1 2 or 0;

X

2 is C(R 12 2 S, NR1' 2 or 0; and each R' 0 and R 1 2 group is independently hydrogen, a hydrocarbylcontaining group, or a heterocyclic group and wherein R' 0 and R" may be connected to form a ring; F is represented by formula: -7d- P \WPDOCS\CRN\SPECI\718295.spc.doc-26/10/X0 wherein:

X

3 is N or CR16; and each R 1 3

R

14

R

15 and R 1 6 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two adjacent R 1 3

R

5 and R" 6 groups may be connected to form a ring; H is represented by formula: ooooo.

0 00* S S S* 0 0

S.*

S

S

*S*

C

S

C

wherein: each R and R 21 group is independently hydrogen, halogen, a hydrocarbylcontaining group, or a heterocyclic group and wherein R 1 5 and R 6 groups may be connected to form a ring; and J is represented by formula:

C

20 R6 R23-N RR RS wherein: each R 5

R

6

R

7 and R' group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two R 5

R

6

R

7 and R" groups may be connected to form a ring; and Ra is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group; sulfonyl dyes represented by the following general formula: -7e- P.\WPDOCS\CRN\SPECl7 1295.spc.doc-26/O/0O

SO

2 6 wherein: each R and R 2 group is independenty hydrogen, a hydrocarbyl-containing group, or a hetrocyclic group with the proviso that at least one ofR 2 and R 2 is or contains a substituted aryl, aminoaryl or heterocydic group; each R 2 and R group is independently a -(CF 2 group wherein m is a number between 0 and 20; and 1 0 n is an integer less than neutral dyes represented by the following general formula: n wherein: each R 2 R, and R group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein any two adjacent R 2

R

3 or R 2 groups may be connected to form a ring; and

R

30 is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and n is an integer less than anionic dyes having the following general formula: -7f- P \WPDOCS\CRNSPECI\718295.spe doc-2(I/0/00 wherein: Z represents the non-metallic atoms necessary to complete a substituted or unsubstituted nitrogen-containing heterocyclic ring; each R is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group; n is an integer less than 5; and wherein M+ is selected from any suitable cation; Scationic dyes having the following general formula:

R

1 5 32

R

F ZeM wherein: S 20 each R 2

R

33 and Re group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein any two adjacent R 1

R

32

R

3 3 or R" groups may be connected to form a ring;

R

3 5 and R 3 6 are as defined above for R 33 and R34; X is O, S, or NR7; Y is N or CR 3

R

37 and R 3 are as defined above for R33; and wherein M- is any suitable anion; cationic dyes having the following general formula: -7g- P:\WPDOCS\CRN\SPECI\718295 spc.doc-2I10/0I wherein: each R 32

R

33 R" and R group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein any two :adjacent R, R, or R groups may be connected to form a ring;

R

3 is independently hydrogen, a hydrocarbyl-containing group, or a 1 heterocyclic group; X is C(R 3 2 O, S, or NR 7 wherein R? is as defined above for R 39 R is as defined above for R

R

4 is an oxo group, a divalent hydrocarbyl-containing group or a divalent *heterocyclic group, and wherein R" and R" may be connected to form an unsaturated ring, and R" and R may be connected to form a ring; and wherein M- is any suitable anion; and 20 cationic dyes having the following general formula: O 4WR4 7 O 41 46 R42 43 wherein: each R 42 to R 7 group is independently hydrogen, halogen, a hydrocarbylcontaining group, or a heterocyclic group; each R, and R' 7 group is independently hydrogen, a hydrocarbyl- -7h- 1'.NWPDOCS\OIRNYEMnlII29-i~-do1-26tiMU containing group, or a heterocyclic group and wherein any two adjacent R" to R groups may be connected to form a ring and wherein R" and R 45 may be connected to form a ring; n is an integer less than 5; and wherein M- is any suitable anion, and wherein said dental impression material exhibits a color change upon curing of at least 10 AE* units.

The present invention still further provides a method of monitoring the curing of a dental impression material in the form of a single-part or multiple-part composition, comprising the steps of: placing against the teeth of a patient an impression material comprising a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst, a crosslinker compound containing at least two SiH groups, a hydrosilation catalyst comprising a complex of platinum and an unsaturated organosilicon material, and one or more 15 S°1 cure-indicating dyes; and visually observing said impression material, wherein said impression material has a first color before the cure reaction is effected and a second color after the cure reaction has been effected to an indication point, and wherein said first and second 20 colors differ by at least 5 AE* units.

The present invention still further provides a dental impression material in *oe the form of a single-part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a catalyst; a crosslinker compound containing at least two SiH groups; a hydrosilation catalyst; between 20 and 90 weight percent filler, a surfactant; and one or more cure-indicating dyes selected from the group consisting of indoaniline dyes, indophenol dyes, quinone monoimine dyes, quinone diimine dyes, -7icyine dyeM ierocyanine dyes. cydlohexadienone dyes, iminocycohexadienone dyes, imidazolylidinecyclohecadienone dyes, dihydronaphthalenone dyes, Uuinodihydironaphthalenone dyes, imidazolylidinediyronaphthalenone dyes, Cdohexadienimine dyes, aryl substituted bis (trifhzorom thy alfnl)hexatrienyi dyes, aryl substituted bs(rfurmehulnyjtMy dyes, afyl substituted bis (fluorO=* exatrienyl dyes aryl substimued his (fiuoromlffonzyl)butenyl dyes oxazlone dyes, cazionic dyes anionic dyes and amphoteric dyes, wherein said ipeson material exhibits a color change upon curing of at leas 10 AE* units.

The present invention still further provides a dental impression material in the form of a single-part or multiple-part composition comprising: a curable silicone polymer contaning at least two fimcdonal groups capable of reacting 'with a SOH group in the presence of a hydrosilazion catalyst,.

a crosslinker compound conzaung at leas two SIMl groups; catalyst capable of catalyzing a hydrosilation reaction; and one or more cuire-indicating dyes, wherein said dye exhibits a color change wthin about 10 minutes at 25 OCwhen 500 jig of said dye, 500p of dichloromethane, 100 tid Of pentamfethyidisiloxane and 10 td of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together.

wherein said dye is represented by the formula R49 RS2

RSI

R3 4/ C-R 4 Yii-K7= RsiX \RS4Cl heeneach of e. and e.

0 is independently selected from the group -7 j- ":'WPDOCSCR MSPECnI 13195.g-d-2611 OM consistings of hydrogen, halogen and an acyclic, alicyclic or aromatic hydrocarbyl group optionally interrupted with one or more heteroatoms, each of R51, W, Re, W5S, and R56 is independently selected from the group consisting of hydrogen and an acyclic, alicyclic or aromatic hydrocarbyl group optionally interrupted with one or more hateroatoms. andoponlyaytw ofR 3 1 e. and Re may together form an alicyclic or aromaticrig The present invention still further provides a dental impression material in the form of a single-part or multiple-part composition comprising: curable silicone polymer containing at leas two ftzncionaJ groups capable of reacting with a SiO group in the presence of a hydrosilation catalyst; a crosslinker compound containing at least two SIR groups; .a catalyst capable Of catalyzing a hydiosilation reaction; and one or more cueidcating dewherein said dye exhibits a color change within -about minutes at 25 *C when 500. pg of said dye, 500 W1 of dichloromethane, 100 p1 of pentamethYldisiloxane and 10 W1 of a hydrosilaion catalyst solution having between about 2 and 3 weight percent platinum are mixed together, wherein said dye is represented by the formula 20R9

NC

N-3~-X4

NCN

N C

NC

2 R66 63 R165 64 wherein X' is N-R' O-R 0 S-R7n or CR 7 Ree and wherein each of WS, R' 9 WO, Re, Re, Re. R 5 Re, is independently selected from the group consisting of hydrogen, halogen, a hYdrocarbyl group optionally interrupted with one or more -7ki m aw .KNr*tL lrnl.ycoi w"' heteroatoms and an acyclic, alicyclic or aromatic heterocyclic group, and each of R, l R, R R 71 R, and R" is independently selected from the group consisting of hydrogen, a hydrocarbyl group optionally interrupted with one or more heteroatoms and an acyclic, alicycic or aromatic heterocyclic group.

The present invention still further provides a dental impression material in the form of a single-part or multiple-part composition comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst; a crosslinker compound containing at least two SiH groups; a catalyst capable of catalyzing a hydrosilation reaction; and :'"one or more cure-indicating dyes, wherein said dye exhibits a color change within about 10 minutes at 25 *C when 500 pg of said dye, 500 pl of dichloromethane, 100 p1 ofpentamethyldisiloxane and 10 pl of a hydrosilation 15 catalyst solution having between about 2 and 3 weight percent platinum are mixed together, wherein said dye is selected from compounds of the formula

NC

NC. NC"N(Eth

NC

*and

NC

NC N(n-Bu2

NC

-71- P:\WPDOCS\CRN\SPECI718295.spe.doc-26/10/00 Presently preferred optional ingredients of the silicone composition include fillers pulverized metals, silica, quartz, calcium carbonate or metal oxides), appropriate polymerization initiators and inhibitors, pigments, stabilizers, surfactants, modifying agents, indicator adjuvants, and copolymerizable and noncopolymerizable cosolvents, and the like. Preferred dental impression "putties" of the present S* r 0 *9 *000 -7m- WO 96/00560 PCT/US95/08383 invention comprise between about 20 and 90 weight percent filler, more preferably between about 40 and 80 weight percent filler, and most preferably between about and 80 weight percent filler. Preferred dental impression "washes" (or "single phase" syringeable materials) comprise between about 10 and 70 weight percent filler, more preferably between about 20 and 60 weight percent filler, and most preferably between about 30 and 60 weight percent filler.

The curable silicone composition of the present invention can be prepared by combining mixing together) the vinyl-containing organopolysiloxane, the organohydropolysiloxane, the platinum catalyst and the cure-indicating dye or dyes.

In one embodiment, the components are pre-mixed into preferably two parts prior to use. For example, part may contain the vinyl-containing organopolysiloxane, the platinum catalyst and the cure-indicating dye, while part may contain the *organohydropolysiloxane and optionally vinyl-containing organopolysiloxane.

Alternatively, the cure-indicating dye may be incorporated in part and not in 15 part or may be in both parts and In another embodiment, the components are provided in one part and further contain an ingredient a catalyst inhibitor) which inhibits the cure reaction. Hydrosilation inhibitors are well known in the art and include such compounds as acetylenic alcohols, certain polyolefinic siloxanes, pyridine, acrylonitrile, organic phosphines and phosphites, unsaturated amides, and alkyl maleates. For example, an acetylenic alcohol compound can inhibit certain platinum catalysts and prevent curing from occurring i at low temperatures. Upon heating, the composition begins to cure. The amount of catalyst inhibitor can vary up to about 10 times or more of the amount of catalyst, depending upon the activity of the catalyst and the shelf life desired for the composition. Alternatively, one may utilize a one-part composition comprising a cure-indicating dye, a vinyl-containing organopolysiloxane, an organohydropolysiloxane, and a platinum catalyst such as disclosed in U.S. Patent Nos. 4,530,879, 4,510,094, 4,916,169, 5,145,886 and Patent Application Nos.

07/626,904 and 07/627,009. Such one-part compositions are stable at room temperature and cure when the catalyst is exposed to visible radiation.

-8- SUBSTITTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 A "cure-indicating dye" is added to the curable composition to provide a visual indication of the extent of the hydrosilation reaction extent of the crosslinking reaction). The cure-indicating dye exhibits a color change in the presence of a silicon-bonded-hydrogen compound and a precious metal hydrosilation catalyst and is characterized in a curable composition by having a first color before the cure reaction is effected and a second color after the cure reaction has been effected to the indication point. The first color and second colors are sufficiently different (or have a sufficiently different intensity) and may be readily observed in the composition using the naked eye or, optionally, a suitable instrument such as a spectrophotometer, colorimeter or fluorimeter. The term "color" is here understood to include visible fluorescence when examined using light of a shorter wavelength, including "black light".

The compositions of the present invention may find utility in a variety of applications in which the visual identification of various stages of curing (such as working-time or setting-time) provides a benefit to the end-user. This feature is particularly beneficial in uses such as the taking of a dental impression where the timing of the cure can affect the quality of the impression. For example, if the dentist removes the impression material from the mouth before it is fully set the impression will likely become distorted as it continues to cure. Similarly, if the dentist delays too long, after mixing the impression material, when placing the material against the teeth, the material will not readily flow against the teeth and therefore not take an accurate impression of them. Each or both of these situations can be avoided by utilizing visual cure indications of the present invention.

Alternatively, these compositions may be used to prepare adhesives, caulking materials, gaskets, sealants, coatings, potting materials or any other application where a cure-indicating material is required. Preferred applications of this invention include areas in which non-stick or low-energy properties of a surface are required such as impression materials, modeling materials or in release coatings for use with pressure-sensitive adhesives.

-9- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/09383 Definitions The term "crosslinked polymer," as used herein, refers to polymers that react with the functional group or groups of the polymer chains R' and R 2 of figure Fl) simultaneously to lengthen them and connect them laterally, to form the crosslinked network characteristic of a silicone elastomer. In contrast to a thermoplastic polymer a polymer that softens and flows upon heating) a crosslinked polymer, after crosslinking, is characteristically incapable of further flow.

The term "Silicone," as used herein, refers to a polymer having, for the most part, alternating silicon and oxygen atoms a polysiloxane chemical structure) and having sufficient pendant functional groups to undergo a setting reaction in the presence of a crosslinker compound and a catalyst compound.

The term "vulcanizing" as used herein, refers to silicones that have as a common attribute the development of a crosslinked elastomer from relatively low molecular weight linear or branched polymers by means of a chemical reaction that sumultaneously forms these crosslinks and effectively extends chain length at room S. temperature. "Room temperature vulcanizing" implies that the curing reaction can proceed at temperatures at or near 25 0 C. For example, the oral cavity of the mouth has an average temperature of approximately 32 0 C and is therefore near room temperature. Certain "high" temperature cured materials are designed to cure only at relatively high temperatures 50 0 C or 100 0 C) and are stable the curing reaction is retarded) at room temperature for prolonged periods.

The term "compound" is a chemical substance which has a particular molecular identity or is made of a mixture of such substances, polymeric substances.

The term "hydrosilation" means the addition of an organosilicon hydride compound to a compound containing an aliphatic multiple bond an olefinic or acetylenic unsaturation), preferably a vinyl-group,

-CH=CH

2 The term "working time" as used herein, refers to the time between the initiation of the setting reaction when the vinyl-containing organopolysiloxane, the organohydropolysiloxane, and the platinum catalyst are SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/08383 mixed) and the time the setting reaction has proceeded to the point at which it is no longer practical to perform further physical work upon the system, reform it, for its intended purpose. When the reaction has proceeded to this later point the material is said to have reached its "gel point." The working time preferably provides enough time to mix and place the composition into its desired form. For many dental impression compositions and applications the working time under conditions of use is preferably greater than 30 seconds, more preferably greater than I minute and most preferably greater than 2 minutes.

The terms "set time" or "setting time" as used herein, refer to the time at which sufficient curing has occurred so that essentially the material's final curedstate properties are obtained. For a silicone impression material the set time is that time at which one may remove the material from the sufhce being replicated without causing permanent deformation of the silicone material. The setting time may be approximated, for example, by measuring the torque of the reacting composition on a oscillatory rheometer. When the torque value reaches a maximum value the material is said to be fulfly set. An arbitrary torque value which is less than the typical maximum value 90% of the maximum value) may alternatively be used as a practical approximation of the set time. In general, shorter setting times .are preferred over longer setting times. For dental impression compositions the setting time occurs at a time preferably less than 10 minutes after initiation of the reaction. More preferably the setting time is less than the sum of 5 minutes plus the working time. Most preferably the setting time is just longer than the desired working time.

As used herein, "solubility" means the capability of a substance to form a solution, either a true solution or a colloidal solution. A true solution is a uniformly dispersed mixture at the molecular or ionic level of one or more substances (the solute) in one or more substances (the solvent). A colloidal dispersion is often called a solution. Since colloidal particles are larger than molecules it is strictly incorrect to call such dispersions solutions; however this term is widely used in the literature, especially when the mixture is only slightly milky. As used herein, "dispersibility" means the capability of a substance to form a dispersion, SUBSTIUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 a two-phase system where one phase consists of finely divided particles (often in the colloidal size range) distributed throughout a bulk substance, the particles being the disperse or internal phase and the bulk substance the continuous or external phase.

Detailed Description of the Invention The present invention provides novel hydrosilation-curable compositions, the cure of which can be monitored visually, comprising: a multiply-ethylenic compound; a compound containing a multiplicity of silicon-bonded-hydrogen groups; a metal or metal complex capable of catalyzing a hydrosilation reaction; i and one or more cure-indicating dye compounds with light absorption or emission in the visible spectrum 400-800 nm) that exhibit a color (including fluorescence) change in the presence of a silicon-bonded-hydrogen compound and a precious metal hydrosilation catalyst. The cure-indicating dye provides the composition with an initial pre-cure color (which color optionally can be mixed with a colored non-cure-indicating dye or pigment) and a different post-cure color. As a .result of this change in color, the setting reaction or curing of the composition can be monitored visually. For example, this cure indication prompts the user to avoid exceeding the working time of the composition or to avoid prematurely removing or stressing the composition prior to its being fully set.

In the practice of the present invention, the curable composition can be a S" multiple-part composition cured by combining crosslinking agents and catalysts or a single-part composition cured by heating and/or exposure to actinic radiation or electron beam energy. Presently most preferred for dental applications are two-part addition-cure compositions of the room temperature vulcanizing variety.

The composition contains a "curable silicone polymer," that is, a polysiloxane having two or more functional groups, vinyl groups, which enable the polymer to be polymerized or cured to a state of higher molecular weight. Suitable silicone polymers are well-known in the art and are described, for example, in "Silicones," Kirk-Othmer Encyclopedia of Chemical Technology 3rd Ed., 20, 922-962 (1982).

-12- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCrIUS95OS383 Suitable ethylenic compounds for use in the present invention include those compounds which undergo a crosslinking reaction with a silicon-bonded-hydrogen compound (alternatively referred to as the "SiH compound" or "crosslinker") in the presence of a hydrosilation catalyst. Typically, the crosslinking reaction is facilitated by a catalyst compound and may be affected by temperature the reaction may proceed at a somewhat greater rate at an elevated temperature or alternatively may be initiated at an elevated temperature). Preferred ethylenic compounds include monomers, oligomers or polymers which comprise pendant or terminal ethylenic "functional" groups groups which "function" by reacting with the aforementioned SiH compound in the presence of a catalyst) such as vinyl, alkenyl or cycloalkenyl groups. Alternatively, the functional group may be situated along the polymer chain along the backbone) and not be in a pendant position.

Of these, vinyl groups are more preferred, and terminal vinyl groups are most preferred. It is understood that, in general, the cured composition's backbone "network" or "structure" comprises both the formerly ethylenic compound and the compound which contained the Sil group. It is understood that either compound could be employed in greater or lesser proportion or have greater or lesser initial S. molecular weight. Furthermore, depending on the combination of ethylenic compound and SiH compound, one could utilize a broad variety of "backbones" in these compounds and thereby achieve a broad variety of cured compositions having a range of physical properties.

Compounds containing aliphatic unsaturation which are useful in the present invention have olefinic or acetylenic unsaturation. These compounds are wellknown in the art of hydrosilation and are disclosed in such patents as U.S. Pat. No.

3,159,662 (Ashby), U.S. Pat. No. 3,220,972 (Lamoreaux), and U.S. Pat. No.

3,410,886 (Joy). In instances where these unsaturated compounds contain elements other than carbon and hydrogen, it is preferred that these elements be either oxygen, nitrogen, silicon, halogen, or a combination thereof. The unsaturated aliphatic compound must contain two or more carbon-to-carbon multiple bonds.

Representative examples of the aliphatically unsaturated hydrocarbons which can be -13- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 employed include diolefins, for example, divinylbenzene, and 1,5-hexadiene. The unsaturated aliphatic compounds can have up to 20 to 30 carbon atoms, or more.

Oxygen-containing unsaturated aliphatic compounds can also be used, especially where the unsaturation is ethylenic, such as divinylether, diallyl ether of ethylene glycol, diallyl ether, diallyl adipate, resorcinol, diallyl ether o-undecenyl, oundecylenate (10-undecenoate), allyl acrylate, allyl methacrylate, and linolenic acid methyl ester.

Halogenated derivatives of the previously mentioned unsaturated aliphatic compounds can be employed, including acyl chlorides as well as compounds containing a halogen substituent on a carbon atom other than a carbonyl carbon atom. Unsaturated compounds containing nitrogen substituents are also useful in the practice of the present invention.

Other unsaturated compounds useful in the practice of the present invention include polymers containing aliphatic unsaturation, such as the polyester resins prepared from polybasic saturated or unsaturated acids with polyhydric unsaturated alcohols, and the polyester resins prepared by reacting unsaturated polybasic acids S: •with saturated polyhydric alcohols.

As previously mentioned, one presently preferred class of compounds for use in the present invention comprises a silicone backbone and two or more functional groups. One typical silicone composition is the polysiloxane referred to earlier and as depicted in formula Fl.

RL- F i-F (F 1)

CH

3 CH3

CH

3 Usually these polymers are made by an equilibrium process from other siloxanes and typically range in viscosity from about 0.01 Pa s to 2500 Pa s. Additional particularly useful unsaturated compounds which contain silicon are disclosed in U.

S. Patent No. 4,916,169 (Boardman et al.) which is herein incorporated by reference. The preferred molecular weight of the polysiloxane often depends upon the desired viscosity of the composition prior to crosslinking. In general, as the -14- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 molecular weight is increased the viscosity of the uncrosslinked composition increases correspondingly. For uses as molding compositions, the average value of n preferably is between 10 and 6000. More preferably the average value ofn is between 50 and 2000, and most preferably the average value of n is between 100 and 1000. Mixtures of more than one molecular weight may likewise be utilized.

The groups R L and R 2 of formula (Fl) represent the "terminal" portions of the polymer chain and are often the sites for the attachment of functional groups, groups which participate in the crosslinking reaction. It is also contemplated that one or more sites depicted in formula (Fl) as having non-functional methyl groups might instead contain a functional group and that R' and/or R 2 then may i comprise a non-functional group such as a methyl group or another monovalent hydrocarbyl or halogenated monovalent hydrocarbyl group as listed below.

Therefore, formula (F1) is intended merely to illustrate a "typical" polysiloxane polymer with terminal functional groups. The site of attachment of the two or more functional groups may be varied as desired and is not believed presently to be of essential importance to the practice of the present invention. The two or more functional groups are in general unsaturated aliphatic groups having 2 to 20 carbon atoms, such as alkenyl groups including vinyl, allyl, butenyl, propenyl, isopropenyl, and hexenyl groups or cycloalkenyl groups including cyclohexenyl, cyclopentenyl, cycloheptenyl and cyclooctenyl groups. A preferred unsaturated aliphatic group is "vinyl. Most preferably, both R' and R 2 are vinyl groups and are located in terminal positions as depicted in (Fl).

When special properties are needed, other non-functional monovalent hydrocarbyl and halogenated monovalent hydrocarbyl groups may be substituted for the methyl groups of formula For example, alkyl groups having 1 to 18 carbon atoms, methyl, ethyl, propyl, butyl, hexyl, dodecyl, octyl, and octadecyl; cycloalkyl groups having 5 to 7 ring carbon atoms, cyclohexyl and cycloheptyl; aryl groups having 6 to 18 carbon atoms, phenyl, naphthyl, tolyl, xylyl; aralkyl groups including benzyl, P-phenylpropyl, 0-phenylethyl, and naphthylmethyl; alkoxy groups having 0 to 18 carbon atoms such as hydroxy, methoxy, ethoxy, and dodecyloxy; and halo-substituted hydrocarbon groups such as dibromophenyl, SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 chloromethyl, 3,3,3-trifluoropropyl and chlorophenyl may be employed in place of all or some of the methyl groups of formula (F 1).

Another compound useful in this invention is a branched polysiloxane having the general formula: R i R v 4-m wherein each R' is a functional group or a nonfunctional group as defined above and wherein at least two but preferably not more than one-half of all the R 1 groups in the siloxane are functional groups, m represents 0, 1, 2, or 3, and n represents a number having an average value from 1 to about 10,000. It is understood that 10 compounds containing more than one branch point as depicted in (F1.1) may be employed.

A particularly interesting class of siloxane polymers useful as suitable •ethylenic compounds in this invention and which contain the functionality described in Fl. 1. are the MQ resins. These polymers contain tetrafunctional SiOa (Q units) 15 and RaRbRCSiO, (M units) where the R, Rb and R! are vinyl, methyl, phenyl, ethyl, hydroxy, or hydrogen. MQ resins where R' and Rb are methyl and Rc is vinyl are most suitable for use as ethylenic compounds in this invention. Typically these •would not be used as the only ethylenic compound in the formulation, but rather in combination with other ethylenic compounds, especially the vinyl terminated polydimethylsiloxane polymers shown in Fl where R' and R 2 are vinyl. The use of certain of these polymers in dental impression materials is disclosed in U.S.

5,403,885 and in the international patent application WO 93/17654.

The preferred amount of the polysiloxane component will vary depending upon the desired physical properties of the silicone composition (such as the desired uncured viscosity, cured hardness, etc.). In part due to the wide range of acceptable molecular weights for the polymer component and the many types of adjuvants which may be added to the polymer this amount will vary widely. The presently -16- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 preferred amount of polymer component is between 5% and 99% by weight. More preferably the polymer component is between 20% and 90% by weight. Most preferably the polymer component is between 20% and 80% by weight.

The crosslinker component contains at least two silicon-hydrogen linkages and can be a polymeric compound or a compound that is not polymeric. These compounds are well known in the art and are disclosed, for example in U.S. Patent Nos. 3,159,662 to Ashby; 3,220,972 to Lamoreaux; and 3,410,886 to Joy which are herein incorporated by reference.

Some classes of compounds having at least two silicon-bonded hydrogen atoms which can be used in the invention are: organohydrosilanes having the empirical formula,

(R

3 )Sic (F2) wherein each R 3 can be the same or different and represents an organic group, preferably selected from the group consisting of monovalent hydrocarbyl groups, monovalent alkoxy hydrocarbyl groups and halogenated monovalent hydrocarbyl groups, c represents an integer having a value at least 1, a represents an integer having a value at least 2, and the sum of a and b equals the sum of 2 and two times c; organohydrocyclopolysiloxanes having the empirical formula, *t HdR 3 (SiO)f (F3) wherein R 3 is as defined above, f represents an integer having a value from 3 to 18, d represents an integer having a value at least 2 and preferably less than or equal to f, and the sum of d and e equals two times f, and organohydropolysiloxane polymers or copolymers having the empirical formula,

(H)B(R

3 )hSijO(j-I) (F4) -17- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 wherein R 3 is as defined above, j represents an integer having a value from 2 to 10,000, g represents an integer having a value at least 2 and less than or equal to j, and the sum ofg and h equals the sum of 2 and two times j.

Among the groups represented by R 3 include, for example, straight-chain and branched alkyl groups having 1 to 18 carbon atoms, methyl, ethyl, propyl, butyl, hexyl, dodecyl, octyl, and octadecyl, cycloalkyl groups having 5 to 8 ring carbon atoms, cyclohexyl and cyclooctyl, aryl, aralkyl, and alkaryl groups having 6 to 18 carbon atoms, phenyl, naphthyl, tolyl, xylyl, benzyl and phenylethyl, and halo-substituted groups thereof chloromethyl, chlorophenyl, and dibromophenyl. Preferably, the R 3 group includes methyl and phenyl. The R 3 group can also be an unsaturated aliphatic group having 2 to 20 carbon atoms, such as alkenyl or cycloalkenyl, vinyl, allyl and cyclohexenyl. When the R 3 group is a group with aliphatic unsaturation, the silicon compound containing siliconoo hydrogen linkages can be reacted with itself to form a polymer.

15 Another compound having silicon-bonded hydrogen useful in this invention is a branched organohydropolysiloxane having the general formula: R 4 R Rm-Si SR4 4-m wherein each R 4 is as defined above for R and wherein at least two but preferably not more than one-half of all the R 4 groups in the siloxane being hydrogen, m represents 0, 1, 2, or 3, and n represents a number having an average value from 1 to about 10,000. It is understood that compounds containing more than one branch point as depicted in (F5) may be employed.

Also useful in the present invention as compounds containing a multiplicity of silicon-bonded-hydrogen groups and which contain the functionality described in are the MQ resins. These polymers contain tetrafunctional SiO,2 (Q units) and RdReRfSiOl2 (M units) where the Rd, and R'are vinyl, methyl, phenyl, ethyl, hydroxy, or hydrogen. MQ resins where Rd and R' are methyl and R f is hydrogen are most suitable for use as ethylenic compounds in this invention. Typically these -18- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCIUS95/08383 would not be used as the only crosslinker component in the formulation, but rather in combination with other crosslinker components, especially the organohydropolysiloxane copolymers shown in (F4).

The amount of the crosslinker component should be sufficient to provide the desired degree of crosslinking of the silicone composition. In part due to the wide range of acceptable molecular weights for the polymer component and/or the crosslinker component, it is presently believed that this amount is best described in terms of the ratio of SiH groups to functional vinyl) groups in the composition. The presently preferred ratio of SiH groups to functional groups is between 1:1 and 20:1. More preferably the SiH:F ratio is between 1:1 and 10:1. Most preferably the SiH:F ratio is between 1.3:1 and 4:1. The presently preferred amount of crosslinker component is between 0.2% and 90% by weight.

S" More preferably the crosslinker component is between 0.2% and 20% by weight.

Most preferably the crosslinker component is between 0.2% and 10% by weight.

Suitable hydrosilation catalysts for use in the present invention include those compounds which promote or facilitate the addition reaction between the ethylenic groups and the silicon-bonded-hydrogen groups. Examples of suitable catalysts include platinum or platinum compound catalysts exemplified by chloroplatinic acid, a complex ofchloroplatinic acid and an alcohol, a complex of platinum and an olefin, a complex of platinum and a ketone, a complex of platinum and a vinylsiloxane, colloidal platinum, a complex of colloidal platinum and a vinylsiloxane etc., palladium or palladium compound catalysts exemplified by tetrakis (triphenylphosphine) palladium, a mixture of palladium black and triphenylphosphine, etc.; or rhodium or rhodium compound catalysts. Also suitable for use in the present invention are radiation activated hydrosilation catalysts. For example, one may employ: (r1 4 -cyclooctadiene)diarylplatinum complexes (as described in U.S. Pat. No. 4,530,879, Drahnak, which is herein incorporated by reference); ('1 5 -cyclopentadienyl)trialkylplatinum complexes (as described in U.S.

Pat. No. 4,510,094, Drahnak, which is herein incorporated by reference); or cyclopentadienyl)tri(o-aliphatic)-platinum complexes and a sensitizer that is capable of absorbing visible light (as described in U.S. Pat. No. 4,916,169, Boardman et al., -19- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 which is herein incorporated by reference) with traditional vinyl-siloxane polymers and crosslinkers. Platinum or platinum compound catalysts are presently preferred.

Alternatively, Pt(II) beta-diketonate complexes as disclosed in U.S. Patent No.

5,145,886 or the photohydrosilation catalyst systems described in U.S. Patent application Serial Nos. 07/626,904 and 07/627,009 are suitable for use in the present invention.

For dental molding compositions, "Karstedt" type catalysts as described below are presently most preferred. Karstedt platinum catalysts are described in U.S. Patent Nos. 3,715,334, 3,775,452 and 3,814,730 which are herein incorporated by reference. In general, to produce a Karstedt catalyst, there must be utilized platinum halide, and a complexing material in the form of an unsaturated organosilicon material selected from: o unsaturated silanes having the empirical formula, Ri';Si;X. (F6) where R is free of aliphatic unsaturationad selected from monovalent hydrocarbon radicals, R' is selected from monovalent aliphatically unsaturated hydrocarbon radicals, X is a hydrolyzable radical, c is an integer having an average value of at least 1, b is an integer having an average value greater than or equal to 2, and the sum of a plus b plus z equals the sum of 2 and two times c for a linear or branched silane and the sum of a plus b plus z equals two times c for a cyclic silane; unsaturated linear or branched siloxanes of the empirical formula, RoR',SiOl&) (F7) where R and R' are as defined above, fis an integer having an average value of between 2 and 10,000, e is an integer having an average value greater than or equal to 2 and the sum ofd and e equals the sum of 2 and two times f and unsaturated cyclic siloxanes of the empirical formula, RdR'SifOf (F8) where R and R' are as defined above, e is an integer having an average value greater than or equal to 2, fis an integer having an average value from 3 to 18, and the sum ofd and e equals two times f SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 A Karstedt catalyst can be made by effecting contact between an unsaturated organosilicon material as defined by formula (F7) or (F8) above, and a platinum halide to provide for the production of a mixture having a concentration of available inorganic halogen, treating the resulting mixture of to effect the removal of available inorganic halogen, and recovering from a platinum-siloxane complex having available inorganic halogen of less than about 0.1 gram atoms of halogen per gram atom of platinum. Preferably the complex is substantially halogen free. As used herein, the term "available inorganic halogen," will designate halogen that can be detected by a modification of ASTM designation D-1821-63 for "Inorganic Chloride." The procedure is substantially as described, except there is utilized in place of acetone a mixture of glacial acetic acid and acetone. The procedure employed for determining gram atoms of platinum in the platinum-siloxane complexes was Atomic Absorption Spectrbscopy. For example, the method ofR. Dockyer and G. F. Hames, Analyst, 84, 385 (1959).

Radicals included by R in formulas F6, F7, and F8 are, for example, alkyl radicals such as methyl, ethyl, propyl, isobutyl, 2-ethylhexyl, dodecyl, etc.; cycloalkyl radicals such as cyclohexyl, cycloheptyl, etc.; aryl and alkaryl radicals such as phenyl, naphthyl, tolyl, xylyl, and the like; aralkyl radicals such as benzyl, tolylethyl, phenyipropyl, etc. Radicals included by R' in formulas F6, F7 and F8 are, for example, aliphatically unsaturated radicals such as ethynyl, 2-propynyl, etc.; Svinyl, allyl, 10-undecenyl, and cycloalkenyl radicals, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and the like.

Unsaturated silanes included by formula (F6) are, for example, tetravinylsilane, triallylmethylsilane, divinyldimethylsilane, trivinylphenylsilane, divinylmethylphenylsilane, divinylmethylethoxysilane, divinylmethylacetoxysilane, and the like.

Included by the unsaturated siloxanes of formula (F7) are, for example, disiloxanes of the formula, RShSiOSiR'h.R. (F9) -21- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCr[US95IOS383 where R, are as defined above, the sum of h and h' is an integer with a value of at least two; the sum of g and h is equal to 3; and the sum of g' and h' is equal to 3.

For example, there are included as disiloxanes of formula 1, 1 -divinyltetramethyldisiloxane, 1 3 -divinyltetramethyldisiloxane, hexavinyldisiloxane, 1,1,3trivinyitriethyldisiloxane, 1,1 3 3 -tetravinyldimethydisiloxane, l,34dvinyl,-l ,3dimethyL-1,3-diphenyldisiloxane, etc.

There are also included by the unsaturated siloxanes of formula (H8), cyclopolysiloxanes. For example, there is included 1,3,5-trivinyl- 1,3,5trimethylcyclotrisiloxane, l,3,5,7-tetrayl-1I, 3

,S,

7 -tetraphenylcyclotetasioxne, l, 3 -d~vnyloctamethylcyclopentasioxane, etc.

Preferably the above-described platmnum-siloxane complexes of platinum and organosiloxanes of formula (F7) and are made in accordance with the practice of the invention, as previously described, utilizing a platinum halide, and an unsaturated linear, branched or cyclic siloxane of formula (P7) or (F8) having at 15 least one structural unit of the formula,

R

where the unsatisfied valences of the above structural unit can be satisfied by R, Rand Oxygen radicals and where R and R! are as previously defined. Most preferably R! is a vinyl group.

The platinum halides which can be employed in the practice of the invention are, for example,

H

2 PtCI 6 *nH 2 O and metal salts such as NaHPtCI 6 -nH 2

O,

KHtC1 6 *nH 2 O, Na2PtCI 6 ,nH 2 Q, K 2 PtC4*nH 2 O. In addition, PtCI 4 *nH 2 O and platinous type halides such as PtCl 2 Na 2 PtCL4 nH 2 O, H 2 PtCL 4 nH 2

O,

NaHPtCL4-nH 2 O, KHPtCI 4 -nH2O, K2PtBr 4 and platinum halide complexes with aliphatic hydrocarbon as taught in Ashby Pats. 3,159,601 and 3,159,662, for example [(CH 2 =CH2)*PtC 2 2 (PtC1 2

*C

3 Ii 6 2 etc. may be employed. Other platinum halides which can be utilized are shown by Lamoreaux Pat. 3,220,972, such as the reaction product of chioroplatinic acid hexahydrate and octyl alcohol, etc.

-22- SUBSTITUT SHEET (RULE 26) WO 96/00560 PCT/US95/0g383 The amount of the platinum Complex component should be sufficient to provide the desired degree of crosslinicing of the silicone composition within a reasonable time. In part due to the wide range of acceptab~le molecular weights for the polymer component, it is presently believed that this amount is best described in terms of the ratio of Pt atoms to functional groups in the composition. The presently preferred ratio of Pt atoms to functional groups is between 1:2 and 1:2000. More preferably the Pt:V ratio is between 1: 10 and 1: 1000. Most preferably the Pt:V ratio is between 1:30 and 1:500. Preferably, the catalyst is present mnan amount from about 5 to about 1000 parts by weight per 1, 000,000 parts by weight of the total composition, more preferably from about 20 to 500 parts by weight per 1,000,000 parts by weight of the total composition.

A"cure-indicating dye" iadetohecrbecomposition to provide isaddtah ual visual indication of the extent of the hydrosilation reaction extent of the *wo crosslinlcing reaction). The cure-indicating dye exhibits a color change in the 15 presence of a silicon-bonded-hydrogen compound and a precious metal hydrosilation catalyst and is characterized in a curable composition by having a first CS color before the cure reaction is effected and a second color after the cure reaction has been effected. Here "color" is taken to include visible fluorescence. The first color and second color are different and may be observed readily in the composition using the naked eye or a suitable instrument such as a spectrophotometer, colorimeter, or fluorimeter. Preferably, the difference in color may be observed readily using the naked eye by comparing the composition's second color to a reference color standard a printed card, printed label or colored plastic part such as a colored plastic dental impression tray) that approximates either the composition's first color a color mis-match is observed) or, more preferably, the composition's second color a color match is observed). Similarly, the composition's second color may be compared to another composition that approximates the first composition's second color. For example, a commonly employed dental impression technique involves a "two-phase" system comprising a "1putty" material and a separate."wash" material. In the present invention, one may choose to add a cure-indicating dye to either or both materials. For example, one of -23- SUBSTrTT SHEET (RULE 26) WO 96/00560 PCT1US95/08383 these materials the wash) could Contain a cure-indicating dye and change color upon curing to match the unchanging color of the other material the putty). Alternatively, the putty and wash could each contain a different cureindicating dye (thus having different initial colors) and change color upon curing to "match" each other. More preferably, the color change is pronounced such that the color change may be readily "recognized" by an observer even without the need for a reference color standard.

The dye's first color before the cure reaction is effected) is typically fhirly intense and may occupy virtually any visibly observable chroma. The dye's second color after the cure reaction is effected) may be either a different color or be no color at all the cure-indicating dye has been- "bleached" to a colorless O S state and the natural color of the composition without the dye is observed). It is 0:0. also expected that a suitable cure-indicatig dye for use in the present invention may change from a visibly colorless state to a colored dye as a result of the curing 96006: 15 reaction. For example, a co lorless dye having strong near-infr-ared absorption may change to a visibly fight absorbing dye, etc. Change of fluorescence color or 0* inenit is another option.

*0 0 The color change of this invention is correlatable with the extent of the 0 hydrosilation reaction correlatable with the extent of cure of the curable 20 composition). The rate of color change can be adjusted depending on the particular cure-indicating dye employed, the amount of cure-indicating dye employed (relative 000 to the other active components of the composition), and/or whether other indicator adjuvants are present in the composition. Similarly, the time at which the color change occurs relative to the crosslinking reaction can be adjusted. As will be demonstrated below this makes it possible to provide compositions which reproducibly exhibit a color change at virtually any desired point in the cure reaction.

Two-part curable compositions typically are formulated to be "shelf stable" storage stable) for relatively long periods of time prior to being combined into one part. This may be accomplished, for example, by separating the catalyst component from the crosslinker component. The curing reaction is begun by mixing -24- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIus9s/osmS the two Parts together. This may be done manually by hand mixing or kneading the two Pastes together until one homogeneous paste is formed) or by employing a static mixer or other mechanical mixer.

The working time of a two-Part material refers to the time between the initiation of the setting reaction, when the vinyl-containing OrganOPOlYsioxane, the OrganOhydrOPOlYslxane and the platinum catalyst are mixed together, and the time the setting reaction has proceeded to the point at which it is no longer practical to perform filrther physical work upon the system, reform it, for its intended Purpose. When the reaction has Proceeded to this later Point the material is said to have reached its gel point. The working time Preferably provides enough time comfortably to mix and place the composition into its desired form but not so much time that the setting time is delayed unreasonably. For dental impression compositions the working time under conditions of use is Preferably greater than Seconds, more preferabl y greater than I minute and most preferably greater than 2 minutes. Longer working times may also be acceptable. An indication of the edo teworking time mybe accomplished by adjusting the timing of the color change to coincide with or just Precede the onset of the gel point of the material. This indication is very useful as it serves to warn the user visually of the onset of the gel and the finish of the working time. If desired, this color change can be adjusted to 20 occur a few moments before this gel point, thus providing a longer warning period .*and allowing the user time to huffy, if need be, to finish the procedure or operation. The setting time of an impression material refers to the time at which sufficient curing has occurred to allow removal of the silicone impression mater ial from the surface being replicated without causing permanent deformation of said 25 silicone. material. The setting time of a coating refers to the time at which sufficient cuighas occurred to allow the coating to be further processed or otherwise used for its intended purpose without physical damage to the coating. For an impression material, the setting time may be approximted by measuring the torque of the reacting composition by means of an oscillatory rheometer held at the desired temperature held at the same temperature as would be encountered in use).

As the material cures the torque value rises. When the torque reaches a maximum SUBSrrnyrE SHEET (RULE 26) WO 96/00560 PCTIUS95/0S383 value the material is said to be fully set. For practical use of dental impression compositions, and for purposes of this invention, the point in time where the torque reaches 90 percent of its maximal value is defined as the setting time (this time is also referred to as In general, shorter setting times are preferred over longer setting times. For dental impression compositions the setting time is preferably less than 10 minutes. More preferably the setting time is less than the sum of 5 minutes plus the working time. Most preferably the setting time is just longer than the desired working time. An indication of the arrival of the set time may be accomplished by adjusting the timing of the color change to coincide with or come just after the set time of the material. This visual indication is very useful as it serves to prompt the user of the achievement of the set and prevents undesirable and inadvertent removal or distortion of the material prior to its being completely set. If desired, this color change can be adjusted to occur a few moments after the set time, thus providing a safety margin.

15 For dental impression materials a cast of the dental tissue is often fabricated by pouring a liquid plaster, wax, or other hardenable material a curable liquid .epoxy material) into the set impression. Unfortunately, the surface of the cast can be marred if the impression material evolves gas during the time that the casting material is in contact with the impression and is itself hardening. The evolved gas can form bubbles on the surface of the casting material and displace the casting material from the surface being replicated forming a permanent defect in the cast.

To avoid this problem it is customary to delay the pouring of the cast until well after the impression material is considered fully set. This allows the impression material to completely de-gas before the casting material is poured into the impression. An indication of the arrival of this desired "pour time" might be accomplished by adjusting the timing of the color change to coincide with or come just after the end of deleterious gas evolution. This visual indication would be very useful as it would serve to prompt the user when the impression is safe to "pour up" and would prevent undesirable and inadvertent pouring of the casting material prior to complete gas evolution from the impression material.

-26- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 In addition to monitoring the over-all cure reaction of a curable composition, the cure-indicating dye can also be used to indicate smaller localized regions on a curable composition where incomplete curing may have taken place. A recurring problem in dental impression making involves localized "poisioning" of the impression material which can delay or prevent curing of the material. This can occur, fbr example, when a "poison" is transferred from the surfatce being replicated to the impression material. This can happen when the dentist or assistant touches the surface of the tooth being impressioned with a contaminant and the contaminant then contacts the impression material. A common source of contaminant is a latex glove worn by the health care provider. The contaminants found on many latex gloves can delay or inhibit the cure of the silicone impression material. Another common source of contaminant includes acrylate-based and methacrylate-based 0 0.:dental composites and adhesives. Unfortunately, the transfer of a contaminant to the tooth surface cannot always be observed readily by the dentist. Likewise, o. 15 localized defects caused by such contaminants may not be observed readily by looking at impressions made from traditional impression materials. However, if this localized delay occurs at a critical area the impression may be ruined, by not accurately representing the tooth being impressed, thereby causing a defective *appliance crown) to be produced. By using the cure-indicating dye of the present invention the health care provider can observe immediately any areas of the impression material that were contaminated. This can be accomplished visually by observing the surface of the impression material after it has been taken out of the :mouth. If any areas exhibit unchanged color (or not completely changed color 0.0 within about 30 seconds) then the* impression may be bad and should be retaken.

This saves the expense of making a crown or appliance that does not fit properly. In addition, the dentist thereby can detect recurring problems in his or her technique and adjust accordingly. Notably, certain regions of the impression may, even under optimal conditions, change color later than other regions. For example, the surface of a tooth is somewhat cooler than the surrounding gum tissue. This can cause the impression material adjacent to the tooth to set more slowly than the impression material adjacent to the gum tissue. This time delay is normally very short.

-27- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383

S.

S

For coating compositions the cure-indicating dye may be employed to monitor (on-line or off-line) the coating process. Extent of cure, uniformity of cure, or overall coating quality may be monitored effectively by observing the composition's color. Preferably, a bleaching reaction will be employed in order to permit more thorough inspection and/or be inconspicuous for the intended use. For example, if one or more regions of the coating are not adequately cured after being exposed to heat or visible or UV radiation) the color of the cure-indicating dye will remain unchanged. In addition, incomplete coatings may be similarly detected.

As previously mentioned, the cure-indicating dye provides a visual indication of the extent of cure of a curable composition. The color change of a dye may be observed using a suitable detection device such as an instrument a spectrophotometer, fluorimeter or colorimeter) or the human eye. Depending on the intended use of the curable composition one or another detection device might be preferred. For example, for dental impression materials it is believed that observation of the color change will ordinarily be made by the naked eye (or optionally with assistance of corrective eyewear). For coating compositions coatings on films used as release liners) it is believed that an off-line or on-line instrument can be utilized effectively to monitor the color change, and thus the cure, of the coating.

The amount of color change exhibited by the dye in a given composition need be only that amount of change that can be accurately measured or recognized by the detection device. It is understood that an instrument such as a spectrophotometer can detect fairly small color changes reproducibly. In contrast, the human eye may not notice or "remember" small color changes, especially when lighting is variable, although the human eye can detect very small color differences when two colors are compared directly side by side comparison using a reference standard color). For dental impression materials the amount of color change is preferably sufficient that when one compares two colors side-by-side using the human eye a color difference is observable. More preferably, the color difference is readily observable, the difference is recognized after just a short -28- SUBSTIUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/08383 observation time. Most preferably, the color change is observable without reference to a side-by-side comparison. That is, the observer can detect and recognize a difference between the second color and the "remembered" first color of the composition.

If desired, the recognition of a color change can be facilitated by providing a conveniently-located reference first or second color standard. The observer can compare the composition's color with the reference first or second color standard.

This allows the observer to detect the color change more easily. If the reference standard matches the first color of the composition, the observer will detect a small change in color of the composition away from the reference first color standard.

This first observation of a color difference can be used as the indication point of interest. If the reference standard matches the second color of the composition, the observer will be presented initially with a contrast in color between the reference :standard and the curable composition a color mismatch). This difference will become smaller, and preferably eventually disappear, as the composition cures.

When the two colors eventually match the dye will have reached its second color and the indication point will have been obtained.

The reference standard may be provided, for example, as a separate color "chip" or printed card. This chip or card may be held against the curing composition 20 for side-by-side comparison. Alternatively, for convenience when using dental impression materials, the reference standard may be applied directly to an impression tray as a paint or label or as the natural color of the molded impression tray).

If desired the curable composition may also comprise an additional cureindicating dye or dyes the composition may comprise two or more different cure-indicating dyes). The additional cure-indicating dye or dyes may be used to provide additional indication points or to enhance one indication point. For example, a second cure-indicating dye and the first cure-indicating dye can together provide a first color to the curable composition before curing has occurred).

The first cure-indicating dye can be tailored to monitor one. point in the cure reaction the extent of working time) and the second cure-indicating dye can -29- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08393 be tailored to monitor a different point in the cure reaction the setting time).

When the composition reaches the gel point the extent of the working time) the first cure-indicating dye changes color or is bleached. This is observable as a color change in the composition (the composition retains the color of the second cure-indicating dye and any remaining color from the first cure-indicating dye). As the reaction proceeds and the set time is reached, the second cure-indicating dye changes color causing the composition to exhibit a third and final color.

In addition, if desired the curable composition may also comprise an additional non-cure-indicating dye or pigment. The non-cure-indicating dye or pigment modifies the color of the composition from its natural state and may combine with the first color of the cure-indicating dye to provide a first composition color that differs from both the first cure-indicating dye color and the natural S• composition color. For example, it is well known that a blue dye and a yellow dye will provide a green color. If the blue dye is a cure-indicating dye a dye that 15 changes from blue to colorless when the indication point is reached) and the yellow dye is a non-cure-indicating dye, the composition will have a green color initially and at the point of interest change to a yellow color. Other combinations of colors can be employed, depending on the desired color change and/or desired initial or final color.

20 The cure-indicating dye should be present in an amount sufficient to provide a visual indication of the extent of the hydrosilation reaction. The amount of cureindicating dye needed will depend on a number of factors including the natural color of the composition and the desired amount of color change less color change may be needed when the detector is more sensitive, more color change may be needed when the color change is poorly visible). In addition, the amount of dye needed will also depend on the dye's tinctorial strength. The cure-indicating dye should have enough tinctorial strength to color the composition effectively and provide for the necessary color change. A common measure of tinctorial strength is the dye's "extinction coefficient." In general, higher extinction coefficient dyes are preferred due to their greater contribution per molecule to color. Lower extinction coefficient dyes, while not preferred, may nevertheless be employed, usually at SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 somewhat higher concentration. Preferred cure-indicating dyes for use in the present invention have a molar extinction coefficient in the visible spectrum of at least 1,000 M'xcm-', more preferably at least 10,000 N'xcm"', and most preferably at least 30,000 M'xcm' 1 For use in dental impression materials, the amount of dye preferably should be a sufficient amount such that the dye's contribution to the composition's color can be easily observed using the naked eye. Preferred impression materials comprise between 0.0001 and 0.1 weight cure-indicating dye (based on the total weight of the curable composition and when normalized to a dye having a molar extinction coefficient of 32,000 M' xcm'), more preferably between 0.0003 and 0.03 weight cure-indicating dye, and most preferably between 0.001 and 0.015 weight cure-indicating dye. Those skilled in the art of dye chemistry will understand that for dyes with a lower molar extinction coefficient :'correspondingly greater amounts of cure-indicating dye will be required to achieve the same color intensity as a cure-indicating dye with a higher molar extinction 15 coefficient. Preferred coating compositions comprise between 0.0002 and 0.2 weight cure-indicating dye (based on the total weight of the coating composition but not including the weight of any volatile solvents that are not present when the coating's color is to be observed and when normalized to a dye having a molar extinction coefficient of 32,000 M'xcm'), more preferably between 0.0006 and S: 20 0.06 weight cure-indicating dye, and most preferably between 0.002 and 0.03 weight cure-indicating dye. A maximum effective amount of a cure-indicating dye is an amount sufficient to allow visible (or, optionally, near-infrared) radiation to penetrate the coating to its full depth and provide a maximal signal consistent with there being a measurable signal from the entire working depth of the coating.

Amounts in excess of an effective amount will tend to absorb all of the visible radiation in the upper portion of the coating and may provide no useful signal from the lower portion to indicate its thickness or extent of cure. When color is bleached upon cure, it becomes possible to monitor at greater depths. Amounts less than the maximum effective amount may be highly satisfactory or even preferred if it is desired that the coating weight be directly proportional to the initially measured or the final signal.

-31- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PTU9/88 PCTIEJS95/08383 Preferred cure-indicating dyes change color very rapidly when the indication time the working time, setting time, etc.) has been reached. The time between the onset of color change and the completion of the color change is referred to as the "transition time". For dental impression materials a "typjical working time is measured in minutes 0.5 to 2 minutes). Based on this time frame preferred cure-indicating dyes used to monitor working time change color within a one minute peiod, more preferably within a 30 second period. Similarly, typical dental imreson materials have a set time of 3 to 7 minutes. Based on this time frame preferred cure-indicating dyes used to monitor set time change color within a three minute period, more preferably within a two minute period, most preferably within a one minute period. When longer indication times are being monitored, a longer transition time the time over which the cure indicating dye exhibits a change of color) can be tolerated. For coating compositions, preferred cure-indication dyes 15 change color rapidly and most preferably exhibit a complete color change prior to the winding of the coated article. In this manner an inspection of the coated article may be made "on-line." In addition to the above-mentioned requirements, the cure-indicating dye (which may be a liid or solid) should be, and preferably is, soluble or dispersible in the composition being colored. A "soluble" cure-indicating dye, as used herein, is 20 a cure-indicating dye that when mixed with the initial or uncured composition (including any optional solubilizing agents, cosolvents; or surfatctants, that are present in the composition) under the desired conditions of use dissolves to form a homogeneous colored mixture. Such conditions of use include temperature over the temperature range encountered during use and cure of the composition), time the amount of time the composition is in the uncured state), and concentration the concentration of cure-indicating dye in the composition).

A

"dispersible" cure-indicating dye, as used herein, is a cure-indicating dye that when mixed with the composition (including any optional solubilizing agents, e.g., cosolvents or surfactants, that are present in the composition) under the desired conditions of use forms a macroscopically homogeneous colored mixture. The dye may be in the form of very small particles suspended in the composition, form a -32- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 two-phase system where one phase consists of finely divided particles (often in the colloidal size range) distributed throughout a bulk substance, the particles being the disperse or internal phase and the bulk substance the continuous or external phase.

The dye particle should be small enough that the dye colors the mixture and is capable of interacting with the composition to change color as desired. An "insoluble" or "nondispersible" dye proposed for cure-indication purposes, as used herein, is a potentially-cure-indicating dye that when mixed with the composition (including any optional cosolvents that are present in the composition) under the desired conditions of use forms a macroscopically heterogeneous mixture. A macroscopically heterogeneous mixture, as used herein, includes phase-separated liquid/liquid systems oil and water); two-phase systems comprising a granular or powdery solid phase in a liquid; and two-phase systems comprising a suspension of large particles in a liquid, wherein the large particles do not color the composition or do not interact with the composition to change color as desired.

1 15 As previously mentioned the composition containing the cure-indicating dye may optionally comprise one or more suitable cosolvents. The cosolvents may be employed to facilitate the dissolution or suspension of the cure-indicating dye and/or other adjuvants in the composition, to facilitate uniform mixing of the reactants, or to adjust the composition's viscosity or flow. Suitable cosolvents for 20 use with silicone compositions include aromatic hydrocarbons, such as xylene and toluene, aliphatic hydrocarbons, such as hexane and mineral spirits, and halogenated hydrocarbons, such as chlorobenzene and trichloroethane. It is desirable that the solvent be transmissive to visible light. The composition preferably contains less than about 70 weight percent cosolvent, more preferably less than 40 weight percent cosolvent, and most preferably less than about 10 weight percent cosolvent.

Preferred cure-indicating dyes are soluble or dispersible, more preferably soluble, in the curable composition without the presence of a cosolvent. The solubility or dispersibility of a dye can be adjusted, if needed or desired, by several means. For example, an otherwise insoluble or nondispersible dye may be "tethered" to another compound that has the necessary or desired solubility or dispersibility in the composition. Preferably, the tethered dye molecule will have characteristics of -33- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT1US95/08383 both compounds the cure-indicating properties of the dye and the solubility characteristics of the other compound). The attachment or tethering may be covalent or ionic. For example, if ionic tethering is employed one may associate an otherwise insoluble cationic or anionic dye to a suitably soluble anion or cation, respectively. The tethering ion may be itself attached to the curable polymer.

Alternatively, an otherwise insoluble neutral dye may be covalently attached to another component to render the resulting larger molecule soluble or dispersible in the composition. Typically this may be done by attaching the insoluble dye to the molecules of the composition, attaching the dye to the curable silicone polymer. Of course, one may also attach a soluble dye to the molecules of the composition. This may be desired in a situation where it is important that the dye not "leach out" or "bloom" from the cured composition where toxicity or environmental issues are of concern).

Suitable cure-indicating dyes ar soluble or dispersible, more preferably 15 soluble, in the curable c~mposition (including any optional solubilizing agents, e.g., cosolvents or surfactants, that are present in the composition) at a concentration sufficient to color the composition effectively. Preferably, the cure-indicating dye is :soluble or dispersible in the composition at a concentration sufficient to color the composition effectively without the need to employ a cosolvent. More preferably, 20 the cure-indicating dye is soluble or dispersible at a sufficient concentration such that the dye's contribution to the composition's color can be observed readily using the naked eye (or for a coating compositions using a suitable detection device).

As previously mentioned, suitable cure-indicating dyes for use in the present invention exhibit a color change in the presence of a multiply-silicon-bondedhydrogen compound, a multiply-ethylenic compound, and a precious metal hydrosilation catalyst when the aformentioned compounds are allowed to react under the desired conditions of use time, temperature, concentration in the composition, etc.). A simple and effective method of testing whether a particular dye is potentially suitable for use in the present invention not yet considering solubility/dispersibility issues) involves mixing the dye with the following model compounds and observing whether or not the dye exhibits a color change. This -34- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 model system differs substantially from the conditions that occur in a curable composition, since this model system does not undergo a "curing" reaction.

Furthermore, and notably, a solvent system is used instead of the polymer composition of a curable composition. Dyes are evaluated according to the following test method (hereinafter referred to as the "pentamethyldisiloxane test").

First, 500 pg (micrograms) of dye is transferred to a 6 pl clear-glass, screw cap vial.

Five hundred pl (microliters) of dichloromethane is then pipetted to the vial, followed by 100 pl of pentamethyldisiloxane. The dye, dichloromethane and pentamethyldisiloxane are mixed until homogeneous. To this solution is added an effective amount of a "hydrosilation catalyst solution." Suitable hydrosilation catalyst solutions and suitable effective amounts of such catalyst solutions for use in this test include the following catalyst solutions: 25 pl of a catalyst solution comprising 25% by weight of a commercially available catalyst (PC075, available from United Chemical Technology, Inc., Bristol, PA) in dichloromethane; 10 p1 15 of a commercially available catalyst solution (PC072, available from United Chemical Technology, Inc., Bristol, PA); or 10 pl of a Karstedt-type catalyst solution in toluene, wherein said catalyst comprises a complex ofPt" and equivalents (1.5 g mols per g atom Pt) of divinyltetramethyldisiloxane and wherein said solution has between about 2 and 3 weight percent platinum. The United 20 Chemical Technology catalyst solutions are further described at page 268 in Silicon ~Compounds Register and Review Silicones Silicon-Containing Polymers Edition, edited by Roy Anderson, G. L. Larson and Craig Smith, Huls America Inc., Piscataway, NJ, which is herein incorporated by reference. The Karstedt-type catalyst solution in toluene is further described in Preparatory Example Ib and on page 13 of "Aspects of Some Divinylsiloxane Complexes of Platinum and Rhodium," PhD thesis by Nicholas John William Warhurst, University of Sussex, March 1990, which is herein incorporated by reference. The vial is capped, agitated for approximately 5 seconds at room temperature (25°C) and the solution observed for color change (e.g.,bleaching). Those dyes that exhibited a significant color change bleaching) within 24 hours and preferably within less than about minutes under these conditions are believed to be suitable candidates for use in the SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT7US95/08383 present invention (subject to their having the desired solubility or dispersibility in the composition as discussed above). To verify that the above test is being performed correctly that the selected catalyst solution is active), one may repeat the above test using a dye which has been demonstrated to bleach under these conditions. For example, dye #2 of Table la is known to bleach in less than about 10 minutes under these conditions and is a suitable dye for use in this invention. In the event that the dye is not soluble in 500 pl of dichloromethane, then one may either utilize additional dichloromethane sufficient to dissolve the dye) or utilize a different solvent which is capable of dissolving the dye, and which is verified to not interfere with the bleaching of dye #2 as indicated above.

The amount of color change exhibited by a particular cure-indicating dye may be measured using a visible light spectrophotometer in conjunction with the above test. A small-volume short-path-length cuvette containing 500 mg of dye, 500 ml of dichloromethane, and 100 pl of pentamethyldisiloxane is positioned in the 15 spectrophotometer and measured for its absorptivity to visible, near-UV and near IR light. The path length (or if necessary the amount of dye) is chosen to provide absorbance less than 4.0 at The absorbance is compared to that of a similar o solution, but that contains 10 or 25 pl, as appropriate, of the previously mentioned catalyst solutions and has been allowed to "bleach" for about 10 minutes as 20 described above). Preferred cure-indicating dyes for use in the present invention exhibit a 10-fold decrease in absorbance (as measured at when tested in this manner a loss of 90% in absorbance). More preferred cure-indicating dyes for use in the present invention exhibit a 100-fold decrease in absorbance when tested in this manner a loss of 99% in absorbance). Most preferred cure-indicating dyes exhibit a 10-fold or 100-fold decrease in absorbance in less than about minutes when tested in this manner.

A simple and effective method of establishing approximate timing signaled by a cure-indicating dye involves mixing the dye with the following model curable composition and observing whether or not the dye exhibits a color change at or near the time when the model curable composition sets, as determined by laboratory testing such as oscillatory rheometry. The model curable composition contains -36- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 compounds selected to perform the function of the catalyst, the SiH compound, and the polymer compound. Dyes are evaluated according to the following test method.

First, approximately 500 ig of dye is transferred to a 6 ml clear-glass, screw cap vial. One ml of stock composition B 1 from Preparatory Example 2 is transferred to the vial via pipette or dropper, the solution is mixed with a spatula for 3 minutes and the mixture is examined visually for coloration of the resin and general solubility of the dye. If necessary, 1 2 drops (approximately 0.015 to 0.03 gins) of dichloromethane may be added to promote the solubility of less soluble dyes. One ml of stock composition C2 from Preparatory Example 2 is transferred to the vial and mixed with a small stick. The composition is placed against a white background and examined visually and manually for the time at which gelation occurs (as evidenced by an increase in viscosity and minimal flow when the vial is inverted) and the time at which the color changes. Those dyes that exhibit color change bleaching) within 2 times the gel time are believed to be candidates for use in the 15 present invention. This procedure may be repeated with various types and amounts of additives to adjust the time of color change for the intended use.

While not intending to be bound by theory, it is believed presently that suitable cure-indicating dyes include those dyes that are reduced catalytically go hydrogenated) in the presence of a silicon-bonded-hydrogen compound and a 20 precious metal hydrosilation catalyst when the aformentioned compounds are allowed to react under the desired conditions of use considering time, temperature, concentration in the composition, etc.). These reactions are exceedingly difficult to study in detail. It is presently believed that the reduction of a the cure-indicating dye affects the chromophore of the dye, interrupting conjugation and thereby altering its apparent color. For example, it is known to the inventors that 2 -Chloro-4-[[ 2 -methyl-4-(diethylamino)phenyl]imino]-2,5-.yclohexadien- 1-one is reduced to 2 -Chloro-4-[[2-methyl-4-(diethylamino)phenyl]amino]-l -phenol in the presence of the silicon-bonded-hydrogen compound acting as a source of hydrogen, and a precious metal hydrosilation catalyst.

For dyes capable of cure-indication, it is believed that there is a competition for different reaction pathways involving the organohydropolysiloxane crosslinker.

-37- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 In a first pathway the SiH groups on the crosslinker react with the unsaturated groups on the organosiloxane, catalyzed by the Pt catalyst, to effect hydrosilation.

In a second pathway the SiH groups on the crosslinker react with other SiH groups (or with sources of protons such as acids), also catalyzed by the Pt catalyst, to generate hydrogen gas. In general the first pathway is dominant when the three ingredients vinyl polymer, organohydropolysiloxane crosslinker, and Pt catalyst) are first mixed. As the reaction proceeds the concentration of unsaturated groups falls dramatically relative to the generally more abundant SiH groups and the reaction pathway begins to favor hydrogen gas production. The hydrogen gas, in the presence of Pt catalyst, is believed to reduce (by catalytic hydrogenation) certain (and perhaps all) of the cure-indicating dyes of the present invention, resulting in a change in color of the dye. It is also believed that the propensity of the dye to be *oo 0reduced has a strong impact on the timing of the color change in relation to the timing of the hydrosilation cure reaction). Dyes that are very easily reduced as 15 indicated by cyclic voltammetry) will generally react and change color sooner than dyes which are less easily reduced. Other factors such as the ratio between SiH groups and unsaturated groups and/or the presence of adjuvants affect the relative rates of hydrosilation and hydrogen production. In this way the color change may be adjusted to coincide with the desired point in the curing reaction.

20 Suitable dyes for use in the present invention may be classified by their reducible chromophore into several generic groups. Representative of these groups include indoaniline dyes, indophenol dyes, quinone monoimine dyes, quinone diimine dyes, cyanine dyes, merocyanine dyes (a hybrid of a true cyanine dye and a true oxonol dye), cyclohexadienone dyes, iminocyclohexadienone dyes, imidazolylidinecyclohexadienone dyes, dihydronaphthalenone dyes, iminodihydronaphthalenone dyes, imidazolylidinedihydronaphthalenone dyes, cyclohexadienimine dyes, sulfone dyes including: aryl substituted bis trifluoromethylsulfonylhexatrienyl dyes, aryl substituted bis (trifluoromethylsulfonyl)butadienyl dyes, aryl substituted bis (fluorosulfonyl)hexatrienyl dyes, and aryl substituted bis (fluorosulfonyl)butadienyl dyes, oxazolone dyes, and ionic dyes including cationic dyes, anionic oxonol) -38- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 dyes, and betaine dyes. By "cationic dye" is meant an ionic dye having a cationic chromophore. By "anionic dye" is meant an ionic dye having an anionic chromophore. Neutral azo dyes and anthraquinone dyes, which do not pass the pentamethyldisiloxane test previously described, are not now believed to be suitable for use in the present invention.

As is well understood in this area, substitution is not only tolerated, but is often advisable. As a means of simplifying the discussion and recitation of certain terminology used throughout this document, the terms "group" and "moiety" are used to differentiate between chemical species that allow for substitution, or which may be substituted ("group"), and those which do not so allow or may not be so substituted. Thus when the term "group" is used to describe a chemical substituent, the described chemical material includes the basic group and that group with conventional substitution. Where the term "moiety" is used to describe a chemical compound or substituent, only an unsubstituted chemical material is intended to be 15 included. For example, the phrase "alkyl group" is intended to include not only pure open-chain, branched, and cyclic hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl, adamantyl, octadecyl, and the like, but also alkyl substituents bearing further substituents known in the art silicon substituted, oxygen substituted, etc.). On the other hand, the phrase "alkyl moiety" is limited to the inclusion of only pure open-chain, branched and cyclic hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl, adamantyl, octadecyl, and the like. As used herein, a "hydrocarbyl-containing S: group" is intended to include not only pure open-chain, branched, and cyclic hydrocarbyl substituents but also hydrocarbyl substituents which bear further substituents known in the art silicon substituted, oxygen substituted, etc.) and/or which are linked to the basic compound by means of a heteroatom other than carbon sulfur, oxygen, nitrogen and silicon).

One class of particularly suitable dyes may be represented by the following general formula (F11): -39- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/08383 wherein each R.

2

R

3 and R' group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, preferably each R 2

R

3 and W. group is independently selected from the group consisting of: hydrogen, halogen, a C,-C~o AAkl a Cr-C~o alkoxy, a C 3 cycloalkyl, a C 6 aryl, a (2 6 -Cis aryloxy, a C 6 -Cis hydroxyaryl, a C 6 -Cis arylcarboxy, a C 6 carboxyaryl, a Cz-C 8 alkenyl, a C,-C 2 o allkmino, a C 6

-C,

8 arylamino, a C 6 -Cis aminoaryl, a.C2-C~ ~difhydromabyl~amino, carboxamide

(-C(O)NR'R

2 and wherein R' and W or and .my be connected to form a sauaed or unsaturated ring, for example, R 3 10 and R'may be joined by or be a -C 6 11-, -(CH 2 3 or -C 3

H

3 N- moiety, more ~Preferably each R W 3 and W. group is independently selected fr-om the group consisting of hydrogen, halogen, a C,-C, 0 alkyl, a CI-Cio alkoxy, a Cs-Cs cycloalkyl, a C 6 -Ci aryl, a C2-C, 0 alkenyl, and a C,-Clo alkylamino, and wherein R.' and R or W. and RW groups may be connected to form a saturated or unsaturated to 8 member ring, for example, R 3 and RW may be joined by a -C 4 or -CMH 3

N-

moiety; most preferably each R R 3 and W. group is independently selected from the group consisting of: hydrogen, methyl, ethyl, propyl, tert.-butyl, methoxy, ethoxy, isopropoxy, tert.-butoxy, a Cs-C, cycloalkyl, a C 6 -Cl 0 aryl, a C2-CIO alkenyl, a C,-Cio alkylamino, chlorine, and bromine, and wherein R 3 and W. may be joined by a -C4H4- or -C 3

H

3 N- moiety; A is 0, S, or NR22, wherein e~ is hydrogen, a hydrocarbyl-containing group, or a heterocyclic group, preferably R22is a group selected from the group consisting of: hydrogen, a C 1

-C

20 alkyl, a C 3 -CIS cycloalkyl, a C 6 -C~g aryl, a C 2 -CI& alkenyl, a C 6 arylamino, and substituted sulfonyl; more preferably R22is selected fr-om the group consisting of hydrogen and -SOC 6 QHs; and SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08393 B is any group capable of providing extended conjugation, thereby rendering the dye capable of absorbing visible, near-UTV, or near-infrared radiation including groups of formula D, E, F, H, or J, wherein D is represented by formula (F 12): Ra

R

9 wherein: each R 5 and R! group is independently hydrogen, halogen, a hydrocarbyl-contiing group, or a heterocyclic group, preferably each R 5 W, k 7 le, and R! group is independently selected from the group consisting of~ hydrogen, 10 halogen, a C 1 -C~o alkyl, a C 1 -C~o alkoxy, a C 3

-C

1 cycloalkyl, a C 6 -Cix aryl, a (2 6

-C

1 aryloxy, a C 6 -Cis hydroxyaryl, a C 6 -CI8 arylcarboxy, a C 6

-C

1 carboxyaryl, a C 2

-C

1 alkenyl, a Ci-C 2 D alkylamino, a C 6

-C

1 arylaxnino, a C 6 -Cis aminoaryl, a C 2 -C~o di(hydrocarbyl)amno, morpholino, and allamido and wherein any two adjacent

R

5

R

6

R

7 R8, and R! groups may be connected to form a saturated or unsaturated ring, for example, R5and W' or R 6 and R 7 may be joined byorbe -C4L r

C

3

H

3 N- moiety; more Preferably each W 5 e 6

R

7 R8 and R! group is independently selected from the group consisting of: hydrogen, halogen, a Ci-Clo alkyl, a C 1

-C

10 alkoxy, a Cs-Cs cycloalkyl, a C 6

-CI

0 aryl, a C 6 aryloxy, a CrCio alkenyl, a C,- Cio alkyilaniino, a C6-Cig arylamino, a C 2 -C~o di(hydrocarbyl)mino, morpholino, and ailcylamido and wherein any two adjacent Re, k 7 and R! groups may be connected to form a saturated or unsaturated 5 or 6 member ring; most preferably each R 5 Re, R 7 R' and R9 group is independently selected from the group consisting of: hydrogen, methyl, ethyl, piopyl, butyl, methoxy, ethoxy, propoxy, a Cs-C, cycloalkyl, a C 6

-CI

0 aryl, benzyloxy, naphthyloxy, a C 2

-C

10 alkenyl, N,Ndialkylamino, N-alkcyl-N-arylaniino, -N(Et)[((CH 3 3

C)

2

(CH

31 SiOCH2CH 2 -41- SUBSTITTE SHEET (RULE 26) WO 96/00560 WO 9600560PCrf[JS95I08383 chlorine, bromine, morpholino, and alkylarnido and wherein R' and R(6 or R 6 and R 7 may be joined by or be a -C 4

H

4

-(CH

2 3 or -C 3 K1 3 N- moiety; E is represented by formula (F 13): R"

X

wherein: XI is C(RI)2, S, NR', or 0, more preferably X1 is S or 0, most preferably X, is S;

X

2 s 2 5,NR 2 ,or 0, more preferably X 2 is or NR',ms preferably X 2 is NRf1* 2 and each R 10 R'and R' group is independently hydrogen, a hydrocarbyl- 10 containing group, or a heterocyclic group, preferably each R' 0 R" and R 1 2 group is independently selected from the group consisting of: hydrogen, a C 1

-C

2 0 ailkyl, a C 1

C

20 aloxy, a C 3 -CII cycloalkyl, a C 6

-C

18 aryl, a CC, aryloxy, a C 6

-CI

8 hydroxyaryl, a C 6

-C

12 arylcarboxy, a C 6 -CI8 carboxyail, a CrCI& alkenyl, a C,-C 20 alkylarnino, a C 6 -Cs arylainino, a C 6

-C

1 aininoaryl, a C 2

-C

2 D di(hydrocarbyl)aniino, and wherein R 1 0 and R" may be connected to form or be a ring; more preferably each R1 0 R" and R 1 2 group is independently selected from t he group consisting of: hydrogen, a'Cl-Clo alkyl, a C 1 -Clo alkoxy, a Cs-Cs cycloalkyl, a C 6 -Clo aryl, a Cr

C

10 alkenyl, and a Ci-Cio alkylainino, and wherein R1 0 and R" may be connected to form or be a ring; and most preferably each R1 0 R" and R 12 group is independently selected from the group consisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a Cs-Ca cycloalkyl, a C 6 -CIO aryl, a Cr-Clo alkenyl, a C 1 Cl 0 allcylaniino, chlorine, and bromine, and wherein any two adjacent W 10 and

R

12 groups may be joined by or be a -C 4

H

4 -(Gil 2 3 or -C 3

H

3 N- moiety; -42- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 F is represented by formula (F 14): 14 3 R Ris/ O wherein: X' is N or CR'6; and each R 3 R1, R 1 5 and R" group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two adjacent R R and R" groups may be connected to form a ring, preferably each R 13

R

15 and R1 group is independently selected from the group consisting of: hydrogen, halogen, a C-C2o alkyl, a C 1 -C2 alkoxy, a C 3 -Cs cycloalkyl, a C 6

-C

1 aryl, a C-C 1 s aryloxy, a Cs-Cs hydroxyaryl, a C 6

-C

1 s arylcarboxy, a C-C carboxyayl, a CrCis alkenyl, a C-C2o alkylamino, a C 6

-C

13 arylamino, a C 6

-C

1 s aminoaryl, a CrC2 di(hydrocarbyl)amino and wherein any two adjacent R 13 and R' 6 groups may be connected to form a ring; more preferably each R R" and R' 6 group is independently selected from the group consisting of: hydrogen, halogen, a C,-Clo alkyl, a CI-Clo alkoxy, a Cs-Cs cycloalkyl, a C 6 -Cio aryl, and a C2-Cio alkenyl; and most preferably each R' 3

R

4

R

5 and R' 6 group is independently selected from the group consisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a Cs-Cs cycloalkyl, and phenyl; H is represented by formula (F 16): R

N

R21 N -43- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95108383 wherein: each 1&and R 2 group is independently hydrogen, halogen, a hydrocarbylcontaining group, or a heterocyclic group and wherein and R 2 may be connected to form a ring, preferably each R20 and e' group is independently selected from the group consisting of: hydrogen, halogen, a C 1

-C

2 o alkyl, a C,-C2D alkoxy, a C 3

-C

1 cycloalkyl, a C 6

-C

1 aryl, a C 6

-C

18 aryloxy, a C 6

-C

13 hydroxyaryl, a

C

6 -Ciu arylcarboxy, a C 6

-C,

8 carboxyaryl, a C 2

-C,

8 alkenyl, a C,-C 2 o alkylantino, a

C

6

-C

1 arylamino, a Cs-C, 3 aminoaryl, a C 2 -C29 di(hydrocarbyl)amino, morpholino, and firyl and wherein e~ and R 2 may be connected to form or be a saturated or unsaturated ring; more preferably each e~ and R 2 group is independently selected from the group consisting of: hydrogen, halogen, a C,-C 10 alkyl, a C,-Cio alkoxy, a Cs-Cs cycloalkyl, a C 6 -Clo aryl, a C 6 -Clo aryloxy, a C2-Cio alkenyl, a Cr-Cio *:alkylainino, a C 6 -Cis arylamino, and 2-fuiryl; and most preferably each Rand e' 1 ~group is idenently selected from the group consisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a Cs-Cs cycloalkyl, a C 6 -Clo aryl, benzyloxy, naphthyloxy, a Cr-Clo alkeyL diethylamino, dimethylamino, chlorine, bromine, morpholino, acetamido, and 2-firyl; and *J is represented by formula (F17): wherein: each R 5 IC R and R' group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two adjacent R 5 R 7 and R! groups may be connected to form a ring, preferably each

W

5

R

6

R

7 and R' group is independently selected from the group consisting of: hydrogen, halogen, a C,-C 2 o ailkyl, a C 1

-C

20 alkoxy, a C 3 -CIS cycloalkyl, a C 6

-CIS

aryl, a C 6

-C

1 aryloxy, a C 6

-C,

3 hydroxyaryl a C 6 -Cis arylcarboxy, a C 6

-C,

3 carboxyaryl, a C 2

-C

18 alkenyl, a Ci-C 2 o alkcylaniino, a C 6 -Cig arylaxnino, a C 6

,-C

13 -44- SUBSTITUT SKEET (RULE 26) WO 96/00560 WO 9600560PCr[US95/08383 axninoaryl, a C 2 -C~o di(hydrocarbyl)amino, morpholino, alkylaxnido and wherein and e r R 7 and R 8 may be connected to form a ring, for example, R' and R" orR7 and R8 may be joined by or be a -CJ1i4-, -(CH 2 3 or -C 3

H

3 N- moiety; more preferably each e 6

W

7 and R' group is independently selected from the group consisting of: hydrogen, halogen, a Ci-C, 0 alkcyl, a C 1 -Cio alkoxy, a Cs-C.

cycloalkyl, a C 6 -Clo aryl, a C 6

-C

1 aryloxy, a C 2 -Cio alkenyl, a C 1 -Cio alkylamino, a

C

6

-C

0 s aryiamino, morpholino, acetarnido and wherein W' and W 6 or W 7 and Ra may be connected to form a 5 or 6 member ring; most preferably each R 5 Re, W 7 and R 8 group is independently selected from the group consisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a Cs-Cs cycloalkyl, a C 6 -Clo aryl, benzyloxy, naphthyloxy, a C 2 -Cio alkenyl, NN-dialkylammio, N-allcyl-N-arylano, chlorine, bromine, morpholino, acetamnido and wherein W 5 and R 6 or W 7 and R8 may be joined by or be a -(CH 2 3 or -CMH 3 N- moiety; and e~ is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, preferably RP is a group selected from the group consisting of: hydrogen, a Ci-C~o alkcyl, a C 3

-CI

8 cycloalicyl, a C 6

-C

18 aryl, a C2-C,, alkenyl, a C 6 -CI9 arylaxnino, and substituted sulfonyl, more preferably RW is selected from the group a aconsisting of hydrogen and -SO 2 C6H,.

A particularly preferred dye is represented by the formula R5 SOR4 \C

C-R

Rs6/ \4

C

wherein each of R" 8 R 49 and is independently selected from the group consisting of: hydrogen, halogen and an acyclic, alicyclic or aromatic hydrocarbyl group optionally interrupted with one or more heteroatonis.

Each of R 51 R1 2

R

53

R'

4

R

55 and R 5 6 is independently selected from the group consisting of hydrogen and an acyclic, alicyclic or aromatic hydrocarbyl SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 group optionally interrupted with one or more heteroatoms. Optionally, any two of

R

51

R

5 2

R

53

R"

54

R

55 and R" may together to form an alicyclic or aromatic ring.

Preferably, at least four of R 4

R

49

R

50

R

51

R

5 2

R

5 3

R

54

R

55 and R 56 are hydrogen, and more preferably at least six are hydrogen.

More preferably, each of R 9 and R5 is independently selected from the group consisting of hydrogen, allcyl and halogen; and each of R 51 R1 2

R

5 3

R

4

R

5 5 and R" is independently selected from the group consisting of hydrogen and alkyl that is optionally substituted by one or more cyano, alkoxy, hydroxy, alkylsiloxy, alkylsilyl, acyl, aryl, halo, arylsiloxy, azylsilyl, amino, and mono or dialkyl amino groups.

Most preferably, at least one of R 2 R5, R 5 and R 5 6 is

CH

2 OSi(CH 3 2

C(CH

3 3

CH

2 OC(O)CH2CH(CH 3

)CH

2

C(CH)

3 CH2 OC()C(CH3) 15

OC

H 2 OCH OCH2CH2 Si(CH 3 3

-CH

2

CI

CH20C(O)NHCH2CHCH 2

CH

3 CH20C(0)NHCH2CH 2

CH

2 Si(OCH 2

CH

3 Another particularly preferred dye is represented by the formula R59 R58ss

NC

NC N X4 NC R62 R60 R61

NC

R66 R63 64 wherein

X

4 is N-R 6 7

R

6 8

O-R

69

S-R

7 o or CR 7 RnR 7 and wherein each of R 8

R

9 Re", R 6 1

R

6 2 RG,

R

65 is independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl group optionally interrupted with one or more heteroatoms and an acyclic, alicyclic or aromatic heterocyclic group, and each of

R

6 7

R

6

R

6 9

R

70

R

7 1

R

7 2 and R 73 is independently selected from the group SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 consisting of hydrogen, a hydrocarbyl group optionally interrupted with one or more heteroatoms and an acyclic, alicyclic or aromatic heterocyclic group.

Preferably, at least four of R' 8

R

5 9 R, R 61

R

62

R

63 Re R 6 5 and R"66are hydrogen, and more preferably at least six are hydrogen.

More preferably, each ofR 6 7

R

68 R, R 70

R

1

R

72 and R is independently selected from the group consisting of hydrogen and alkyl that is optionally substituted by one or more cyano, alkoxy, hydroxy, alkylsiloxy, alklsilyl, acyl, aryl, halo, arylsiloxy, arylsilyl, amino, and mono or dialkyl amino groups.

Most preferably, at least one of R 6 R, R, R 70 R7, R, and R" is

CH

2

CH

2 OSi(CH 3 2

C(CH

3 3

CH

2

CH

2

OC(O)CH

2

CH(CH

3

)CH

2

C(CH

3 3

CH

2

CH

2

OC(O)C(CH

3 3

CH

2

CH

2

OCH

2

OCH

2

CH

2 Si(CH 3 3 CH2CH2C 15 CH2CH2OC(O)NHCH 2

CH

2

CH

2

CH

3 CH2CH20C())NHCH2CH2CH2Si(OCH 2 CH)3 Particularly preferred compounds of this formula have the structure NC N C NC N(Et

NC

NC

NC NC N N(n-Bu) 2

NC

-47- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/09393 Another particularly preferred dye is represented by the formula

R

R827~R85 wherein each of e 7 k 7 e 7 R~n, R 79 R8", and R8 5 is independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl group optionally interrupted with one or more heteroatoms and an acycic, alicyclic or aromatic heterocyclic group, and each of and e' is independently selected from the group consisting of hydrogen, a hydrocarbyl group optionally interrupted :with one or more heteroatoms and an acydic, alicyclic or aromatic heterocyclic group- Preferably, at least four of e 7 e 7

R

76 R7, R 7 n, R, Rs', and R" ar hydrogen, and more preferably at least six are hydrogen.

More preferably, each of R, R82 R 8 is independently selected from the Cgroup consisting of hydrogen and alkyl that is optionally substituted by one or more :cyano, alkoxy, hydroxy, alkylsiloxy, alkylsilyl, acyl, aryl, halo, arylsiloxy, arylsilyl, 5 arnino, and mono or dialkylamino.

Most preferably, at least one of Reis

CH

2 OSi(CH 3 2

C(CH

3 3 S

CH

2

OC(O)CH

2

CH(CH

3

)CH

2

C(CH

3 )3

CH

2

OC(O)C(CH

3 3

CH

2

OCH

2

OCH

2

CH

2 Si(CH 2 2

C(CH

3 3

CH

2

CI

CH2OC(O)NHCH 2

CH

2 CH2CH 3 CH2OC(O)NHCH 2 CHCH2Si(OCH 2

CH

3 3 It will be apparent to those of ordinary skill in the art that further substitution of ailkyl groups not involved in the conjugated electronic portion of the -48- SUBSiTTUTE SKEET (RULE 26) WO 96/00560 PCTIUS95/08383 molecule are logical points for changing or enhancing physical properties of the molecule, such as crystallinity, solubility, melting point, toxicology or biological activity, etc. Such substitution may be made without losing the essential characteristics of the molecule as a dye, it will still exhibit color and bleaching propensity that is the same or somewhat modified from the color and bleaching characteristics of the core dye structure.

Another class of particularly suitable dyes may be represented by the following general formula (F18): S0 2

R

26

R

wherein: 10 each R 24 and R 2 group is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group with the proviso that at least one of R 24 and R 25 is or contains a substituted aryl, aminoaryl or heterocyclic group, preferably each R 24 and R group is independently selected from the group consisting of: hydrogen, a C-

C

2 o alkyl, a Ci-C 2 o alkoxy, a C 3 -Cag cycloalkyl, a C 6

-C

1 3 aryl, a C 6 -Cs aryloxy, a C 6 15 Cig hydroxyaryl, a C 6 -Cis arylcarboxy, a C 6 -Cs carboxyaryl, a C2-Cs alkenyl, a C-

C

2 o alkylamino, a C 6 -Cjs arylamino, a C 6 -Ci aminoaryl, a Cz-Czo di(hydrocarbyl)amino; more preferably each R 24 and R 2 group is a C 6

-C

1 8 aminoaryl group; each R 26 and R 2 group is independently a -(CF 2 group wherein m is a number between 0 and 20, more preferably m is a number between 0 and 10, most preferably m is 0 or 1; and n is an integer preferably less than 5, more preferably n is 1 or 2.

-49- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCr/US95/08383 Another class of particularly suitable dyes may be represented by the following general formula (F 19): wherein: 5~2 eah0,RRRadR ru sidpnetyhdoehlgn R' ahR' and group is independently seeteyrodhegou onnf hyrogen, halogen, a C 1

-C

2 D alkyl, a Ci-C~o alkoxy, a C 3 -CI3 cycloalkyl, a C 6

-C,

1 aryl, a C6-Cis *.**aryloxy, a C 6

-C

18 hydroxyaryl, a C6-Cis arylcarboxy, a C 6 -C~s carboxyaryl, a C 2 -Cis 10 alkenyl, a CI-C~o alkylarnino, a C 6 -Cis arylaniino, a C 6

-C

1 amninoaryl, a C2-C 2 o di(hydrocarbyl)aniino, carboxamide and wherein any two adjacent

R

2 3 'or e2 group may be connected to form a ring; more preferably, each R1, R 2 and e2 group is independently selected from the group consisting of: hydrogen, halogen, a CI-Cio alkyl, a Ci-Clo alkoxy, a Cs-Cs cycloalkyl, a C 6 -Clo 6696.0 1 5 aryl, a C2-Cio alkenyl, and a CI-Clo alicylamino, and wherein any two adjacent R',

R

2 KRor R29 groups may be connected to form a saturated or unsaturated 5 to 8 member ring; most preferably each R1,, R' and R29 group is independently selected from the group consisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a Cs-Cs cycloallcyl, a C 6

-CI

0 aryl, a CrClo alkenyl, a Ci- Cl 0 allcylaxnino, chlorine, bromine;

R

3 0 is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, preferably R 30 is a group independently selected from the group consisting of: hydrogen, halogen, a CI-C~o ailkyl, a Ci-C 20 alkoxy, a C-I cycloalkyl, a C 6 -Cis aryl, a (2 6 -CI& aiyloxy, a C 6 hydroxyaryl, a C 6

CIB

azylcarboxy, a C 6

-CI

8 carboxyaryl, a C 2

-C,

3 alkenyl, a CI-C~o alkylamino, a C 6 -CI8 SUBSTITE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 arylamino, a C 6

-C

1 a aminoaryl, a C 2 -C20 di(hydrocarbyl)amino; more preferably R 3 0 is a group independently selected from the group consisting of: hydrogen, halogen, a CI-Cto alkyl, a Ci-Clo alkoxy, a Cs-Cs cycloalkyl, a C 6 -Clo aryl, a C2C-io alkenyl, and a Ci-Clo alkylamino; and most preferably R 3 0 is selected from the group consisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a Cs-Cs cycloalkyl, and a C 6 -Cjo aryl; n is an integer preferably less than 5, more preferably n is 1 or 2.

Another class of particularly suitable dyes includes anionic oxonol dyes having the following general formula 20 0 R281 IR28 i

M+

n

S

wherein: .5.

Z represents the non-metallic atoms necessary to complete a substituted or unsubstituted nitrogen-containing heterocyclic ring, preferably the non-metallic atoms are selected from the group consisting of O, N, C and S, each R 2 is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group, preferably each R 28 is independently selected from the group consisting of: hydrogen, a CI-C2o alkyl, a C 3 -Cag cycloalkyl, a Cs-Cis aryl, a C 6 -Cs hydroxyaryl, a C 6

-C

1 s carboxyaryl, a C2C-C alkenyl, a C 6

-C

1 g aminoaryl; more preferably each R 28 is independently selected from the group consisting of: hydrogen, a C 1 -Clo alkyl, a Cs-Cs cycloalkyl, a C 6 -Cio aryl, and a C 2 -CIO alkenyl; n is an integer preferably less than 5, more preferably 1 or 2; and wherein M+ is selected from any suitable cation including sodium, triethylammonium and the like.

-51- SUBSTITUTE SHEET (RULE 26) WO 96100560 PCTIUS95/IS0383 Another class of particularly suitable dyes includes cationic dyes having the following general formula R 31 R

R

36 wherein: each R 1

R

32

R

33 and R" group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group; preferably each R3', R 32

RU

3 and R" group is independently selected from the group consisting of hydrogen, halogen, a Ci-C2o alkyl, a Ci-C2o alkoxy, a C 3

-C

1 s cycloalkyl, a Cs-Cas aryl, a C 6

-C,

5 aryloxy, a C-Cs hydroxyaryl, a C 6

-C

1 s arylcarboxy, a C 6 carboxyaryl, a C 2

-C

1 s alkenyl, a Ci-C2o alkylamino, a C 6

-C

1 s arylamino, a C 6

-C

1 8 aminoaryl, a C2rC2 di(hydrocarbyl)amino, carboxamide

(-C(O)NR'R

2 and wherein any two adjacent R" R 2

R

3 or R groups may be connected to form a ring; more preferably each R 3

R

32 I R 33 and R group is independently selected from the group consisting of: hydrogen, halogen, a CI-CIo alkyl, a C,-Clo alkoxy, a Cs-Cs cycloalkyl, a C 6 -Clo aryl, a C 2

-C

10 alkenyl, and a C,-Clo alkylamino, and wherein any two adjacent R, R 32

R

3 or RU groups may be connected to form a to 8 member ring; and most preferably each R 1

R

32

R

33 and R3 group is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a Cs-Cg cycloalkyl, a C-Co aryl, a C 2 -CIo alkenyl, a CI-Clo alkylamino, chlorine, bromine, and wherein R 33 and R 34 may be joined by a -(CH 2 3 or -C 3

H

3 N- moiety;

R

3 and R' are as defined above for R 33 and R 3 X is O, S, or NR 37 Y is N or CR 3

R

37 and R 3 are as defined above for R 33 and wherein -52- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCT113S95/08383 M- is any suitable anion.

Another class of particularly suitable dyes includes cationic dyes having the following general formula (F3 1): R32 R 3 34 wherein: each W 3

,K

2

,K

3 and Re group is independently hyrgn halogen, a ~hydrocarbyl-containing group, or a heterocyclic group, preferably each W 31

W

3 3 and e~ group is independently selected from the group consisting of hydrogen, halogen, a C 1 -C~e alkyl, a C 1 -C~o alkoxy, a C 3

-C

13 cyCloalkyl, a C 6

-C

13 aryl, a C 6 -Cla aryloxy, a C 6 -CI& hydroxyaryl, a C 6

-C

1 arylcarboxy, a C 6

-C

13 a. carboxyaryl a C 2

-C

1 alkenyl, a C 1 -C~o alkylamino, a C 6

-C

1 arylamino, a (2 6

-C

13 aminoaryl, a CxrC 2 di(hydrocarbyl)amino, carboxamide

(-C(O)NR'R

2 and Wherein any two adjacent R 31 I, W 2

R

3

W

3 or egroups may be connected to form a ring; more preferably each RW', R 2 R, and R34 group is independently selected from the group consisting of: hydrogen, halogen, a C 1

-C

10 alkcyl, a Ci-Cio alkoxy, a Cs-Cg cycloalkyl, a C 6 -Clo aryl, a CrCio alkenyl, and a C,-Clo alkylamnino, and wherein any two adjacent R 31

WR?

3 or R 3 4 groups may be. connected to form a to 8 member ring; and most preferably each W 3

R

32

R

3 and R 3 4 group is independently selected from the group consisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a C,-Cs cycloalkyl, a C 6 -Cl 0 aryl, a C 2

-CIO

alkenyl, a C I-C Io alkylamino, chlorine, bromine, and wherein W 33 and e~ may be joined by a -C 4

H

4

-(CH

2 3 or -CMH 3 N- moiety;

K

39 is independently hydrogen, a hydrocarbyl-containing group or a heterocyclic group, preferably

R?

9 is a group selected from the group consisting of: -53- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95OS383 hydrogen, a Ci-C~o alkyl, a C 3

-CI

8 cycloalkyl, a C 6

-C

13 aryl, a C 6 -CI8 aryloxy, a C 6 Cis hydroxyaryl, a C 6 arylcarboxy, a C 6

-CI

8 carboxyaryl, a CrCis alkenyl, a C 1 C~ alkylamino, a Cs-Cis arylarnino, a C 6

-C,

3 arninoaryl, a C 2

-C

2 o di(hydrocarbyl)aniino; R40 is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, preferably e 4 is a group selected from the group consisting of: hydrogen, halogen, a C 1

-C

2 o alkyl, a C 1 -C~o alkoxy, a C 3

-C

1 8 cycloalkyl, a C 6

-C

1 aryl, a C 6 -Cig aryloxy, a C 6 -CiB hydroxyaryl, a C 6 -Cis arylcarboxy, a C 6 -Cis carboxyaryl, a C 2 alkenyl, a C 1 -Cm alkylaniino, a C 6 -Cis arylarnino, a C 6 aminoaryl, a Cr 2 o di(hydrocarbyl)amino, and carboxamide; X is C=R 4

C(R

3 2 0, S, or NR37, more preferably X is C=R",

:C(R

38 2 or S, wherein

RW

7 is as defined above for R? 9 R'is as defined-above for R W is an oxo group, a divalent hydrocarbyl-contining group, or a divalent heterocyclic group, wherein R" and e~ may be connected to form an unsaturated ring, for exaple, e' and e~ may be joined by a -C 3

H

3 moiety, and wherein R and Re may be connected to form a saturated or unsaturated ring; and wherein is any suitable anion.

Another class of particularly suitable dyes includes cationic dyes having the following general formula (F32): R 4 R 47 461M

R.

wherein: each R 42 to WI 5 group is independently hydrogen, halogen, a hydrocarbylcontaining group, or a heterocyclic group, preferably each R 4 2 to R' group is independently selected from the group consisting of: hydrogen, halogen, a C,-C 2 o -54- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 alkyl, a CI-C 2 o aikoxy, a C 3 -,Clg cycloalkyl, a C 6 -CI9 aryl, a 0 6

-CI

3 aryloxy, a C 6

-C

18 hydroxyaryl, a C 6

-C

18 arYlcarboxy, a C 6 ,-Cls carboxyaryl, a C 2

-C

18 alkenyl, a CI-C 20 alkylanino, a C 6

-C,

1 arylaniino, a (2 6 -Cis aniinoaryl, a C 2

-C

2 o di(hydrocarbyl)anmino, each R 4 R46 and W' 7 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, preferably each R" 1

,R

and R group is independently selected from the group consisting of: hydrogen, a

CI-C

2 o alkl, a C 3

-CI

1 cycloalklA a C 6

-C

1 aryl, a C 6

-C

1 aryloxy, a C 6

-C

1 hydroxyaryl, a C 6

-C

1 arylcarboxy, a C 6 carboxyaryl, a C 2

-C,

8 alkenyl, a C 1 -C~o alkylamino, a C 6

-C

13 arylainino, a C 6

-C

1 aminoaryl, a C2-C 2 o di(hydrocarbyl)amino, wherein any two adjacent to e' groups may be connected to form a ring and wherein R44 and W 45 may be connected to form a ring; more preferably R 40, W' 1 R 4 6 and W 47 are methyl and to RW' are hydrogen; n is an integer preferably less than 5, more preferably 1, 2 or 3; -and wherein M- is any suitable anion.

Suitable cure-indicator dyes for use in the present invention include neutral dyes such as: 4 4 -(Dimethylamino)phenyl]imio]-2,5 'clohexadien- 1-one; 2- I -one; 4- 4 -(Diethylainino)phenyl]knino].1 4 -dihydronaphthalen-I -one; (Dimethylamino)phenylimxino-1 4 -dihdronaphthalen- 1 -one; 4-[[2-methyl-4- (diethylamino)phlenyllixnino]- 1, 4 -dihydronaphthalen. 1-one; 3-Methoxy4-[[2- -one; 3-Chloro-4-[[2mehl4(it~aiopeylhio-,-coeain -one; 2-Methyl-4-[[4-(4morphoinyl)phenyl]ino]2,s..qclohexden 1 -one; 2,6-Dichloro-4-114-(4morphoinyl)-pheny]mino]2,s..,ccohexadien 1 -one; 2,6-Dimethyl-4-[[4-{4- 1-one; 2,5-Dichloro..4-[[4- 1 -one; 3-MethoXY-4-[[3-methoxy.

4 -(diethylamiino)phenyliino]2,5-cyclohexadie- 1-one; 2 ,6-Dichloro-4-[[2-niethyl- 4 -(diethylanmino)pheny]iiino]2s5cyclohexadien 1 -one; 3 -[[4-(Diethylamino)-2methylphenyl]imino]-6&oxo.N-pheny..

I,

4 -cyclohexadiene-l1-carboxaniide; 2,5-Dichloro-4-[[2.

SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT1US95/08383 methy[ 4 -(diethylaino)-pheny]inmjno]-2,5-~ccohexadien- 1 -one; 2,6-Dichloro-4- 4 -(acetamido)pheny]irnino]-2,5-cyclohexadien- 1-one; 2,6-Dichloro-4-[4-ethoxy 1 -one; 2,6-Dichloro.-4-[(2-methyl-4.ethoxy 1-one; 2,6-Dimethyl-4-hydroxy phenylirino]- 2,5-cyclohexadien- 1 -one; 2,6-Dichloro-4+4-methoxcy 1 hexadien- 1 -one; x~hnliin]25-cyclohexadien- 1 one; 2 6 -Dichloro-44[(2,4-dimethoxyphenyl)iniino]2,5-clohexadienI -one; 2,6- Dich~oroA4[(4-methoxypheniyi)iino].25-cyclohedijen. 1-one; 4-(phenyliniino)- 1 -one; 4-(l1 -naphthyfimiino)2,5ycoheadien 1 -one; 4-(2naphthylinino)-2,5--cyclohexadjen. 1-one; 2,5-Bis(phenylamino)-4(phenyiiio).

2 ,5-cyclohexadien.. 1 -one; 2,-irm--(,-Ermpey~mn]25 cyclohexadien- 1-one; 2 3 ,5-Tric~oro-4-[(2,4,6-trich~oropheny)iino]-2,5cyclohexadien- 1 -one; 2,-ihoo-4[-dmtyaiopey]5pey-2) imidazo-2ylidine]-2,5s<cycohexadien. 1-one; 2,6-Dichloro44,5-bis(4hyfroxy-.

pheny)(2)iidazo2ydine]25..Iycoh ien. -one; 2,6-Dimethoxy-4-[4,5bis( 2 -fiyl)-(2H)-imidazo1.2.ydne]2s..ycohxadien 1-one; 2,6-Bis[ 1, 1 one; 4 -(phenylimino)-2,5-cyclohoen-je. 1 -imine; Mono[(3-methyl-2-(3H}.

beztizoy eehyrzn]254y heain-,4-dione; 4-[3-Cbloro-4-oxo- 2 ,5-cyclohexadien-.1 -ylid ine)amino]- 1,2-dihydro-1I,5-dimethyl-2-phenyl-(3H).

pyrazol-3-one; 4 3 ,5-Dich~oro-4-oxo-2,5-cyclohexadien I -ylidine)amino]- 1,2- *dihydro-1,-ieh 2-hnl(H-przl3oe 3-[(3,5-Dichloro-4-oxo-2,5cyclohexadien- Il-y~idine)axnino]-2, 5-dihydo4,5-dimethyl.. I -phenylpyrrol-2-one; 4- (Phenylsulfonyl)ixnino- l-[ 4 -[(phenylsulfonyl)i nino]-2,5-cclohexadien- I -ylidenyl]- 2 ,5-cyclohexadiene; 4 6 6 -Bis[(trifluoromethy)sjfony].1 dirnethylbenzenamine; 4 4 4 -Bis[(trifluoromethyl)sulfonyl] 1 ,3-butadienyl]-2ethoxy-N,N-dimethylbenzenarrjin; 4 4 4 -Bis[(trifluorometbyl)sulfonyl] 1 ,3-butadinl-,-iehx-,-iehleznnie 9 -[4,4-Bis[(trifluoromethyl)sulfonyl]..1 7 3 -butadienyl]-2,3,6,7-tetrajlydro-( I 4 4 4 -Bis[(trifluoromethyl)sulfonyl]. l 3 -butadieny]-2,-N,Ntetramety.

benzenaxnine; 4 -[5,5-Bis[(trifluoroniethyI)sulfony1]..2,4..pentadienyidene].1,4- -56- SUBSTTUTE SHEET (RULE 26) WO 96/00560 P~U9I8S PCTIUS95/08383 dihydro- 1 -methyiquinoline; 6 6 -Bis[4-(dimethylaniino)phenyl]I ,3,5-hexatriene- 1, 1 bis(sulfonylfluoride); 4-[4,4-Bis[(trifluoromethyl)sulfonyl]- 1,3-butadienyl]-N,Ndimethylbenzenamine; and 4- 3 4 -(DimethyLaxnino)phenyl]-2-propenylidene]-2 phenyl-5(4H)-oxazolone; anionic dyes having the following anions: Dityhxhdo246tix--yiidnl-,-etdeydn]13ehl 2 4 6 (1H,3H,5H)-pyrixnidenetrione; and cationic dyes having the following cations or having the cations of the following cationic dyes: 3H-Indoliuin, (dimethylamino)phenyl]-2-propenyidene] I -methyl-2-phenyl; Benzothiazolium, 3- (3ain--xpoy)2[4[i(-hlrehlaiopey~z]&ehx- Benzothiazoliwn, 3 3 -aznino- 3 -oxopropyl-2-[[4{dietiylanio)phenyl]azo].& ethoxy-; Benzothiazoliurn, 3 3 -amino-3-oxopropyl)-2-[[4-(diethylamino)-2 ~methylphenyl]azo]..6.ethoxy-; CAS 12221-40-8; CAS 12270-14-3; CAS 12221- 31-7; CAS 12221-34-0; Benzo~a]phenoxazin-7-ium, 9-(dimnethylaznino)-; bis[4-dimethylaznino)phenyl].. 1 ,3-butadienyl]- 1 -ethyl quinolinium; 4-[44,-bis[4- (dimethylarnino)phenyl]- 1 .3-butadienyl] 1 -ethyl quinolinium; Naphtho[2, 1d~thiazolium, 2 4 4 -bis[4-{dimethylamino)phenyl] 1 ,3-butadienyl]-3-ethy-; 2-[2- 4 -(dimethylanlino)phenyl]ethenyl]-l1-phenyl-3-methyl quinoxalinium; Quinoliniuni, Benz[cd]indoiuxn, 2 4 -(diethylamino)-2-ethoxyphenyl]- 1-ethyl-; 2 (Dmehlaio~tr]1 3 -dimnethylquinoxalinium; 2-[3-(5-chloro-l,3-dihydrol, 3 3 -trimethyl-(2H)-indol-2-ylidene)1.-propenyl]. I-methylquinoxafinium; C. I.

Basic Blue 40; Benzothiazolium, 2 4 -[ethyl(2-hydroxyethyl)amino]phenyl]uzo]-6 methoxy-3-methyl-; Benzothiazoliun, 2 4 -[ethyl(2-hydroxyethyl)amino]phenylazo]-6-niethoxy-3-methyl-; C. I. Basic Blue 42; C. I. Basic Blue 53; 3H- Indolium, 5-chloro-2-[5-(5-chloro- 1,3-dihydro- 1,3 ,3-trixnethyl-2H-indol-2-ylidene)- 1 ,3-pentadienyl]- 1,3,3-trimethyl-; Basic Blue 142; Benz[cd]indolium 2-[2-(9-ethyl- 9 H)-carbazol-3-yl)ethenyl]-l -methyl-; Benz[cd]indolium (dimethylamino)pheny1]-2-phenylethenyl]-.1-methyl-; Benz[cd]indolium, 2-[2,2bis[ 4 -(dimethylamino)phenyl]ethenyl]-.1-methyl-; Benzfcd]indolium dihydro-lI-methyl-2-phenyl- lH-indol- 3 -yl)-2-(2methylphenyl)ethenyl]-.1 -methyl-;, -57- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTfUS95/08383 Pyriznidinium, 4-[5-(2,3-dihydro-1I,3-dimethyl-2-oxo-; 4(1 H)-pyrixnidinylidene)- 1,3pentadienylj-2,3..dihydro-1I,3-dimethyl-2-oxo-; 3H-Indolium, 1,3-dihydro- 1,,-rmty-H-no 1ldn~mty]55dmthl2ccoeeylidene]methyl]- 1,3,3-tnimethyl-; Benz~cd]indolium, 2-[ 2 -[4-(diethyLaznino)-2methylphenyl]ethenyl]-l1-methyl-; 3H-Indolium, 3 -[3-[4-[(dimethylnnuino)phenyl].2 propenylideneJ-l1-methyl-2-(4-methoxyphenyl).; 3H-Indolium, 3-[2,5-dimethy.,l- 1phenyl-(1 H)-pyrrol-3-yl)methylene] 1,2-dimethyl-; 3H-Indoliuxn, 3-[2,5-dimethyl-

I-

phenyl-( lH)-pyrrol-3-yl)methylene]-l1-methyl-2-phenyl-; 2-[2-[2-chloro-4- (dimethylanino)phenyl]ethenyl]1methylbenz[cd]indoiu; C. 1. Basic Violet 22; C. 1. Basic Red 15; Benzcd]indoium, 2 2 4 -(dimethylaznino)phenyljethenyl] methyl-;~ Bezr~noiM-2[-dmtynio--toyhnleh lmethyl-; and 3H-Indoliurn, 2- I -cyano-44-bis[4-(dimethylamio)phenyl]- 1,3- S. butadienyl]- 1,3,3-trimethyl-.

Presently particularly preferred dyes for use in the present invention include: 4 4 -(Dimethylarino)phenyl]imiino]-25.cyclohexadien. 1 -one; 2-Chloro-4-[[2- O V e t h I 4 i e t y b m i o~ p e n y l i n i n o ,5 y c l o o m d e n 1 o n e 4 4 (Diethylamino)phenylliniino].. ,4-azydronaphthalen- 1 -one; (Dimethylamino)phenylliinno..1 ,4-dhydronaphthalen-I -one; 4-[[2-methyl4.

(diethylamino)phenyl]iznjno].. I,4-diydronaphthalen- 1 -one; 3-Methoxy-4-[[2mehI-dewimn 1nllnio-,-cdhxde--one; 2-Methyl-4-[[4-(4seemorpholinyl)phenyllimino]..2,s..cyclohexadien.I -one; 2,5-Dichloro-4-[[4- (dehlmn~hny~nio-,-y 1oode--one; 3-[[4-(Diethylaniino)-2methylphenyl]imino]-6..oxo.Nphenyl-1, 4 cyclohexadiene- I-carboxamnide; 2,6-Dichloro-4-[[4- (acetanido)phenyl]imino]-2,5-cclohexdien-. 1 -one; cyclohexadien- 1 -one; 4 2 -naphthylimino)-2,5-cyclohexadien. 1-one; -one; 4-[5,5- Bis[(trifluoromethyl)sufonyl]2,4pentadeylidenel-1 I,4-dihydro-lI-methyiquinoline; 6 6 -Bis[4-(dimethylaxnino)phenyl] 1,3 ,5-hexatriene- 1, 1 -bis(sulfonylfluoride); 4-[4,4- Bis[(trifluoromethyl)sulfonyl]. -utdey]-,-ietybnennie and 4-[3- -58- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 A variety of adjuvants may be utilized to modify the relationship between the color change and the extent of cure. These adjuvants are generally added to the primary compositions of this invention in an amount suitable to obtain the desired interactions. Several suitable classes of indicator adjuvants include active proton sources such as alcohols, acids, and water. Alternatively, a variety of hydrosilation inhibitors well known in the art may also serve as adjuvants such as acetylenic alcohols, certain polyolefinic siloxanes, pyridine, acrylonitrile, organic phosphines and phosphites, unsaturated amides, alkyl fumarates, alkyl maleates and the like.

As previously mentioned the composition containing the cure-indicating dye optionally may comprise one or more suitable solubilizing agents surfactants).

The surfactants may be employed to facilitate or maintain the dissolution or Sdispersion of the cure-indicating dye and/or other ingredients in the composition, to facilitate uniform mixing of the reactants, or to adjust the composition's viscosity or flow. The surfactant may also be employed to modify the surface wetting characteristics of the composition. In particular, the surfactant may be desired when the composition comprises a filler. Suitable surfactants for use with silicone compositions include surfactants selected from the group consisting of ethoxylated nonionic surface active agents and cationic or amphoteric fluorochemical surface active agents such as those disclosed in U.S. Patent No. 4,657,959 (Bryan et al.) which is herein incorporated by reference. Preferred surfactants contain one or more solubilizing groups one or more siloxane groups, hydrocarbyl-containing groups or perfluoroalkyl groups) which render the surfactant soluble or dispersible in the silicone composition.

A preferred class of ethoxylated surfactants containing a siloxane solubilizing group has the average formula R R R II

I

R R

R

x- y R O0(C 2

H

3 R20)a(C 3

H

6 0) R 3 -59- SUBSTTUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 where each R is independently a monovalent hydrocarbyl radical, R' is a divalent hydrocarbylene radical, each R 2 is independently hydrogen or a lower hydroxyalkyl radical, R 3 is hydrogen or a monovalent hydrocarbyl radical; x, a, and b are independently greater than or equal to zero; and y is independently greater than or equal to one. Preferably in compounds of Formula I, R is methyl, R I is methylene

CH

2 ethylene (-CH 2

CH

2 propylene (CH 2

CH

2

CH

2 or butylene

(-CH

2

CH

2

CH

2

CH

2

R

2 is hydrogen, R 3 is hydrogen, methyl, ethyl, propyl, or butyl, x is a number from zero to 100, y is a number from one to five, a is a number from 5 to 300, and b is a number from zero to 300; more preferably R is methyl, R' is ethylene or propylene,

R

2 is hydrogen, R 3 is hydrogen, methyl, or butyl, x is a from zero to 80, y is a number from one to five, a is a number from 5 to 2 00, and b is a number from zero to 200; most preferably R is methyl, R 1 is propylene, R 2 is hydrogen, R 3 is hydrogen, methyl, or butyl, x is a iumber from zero to 60, y is a number from one to five, a is a number such that the product of y times a is zero to 200, and b is a number such that the product ofy times b is zero to 2 0 0 and the sum of the product of a times y and b times y is five to 200.

Another preferred class of ethoxylated surfactants has the average formula RSi (OSi)x(OC 2

H

3 R)(OCH)bOR3 3 where R, R 2

R

3 x, a and b are as defined above for formula I. Preferably in compounds of Formula II, R and R 3 are -CH 3

R

2 is hydrogen, a is five to 20 and b is zero.

Ethoxylated surfactants of Formulas I and II above are described in Union Carbide Corp. product literature ("Silwet Surfactants," dated August, 1992; "Organomodified Oils dated April, 1982; "UCAR-SIL EPS Silicone Hydrophilic Finish," dated March 1984 and available from OSi Specialties, Inc., Danbury, CT) and in U.S. Patent Nos. 3,505,377, 3,980,688, and 4,431,789, the disclosures of which are incorporated herein by reference. Several of such ethoxylated surfactants are available from OSi Specialties, Inc. as "SILWET" SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 surface active copolymers. Preferred SILWET surface active copolymers include SILWET L-77, L-7607, L-7630, L-7002 and L-7200.

An additional preferred class of ethoxylated surfactants has the average formula

R

3 [(iR0)SiO2i(OC 2 3

R

2 )(OC3 H)dOT m where R 2 and R 3 are as defined above for Formula I, each R 4 group is independently a monovalent hydrocarbyl radical with the proviso that at least a majority of the R 4 groups are sterically hindered alkyl radicals having at least three carbon atoms, c is at least four, d is greater than or equal to zero, and T is hydrogen, a monovalent alkyl or alkenyl radical, or a group of the formula -Si(R)2[OSi(OR) 3 2 Preferably 10 in compounds ofFormula II, R 2 is hydrogen, R 3 and T are -CH 3 R' is sec-butyl, c °oo is five or more and d is zero. Representative ethoxylated surfactants of Formula m are described in Olin Corp. product literature ("Silicate ClusterO Fluids") and in U.S. Patent Nos. 4,160,776, 4,226,794, and 4,337,168, the disclosures of which are incorporated herein by reference. At least one such surfactant is experimentally available from Olin Corp. as a "SILFAC" polyethoxylated silicate cluster compound bearing the experimental designation "SILFAC 12M".

An additional preferred class of ethoxylated surfactants has the average formula (R'O)3Si(OC2H 3

R

2

).(OC

3 sI 6 )OT'

IV

where R 2 and R 4 are as defined above for Formula m, e is at least four, f is greater than or equal to zero, and T' is hydrogen, a monovalent alkyl or alkenyl radical, or a group of the formula -Si(OR) 3 The preparation of these ethoxylated surfactants is described in U.S. Patent No. 4,657,959. Preferably in compounds of Formula IV,

R

2 is hydrogen, R 4 is sec-butyl, e is ten to 20, f is zero and T' is -Si(sec-butoxy) 3 -61- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 Suitable ethoxylated surfactants containing hydrocarbyl solubilizing groups are shown in "Surfactants and Detersive Systems", Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Ed., 22, 360-377 (1983), the disclosure of which is incorporated herein by reference. A preferred class of such ethoxylated surfactants has the average formula RS[(OC2HR2)(OC3sH)OR 3 I t. 3

V

where R 2 and R 3 are as defined above for Formula I, R s is a saturated or unsaturated alkyl or alkylphenyl radical having at least seven carbon atoms, g is a number from zero to 100, 1 is a number from zero to 100, and the sum ofg and I is at least three.

Suitable ethoxylated surfactants containing perfluoroalkyl solubilizing groups are described in U.S. Patent No. 2,915,544, the disclosure of which is 15 incorporated herein by reference. A preferred class of such ethoxylated surfactants has the average formula Rf-[Q(C2 H3R20)(CH~-Co)RI2

VI

20 where R 2 and R 3 are as defined above for Formula I, Rfis a fluorinated, monovalent or divalent, aliphatic, preferably saturated organic radical containing at least four carbon atoms and preferably a terminal perfluoromethyl group, Q is a polyvalent divalent) hydrocarbylene linking group

-C

2 or -SO 2 NR- where R is as defined above), h is greater than or equal to one, and i is greater than or equal to zero.

The surfactant used in the present invention can also be a cationic or amphoteric fluorosurfactant. Such fluorosurfactants contain at least one perfluoroalkyl solubilizing group Rf where Rfis as defined above for Formula VI.

The cationic fluorosurfactants contain at least one cationogenic group which is the radical of a base having an ionization constant in water at 25°C of at least about 6. The amphoteric fluorosurfactants contain at least one such cationogenic group -62- SUBSTITrTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 and at least one anionogenic group which is the radical of an acid having an ionization constant in water at 25 0 C of at least about 10 6 Suitable fluorosurfactants are described, for example, in U.S. Patent No. 4,484,990, the disclosure of which is incorporated herein by reference.

Other suitable solubilizing or wetting agents include substances such as poly(ethylene oxide), poly(propylene oxide), and copolymers of ethylene oxide and propylene oxide. Suitable such substances have the average formula

R'O(C

2

H

3

R

2 0)(C 3

H

6 OkR 3

VII

where

R

2 is as defined above for Formula I, each R' and R' group is independently hydrogen, a hydrocarbyl-containing S* group, or a heterocyclic group, preferably R 2 is hydrogen and each R' and R 3 is selected from the group consisting of hydrogen, a CI-C2o alkyl, and a alkylphenyl group, more preferably each R' and R 2 is hydrogen; j is a number having an average value between 0 and 25, more preferably j is number having an average value between 5 and k is a number having an average value between 0 and 100, more preferably k is a number having an average value of 0; and wherein 20 the sum ofj and k is at least 3.

Preferred wetting agents of this class include hydroxy terminated poly(ethylene oxide), hydroxy terminated poly(propylene oxide), and hydroxy terminated copolymers of ethylene oxide and propylene oxide (also known as polyethylene glycols, polypropylene glycols, and copolymers thereof).

The following examples are offered to aid in the understanding of the present invention and are not to be construed as limiting the scope thereof Unless otherwise indicated, all parts and percentages are by weight -63- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCI/US95/08383

EXAMPLES

Preparatory Example la Preparation of a Karstedt catalyst A three neck flask was fitted with a mechanical stirrer, reflux condenser, thermometer, and nitrogen purge and placed in a water bath. The flask was charged with 3,000 parts ethanol and 1,200 parts l,l,3,3-tetramethyl-1,3-divinyldisiloxane and then purged with nitrogen for 5 minutes. Six hundred parts hexachloroplatinic acid was added to the solution and the mixture stirred until the acid was substantially dissolved. Eighteen hundred parts sodium bicarbonate was then added over a 5 minute period. The water bath was heated to 60*C and then stirred for hours. After it had cooled, the solution was filtered, washed with 150 parts ethanol and transferred to a flask containing 6,000 parts dimethylvinylsiloxy terminated polydimethylsiloxane with a viscosity of 0.3 Pa s and a molecular weight of about 10,000 g/mol. The flask was placed on a rotary evaporator and stripped at 45 0

C

15 until the vacuum reaches 0.5-1.0 Torr to produce a Karstedt type catalyst solution with a platinum concentration of approximately 2.3-3.0%.

Preparatory Example Ib Preparation of a Catalyst Complex of Pt and Divinyltetramethyldisiloxane Preparation of Bis(1,5-cycooctadiene)platinum(0): To a suspension of lithium ribbon (0.7 g, 100 mmol) in diethyl ether (80 ml) at 0C under argon was added freshly distilled 1, 3 ,5, 7 -cyclooctatetraene, g, 24 mmol), and the resultant mixture was allowed to come slowly to room temperature and was stirred overnight. A 2.0 ml aliquot of the dark orange solution was hydrolyzed in approximately 2 ml of water, approximately 1 mg of phenolphthalein was added, and titration with 1.00 N HC1 required 1.05 ml to reach the endpoint, indicating a 0.25 M solution of(COT)Li 2 A substantial amount of white solids settled from the solution.

A 250-ml three-necked round-bottomed flask equipped with a magnetic stir bar and fitted with a 60-ml addition funnel was flushed with argon and charged with -64- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 3.7 g, 10 mmol finely ground (COD)PtCl 2 (as described by McDermott, White, and Whitesides, in J. Am. Chem. Soc. 1976, 98, 6521) and (15 ml). The mixture was cooled to minus 40*C, and the addition funnel was charged with the 0.25 M solution of(COT)Li 2 in diethyl ether, prepared above, (41 ml, 10 mmol), which was added dropwise to the rapidly stirred slurry over a period of 45 min. After the addition was complete, the orange mixture was allowed to warm to 0°C over the course of 1 hour. Volatile materials were separated at reduced pressure until the residue was quite dry. Argon was readmitted to the flask, and the orange residue was extracted at room temperature with five 50 ml portions of toluene. The combined extracts were filtered through a short column of alumina (8 x 2.5 cm, neutral Brockman activity II). The column was washed with an additional 50-ml portion of toluene, and the volume of the filtrate and washings was reduced by approximately one-half under reduced pressure. The reddish-brown solution was cooled to minus 20 0 C and allowed to stand for approximately 60 hours during which time white crystals formed. The mother liquor was separated, and the crystals were washed with four 5 ml portions of diethyl ether and dried under vacuum to yield a first crop of 1.09 g product. The mother liquor was concentrated to dryness under reduced pressure, and the brown residue was washed with five ml portions of diethyl ether and dried under vacuum to give a second crop of 0.58 4 20 g. The 'H NMR spectra of the first and second crop were identical, consistent for the desired complex and in agreement with published data by Spencer (Spencer, J.L.

Inorg. Synth. 1979, 19, 213).

Preparation of: Tris(1,3-divinyl-1,1,3,3- tetramethyldisiloxane)diplatinum(0): Bis(l,5-cyclooctadiene)platinum(0) (600 mg, 1.46 mmol) was added in small portions to a rapidly stirred solution of 1,3-divinyl-1,1,3,3tetramethyldisiloxane (405 mg, 2.17 mmol) in diethyl ether (15 ml) at room temperature under argon. The mixture was stirred overnight, and concentration under reduced pressure afforded a colorless oil. The crude product was purified by first eluting from Florisil with diethyl ether followed, after concentration, by flash chromatography on silica gel with 98:2 hexanes diethyl ether. The product was SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS9SIOS383 obtained as a colorless oil, homogeneous by TLC, which crystallized on standing.

1 K, 1 3 C, 29Si and '"Pt NMR analyses were consistent for the desired complex and in agreement with published data by Hfitchcock et al. (Hitchcock, Lappert, Warhurst, Angew. Chem., In. Ed Engi. 1991, 30,438).

The above complex (with the theoretical structure of F25) was dissolved in toluene to provide a catalyst solution having between about 2 and 3 weight percent platinm.L Nbpi) ~~si a a a Preparatory Example 2 Stock "catalyst" compositions and stock "base" compositions were prepared by combining the following ingredients as listed in Table P2: Table P2 Ingedient Structure ~Stock Compoitio BI Ci B2 C2 [Viyl terminated F21 78.35 97.95 78.35 97.95 poly Itysiloxanei Crosslinker' F22 21.97 21.97 Inhibitor 3 F23 0.06 0.06 Catalst 4 F24 2.05 2.05 Dichioromethane 1003 100.0 "Vinyl terminated polydimnethylsdoxane", (vinyldimethylsiloxy)-terniated polydimethylsiloxane with a viscosity of approximately 2 Pa s ("LMWP") and available as Y-7942 from OSi Specialties, Inc., Danbury, CT.

\CH

3 'CH 3 CH 3

CH

3 CH 3 CHt 3 300 -66- SUBSTIUT SHEET (RULE 26) WO 96/00560 WO 9600560PCT/US95OS383 2 "Crosslinker" organohydropolysiloxane having a viscosity of approximately 24 to 3 8 niPa s and approximately 0.2 hydride ("XL and available from OSi Specialties, Inc., Danbury, CT.

CH

3 H

CH

3

CH

3

CH

3 -Si-O Si-O- Si-O Si-CH 3 I I I I

CH

3

CH

3 LC1 3

CH

3 6 /6.8 3 "Inhibitor" l,3-divinyltetramethyldisiloxane ("DVTMI)S") and available from United Chemical Technology, Inc., Bristol, PA.

CH

3

CH

:CH1 3

CH

3 4 "Catalyst" Karstedt type platinum catalyst comprising 2.55 wt platinum catalyst in vinyl terminated polydimethylsiloxane (as described in Preparatory Example Ila and as shown with the approximate formula of structure F24).

(F24) .::Preparator-y 0 00Example 3 Preparation of Various Dyes Preparation of: 2 -Chloro-4-[[2-methylA4-(diethylanino)pheny]iio] I -one: 1450 parts K 3 Fe(CN) 6 595 parts Na 2

CO

3 and 4150 parts water were added to a 12-liter round bottom flask equipped with a mechanical stirrer, thermometer, and addition funnel. The mixture was heated to 5 5 OC with stirring. A solution of 227 parts 4 -NN-diethyl-2-methylphenylenediamne monohydrochloride, 128 parts o-chlorophenol, 1960 parts ethanol, and 2500 parts water was charged to the -67- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 addition funnel and added dropwise to the stirred, heated solution. After the addition was complete the reaction mixture was maintained at 55 °C with stirring for 20 minutes. The warm mixture was filtered with vacuum and the resulting filter cake was placed in a solution of 296 parts ethanol and 1125 parts water to form a slurry. The dye was isolated by vacuum filtration. This process was repeated two times, first with 296 parts ethanol and 1125 parts water, then with 608 parts methanol. After the final vacuum filtration the filter cake was dried at 40 °C under vacuum for 48 hours. Yield was The final product can be recrystallized from ethyl acetate or ethanol.

The preparation of other indoaniline dyes is described by Masafumi Adachi et al. in the Journal of Organic Chemistry Org. Chem. 1993, 58, 5238-5244) which is herein incorporated by reference. This paper describes a procedure of preparing dyes by oxidative condensation of suitable p-phenylenediamines and phenols using ammonium persulfate as the oxidant (following the procedure 15 outlined in by Vittum et al. in theJ. Am. Chem. Soc. 1946, 68,2235).

The preparation of various sulfone dyes is described in U.S. Patent Nos.

3,933,914, 4,018,810, and 4,357,405; U.S. Patent Application Serial No.

07/730,225; and in Zhurnal Organicheskoi Khimii, Vol. 15, No. 11, pages 2416 and 2417 (Nov. 1979), which are herein incorporated by reference.

Example 1 A variety of dyes were evaluated as cure indicators by the following procedure. Approximately 0.0005 grams (500 jg) of a dye, as listed in Table la, was transferred to a 1.5 dram (6 ml) clear glass vial containing two drops 200 mg) ofdichloromethane. Approximately 1 ml of stock composition B2 was transferred to the vial and the solution mixed with a spatula until homogeneous.

Approximately 1 ml of stock composition C2 was transferred to the colored solution, a timer started and the composition was mixed thoroughly for 30 seconds.

The composition was placed against a white background and visually examined for the time at which "gelation" and visual color change occurred. Gel times were recorded and it was determined if a color change occurred before the gel -68- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 *1 point, within two times the gel point and/or following 24 hrs; at room temperature.

Set out in Table l b are the results observed for these dyes.

Table lIa.

Dye Identification 1 4 Furtheridentification and/or: Coiment 1 4-f-Dtehbiopeyliio-,-ylhue--n Phenol Blue 2 2 -Chloro-4-[2-metIy4.diehy~an)phelinoI..zs. CAS 68 155-95-3 cyclohexadien- 1-one 3 4-1-Dehkiopo~iiw-.-hdoahhlnl Colour Index one 49705;C.I. Solvent Blue 22 4 4 4 -(DimezhYlamino)phenylimino1,4diydronaphhalen1.. Colour Index 49700 one 4 2 -methiYl-4-(diethylamino)phenyIjimino]-1,4dwhdronaphtbalen-I -one 6 3 -Mdiox4-[[2-methyl-4-diethy~aino)pheWIjimino..2,5 cyclohexadien- 1-one 7 3,-DCor4fmhl4-(d- Lmhoiw~hllomin 2 cyclohexadien-l-one 11 2 6 -mz4-[ 4-rphopholl)pijjro2,5 cyclohexadien- 1-one 12 2 ,6-Dichloro-4-[l4-(4-morhyolino)pheyJimino-25cyclohexadien- 1-one 13I 2,-Dmethoy-4[(-mpho4yl h l~ii 0 2 ,5 cyclohexadlien- 1-one 14 2,-ihoo4[4(ityaiopeylmn]25 cyclohexadien-l-one lcyclohexadien--ao nd 14 q,ionety-4(ith~rnopeyliio]2 cvclohexadien- 1-one 19 2,6-Dichloro-4-[(2-methl4.(etyhyln)imzyinJ,-25 cyclohexadien- 1-one 2,6-Dimethvl-4-[4.hydroxy LO one SUBSTTUESHET(RULE26) WO 96/00560 PCIUS9S108383

S

Dye 1.4Table I a Dye Idetifcatinl-Further Identification and/or Comments 21 2 6 -Dichloro4i(4-methoxY-1..naphthy)iio] 2 cYclOhexadien- 1-one 22 7- 6 -DichOro-4-f4.benzlOxY)PhnYlimio.

2 cYclohexadien- 1-one 23 2 k6DlhOro4{(2,4dimchoxypheyl)iminoJ.

2 cyclohexdien- 1-one 24 sameas #18 same as#21 27 sumeas #23 28 sameas #23 29 44 heyimiw).ScycohxWden-1.,ne 30 4 -(l-naphtimio)2,5cycloexden-1..one 31 4 2 -naphthyimino)..2,5-cyclohexadjen-1.one 32 sme as #31 33 sameas #29 34 2,ammOph enyl)4(hyimi).. 35 saw as 36 snas 37 2 5-D ibrmo124-I(2,4bro1nY)io 2 0 ohan- 38 sam as #37 39 23 -Tlro--[2,h6uior2,4,6j)WijJ.,.~ cyclohexadien-l-one 40 2,-ih~o-41-dmtyai peyj5p~y_2) iidzo-2.yvdine-2,-cyclohefjen-j.

0 41 2,6-Di chloo4 ro,.bs4h 4,sgxy h J)-2H.mi 1 2 Ylidinej-2,5.cvclohexadeon-1..one £-,oluaoxy 4 4 5 bis( 2 fury1)2H..midaoI.2ylidineI.2,5cyclobexadlien-l-one 43 2,6-Bisf 1, 1 (iehlehl41,-i(-uv)(H-mdzl2 I -one 44 4 same as #44 146 Monof( 3 -mehl1Y23H)benzotlazIyiene)hymzno] 2 ,5 cyclollCxadene-1,4-dione 47 3Clr--x-.5ccoeain1yldn~mnj12 Idihydro -1.S-dimetl-y2phenyl.3H.pyr 3 ne CAS 38901487-0 SUBSTIUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/08383

S

S. S

S

S

5*

S

Dye Identification'.

4 Table Ianifcaio and/or.*Commenis 48 3 ,5-Dichloro-4-oxo-2,5-cyclohexadien-1-yljdiue~aznoJ42- CAS 51090-28-9 dihydro-I,5-diethyl-2-phenl.(3H)-pyrazol-3one_______ 49 3 3 ,5-Dcloro4-oxo-2,5-cycohexadien--ylidinamino-2,5 dihydo-4,5-dimethy1-1-pbenAYlprrl-2-one 4-(Phemuffony1)mino-l-[4-[(pheny~sufonyl~jminoj.2,5- 51 5-[5-(1,3-DiethLhexahydro-2,4,.tiaw5oxos.yijnti)Z4 CAS 54444-01-8 penadenyidue-I,3..ihyfl-2,4,6(IIL,3HSH)pyrimidenetrione (trietlammonium salt) 52 4 -16, 6 -Bis[(trfluormethyl)sulfonyll-1,3,s..heazrienyl-N CAS 58558-784 53 4-(4,4-BisI!triluoromethyl)sufonyll-.4,3.bi lI-2..eioxy.

54 4.4-Bs[ lureaysuoul43bd 4J25 55 9..(4,4-Bis[ (trfiuoromehyl)su~nyl..3-bua jenl.2,3,67. CAS 149679-65-2 tetRhydrN1HK5H)-behizoii1oizin 56 4-[4, 4 -Bis[(ttluomedfyl~sfonyl].1,34outagjienyIJ..2,6N1.

57 4 -S,-Bis(zrfluromethyl)sulfony1)-.4penttjienyliaenejj4- 58 6,6-Bis[4-(dimethylamino)phenyl ,3,5-hexatriene-1, 1- CAS 149679482-3 bissUffonylfluoride) 59 4 4 4 -Bis[(zzUfluoromethyl)ufonyll,3buzadinylj-NN. CAS 5W59-02-7; dimehylbenzumn 60 4 3 -(4 4 Dm~ymo)peny.2prpenylidenej-2.pel- 5(4H)-oxazolone 61 2,6-Dichloo- 4-.(ace cyclohexadien-1-mn A C. I. Disperse Yellow 4; Colour Index 12770 azo dye B C. I. Solvent Yellow 14; Colour Index 12055; Sudan Orange R azo dye C C. L Solvent Red 24; Colour Index 26105 bis azo dye D C. I. Solvent Orange 7; Colour Index 12140 azo dye E C. 1. Solvent Red 27; Orient Oil Red 5B bis azo dye F C. I. Solvent Red 23; Colour Index 26100 bis azo dye G C. I. Solvent Red 24; Colour Index 26105: Sudan Red 380 bis azo dye H C. 1. Solvent Red 182; Kavaset Red 802 bis azo dye I C. Solvent Blue 35; Colour Index 61554; Sudan Blue 670 antraquinone i C. I. Solvent Blue 104; Nitrofast Blue 2B, anhau ne K C. I. Solvent Blue 36; Colour Index 61551; SuiniplastBlue OA ,anthraqinone -71- SUBSTITUT SHEET (RULE 26) WO %100560 WO 9600560PCTIIUS95/09393 Table la Identification1.

4 Further Identification Comnrts L C. I. Solvent Violet 13; Colour Index 60725; Oplas Violet 730 anthraquinone M C. I. Sohrent Blue I 1; Kayaset Blue 9 4 anthraqu ine N C. 1. Acid Orange 52; Colour Index 13025; Methyl Orange azo dye 0 C. I. Acid Red 88; Colour Index 1:5620; Fast Red A azo dye P C. I. Acid Yellow 36; Colour Index 13065; Metanil Yellow azo dye Q C. L Acid Violet 3; Colour Index 16580; Victoria Violet azo dye 77 3H-Indolium, 3-[3-[4-(dimetlamino)phenylj-2-propenylidene]- (:pentfuoroethyl)-cycohexanesulfonate salt 78 Bezohazlim 3-(3-amino-3-oxopopyl)-2-[[4-[bis(2- CAS 57230-19-0; chlorethyl)anojphenyllazo].6-methoxy-, 1.2,2,3.4,5,5,6,6- C. L Basic Blue decfluoro4-penafluoroethyl)cyclohexanesulfona salt Colu Index 11076 79 Beztizlum3-(3-aznino-3.nvnnmnu1I)-2-[[4- CAS 12221-38-4; (diethynomd)phenylazo-6-etxy-, chloride C .BscBu 7 ___Colouir Index 11075 3-(3-amino-3-oxopropyl)-2-[[4- CAS 12221-39-5; (diethyLamin)..2-methylphenylJazoJ.6.edioxy. Basic blue 87; 1,2,2,3,3,4,5,5,6,6-decafluoro-4- (jpenafluoroethylcycobexanesuffonate salt Colour Index 11185 9 1 CAS 122214048 C. L. Basic Blue 68 82 CAS 12270-14-3 C. 1. Basic Blue 76; Calcozing Blue 2B 83 CAS 12221-31-7 C. L Basic Blue 57 4 CAS 12221-34.0 C. 1. Basic Blue Benzofa~phenoxazin-7-ftum, 9-(dimcthylamino)-, C. L. Basic Blue 6; 1,2,,3,3,4,5,5,6,6.decafluoro-4-(pentafluoroetayl).- Meldola Blue cyclohexanmsufonate salt 86 2-[4,4,-bis[4-dimethylamino)phenylJ-1,3-buadienyl]-I -ethyl quinolinium, 1,2,,3,3,4,5,5,6,6-decafluoro-4- (pentafluoroethyl)cyclohexaesulfonate salt 87 4-[4,4,-s4-(dimetyLrAmi)penyl-1,3butadienylj 1 -ethyl CAS 80989-42-0 quinolinium, 1,2,,3,3,4,5,5,6,6-decafiuoro-4- (cation) (pentafluoroethyl)cyclohexnesulfonate salt 88 Naphtho[2,1I-dlthiazolium, 2-[4,4-bis[4- (dimethylaniino)phenylJ-1,3-butadienyl]-3-etyl-, 1,2,2,3,3,4,5,5,6,6-decafluoro-4- (pentafluoroethyl)cyclohexanesulfonate salt 89 2-[2-[4-(dimethylamino)phenyllethenylj-1-pheniyl.3-methyI quinoxaliniurn chloride Quinlinium 2-13-(5-chloro-1,3-dihydro-1,3,3-trimethyl-(2H)indol-2-ylidene)-1-propenyl]-1-metiyl-, 1,2,2,3,3,4,5,5,6,6decfluoro-4-(pentafluoroethyl)cyclohexanesulfonate salt -72- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCT71US95/08393 4*

S

S

S*

'S S

S

Dyen Identificafion'4 alel Further Identification' and/or Comments 91 Benzothiazolium, 2 4 -(dimetliylamiino)phenyllazoj.6-methoxv- C. 1. Basic Blue 54 (pentafluoroethyl)cyclohexanesulibnate salt 92 Benz~cdjindolium, 2*[(diethyLamio)-2-thoxyhenyJ..l-ethyl.

1 2 2 3 3 4 ,5,5,6,6-decafluoro-4-{petafluroetjyl).

cyclohexnesulfonaze salt 93 2 -[p-(DimethyLvaino)syry-1,3dimeyqioxiiu methylsulffte salt 94 2 3 -(Sclor-,3-dihvdro-,3,3-imethyl{2l)-indol-2.

1, 2 2 3 ,3,4,5,5,6,6-decafluoro-4- (Pentafuoroethyl~cyclohexanesulfonate salt C. I. Basic Blue 40 (tested as PECH Sulfonate salt) Maxilon Blue RL 96 Beztizlw,2-[[4-[ethyl(2- C. I. Basic Blue 4 1; h -royethyl amnojphenyljazol.6.mehoxy-3mezjhyl, Colour Index 11105; hdylsuilfate salt Deorlene Fast Blue RL;Basacryl Blue X- 3GL 97 Beztizlu,2-[[4-fethyl(2- C. L Basic Blue 4 1; hydroxyethyl)aminolphenylJ~zo]-6.methoxy..3..myl., Colour Index 11105, 1, 2 2 ,3,3,4,5,5,6,6-decfluoro-4. Deorlene Fast Blue (pentafluoroethyl)cyclohexanesufonate salt RL~Asacryl Blue X- 3GL 98 C. 1. Basic Blue 42 (tested as PECH Sulfonate salt) 99 C. 1. Basic Blue 53 Basacryl Blue 3RL 100 3H-Indolium, S-chlorco-2-[5-(5-cbloro.1,3..ihydro.1,3,3..

timihyl2Hindol2-ylidne)1,3.pentadjjnyl.,33-trimetyl.

l.

2 2 3 3 4 .,5,,6,6-decaAluoro4pentafluwotyl).

cyclohexanesuifonate salt 101 Basic Blue 142 102 Benzfcdlindoliuzn, 2-12-(9-ethyl.(9H).carbazol3y)etjhenylJ.ll methyl-, l,2.

2 3 3 ,4.5,5,6,6-decafluoro.4- (Pentafluoroetvl)cyclohexanesulfonate salt 104 Benzfcdjindolium, 2 2 4 -(dimethvlamino)phenylj-2 phenvlethenyl]-l -methvl-, (pentafluoroethyl)cyclohexanesuzifonate salt 105 BenzfcdJindoliuzn, 2-(2.2-bisl4- (dimthylamino)phenyllethenylJ4.-metyl. chloride salt 106 Benz[cd]indolium, 2-[2,2-bis(4- (dimethylamino)phenylethenll-methi. iodide salt 107 Benzlcdlindolium, 2 -1 2 2 3 -dihvdro-l-metjiyl-2-phenl1Hindol- 3 -yl)..2-(2..methvlphenvl)ethenyll-.l.methyl., l,2,2,3,3,4,5,5,6,6-decafluoro-4- (penzafluomethvl)cclohexanesfoat salt -73- SUBSTIUT SHEET (RULE 26) WO 96/00560 PCTIUS9SIO8383 V V V. V

V

V.

V.

V

V V

V

V V V. V V. V

S

V

V.

V

V

Table la De# et fu~onl 4 Further Identification 1108 Pyriridinijzrn 2.3-dihydrl,3.dimetl2ox-(1H- an/r omet PYfifidnylidene)41,3-pa~dienyIJ-2,3dihydro-1.3-djmnethyl-2 109 3H-Indolium, 2 -[[3-I(1,3.iydro-1,3,3-rimeuiyl.2H1.indgol.2yhide)mehyl]5,5ie1hyl2cycohxn.1lydnemehl..

1,3,,3-triredayl-, l, 2 3 3 ,4,5,5,6,6-decafluoro4.

(penafluoroeshyl) 1- -mn lft salt 110 samneas #100 III Beazledljudlium, 2-f2-f 4-(diethylaminO)-2nethYlphenYllethenYlj1-methy., lZ 3 34,5,5,6,6qiecluoro.

4-(Pentafluozuethyl)cyclohemazesufonate salt 112 3H-Indolium, 3-[3.[4.[(dehyaiopey)2 Prpni dee-.methy-2(4.mez~xyphenyI)., ylnyene-12dinetyl., rifluo If salt 114 3H-Indoliurn, 34(2 5-dime hyl-l-pbe .(1H>.pyr-3..

yl)meshyle]e-1-methyl2-pheuyl. riluoomtiaeslont 115 2 2 2-chloro4(dimeft ymin pi~ljhj.

rnedylbez~cdindolium, l.

2 2 3 3 4 ,5,5.6,6-decajjiw..4 (Penzfluormethy1)-cyclohexaneswjjnate salt 116 sam a;#77 117 C. I. Basic Violet 22 (tested as pECH Sulfonate salt) Basacryl Violet RL 118 C. I. Basic Red 15 (tested as PECH Sulfonate salt) Geaacryl Brilliant

B

119 same as #94 120 sarneas# III 121 Benzlcdlindoliurn, 2 2 4 -(dimethyin)phxlhenyfl )J.l.

miethyl-, l, 2 9 3 3 4 ,5,5,6,6.decfluoro-4-petaiuoreahyl..

cyclohexanesulfonate salt 122 BenzlcdlindoliuL2[2.14(dimethyaznno).

2 ethoxyphenyllethenylj.1.inethyl, iodid e salt 1123 3H-Indoliurn. 24 I-cyano- 4 ,4-bisl4-<dimezvlammo)penyll13butadienylJ-1,3,3-trimethll, l, 2 2 3 3 ,4,5,5,6,6.decafluoro4-..

(Penzafloethvl)-cvclohexanesulfonate salt I Table b ~Dye jInitial Color Gel tume Color Change Solubility in Color I# I (seconds) at 2xGT 3 at 24 hours Isilicone, Change I purple 265 bleached blahdS -74- SUBSTTTE SHEET (RULjE 26) WO 96/00560 PCT/US95/08383 **0WSR

S

SS

S.

S.

V

S.

*5 5

S

S* S Table lb Dye Initial Color Gel time Color Change Solubility-in Color (seconds) at 2xGT 3 at24 hours silicone? Change 2 blue 290 bleached (light bleached S yellow) 3 blue 320 bleached (light bleached S yellow) 4 blue 320 bleached (light bleached SS Sdow) blue 245 bleached bleached S 6 blue 217 bleached bleached S 7 blue 250 bleached blehed

I

8 purple 267 bleached bleached S 9 purple 305 bleached bleached S blue 293 bleached bleached

I

II Ipurple 255 no change bleached 12 blue/green 270 bleached bleached S 13 blue 230 bleached bleached

I

14 aqua 288 no change bleached

I

15 green 240 bleached bleached S 16 blue 505 bleached before bleached S 17 green 282 partially bleached bleached 18 purple 277 no change- bleached 19 purple 284 no change bleached orange 257 partially bleached

I

_________bleached 21 blue 270 partially bleached S bleached 22 lavender 240 bleached bleached

I

23 purple 261 bleached bleached S 24 purple 290 no change bleached blue 330 partially bleached bleached 26 purple 335 no change bleached___ 27 purple 420 no change bleached_ 28 purple 330 color changed bleached

I

29 orange 246 bleached bleached

SS

magenta 270 bleached bleached S 31 orange 264 bleached bleached S 32 orange 333 bleached bleached S 33 orange 330 bleached bleached S 34 orange 240 bleached bleached S orange 240 bleached bleached S 0S S a

S

SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 ioo.o.

go 0Go 0o 5*o o oooo

S.:

08 Ioo@@g Table lb Dye .Iitial Color Gel time Color Change Solubility in Color _(seconds) at2xGT 3 at 24 hours silicone 2 Change 36 magenta 270 bleached bleached 37 magenta 600 no change bleached 38 orange 240 no change bleached 39 red, low 270 bleached bleached intes.

blue/green 290 slight bleaching bleached

I

41 orange 250 slight bleaching bleached S slight bleaching 42 magenta 317 bleached bleached S slight bleaching 43 orange 240 no change bleached 44 orange 250 bleached bleached I orange 450 no change bleached S slight bleaching 46 orange 241 bleached bleached S slight bleaching 47 onge 258 bleached bleached SS 48 magenta 260 no change bleached S no change 49 orange 227 bleached bleached S sli orwge 240 bleached bleached 51 fluor. blue 246 bleached bleached S 52 purple 330 bleached bleached S 53 purple/pink 313 bleached bleached S 54 purple/pink 310 bleached bleached S 55 purple 326 bleached bleached SS 56 purple 332 bleached bleached SS 57 purple 310 bleached bleached SS 58 blue 2M8 bleached bleached S 59 magenta 306 bleached bleached S magenta 313 bleached bleached SS 61 lavender 315 not measured bleached S (intense) A yellow 270 no change B orange 290 no change no change C red 298 no change no change D orange 276 no change no change E red 212 no change slight F red 194 slight darker darkening G red 247 no change no change H red 80 no change I blue 377 no change no change J blue 237 no change no change -76- SUBSTITUTE SHEET (RULE 26)

I

WO 96/00560 WO 9600560PCTIUS95/08383 Table Dye Initial Color GW time Color Chage Solubility in Color (seconds) at 2xGT 3 at 24 hours silicone 2 Change K blue 103 no change L blue 90 no change M blue 81 no change N orange 300 no change slight bleaching_____ 0 lavender 235 no change nochange P Yellow 270 no change no change Q purple 291 no change nochange 77 blue 150 bleached before bleachedI gel time_ 77 blue 219 bleached bleachedI I79 blue 261 bleached before bleachedI imke 80 blue 259 bleached bleachedI 81 purple 256 bleached bleachedI 82 blue 236 bleached bleachedI 83 blue 266 bleached bleachedI 84 blue 290 bleached bleachedI purple 182 bleached bleached 86 blue 270 bleached before bleached 8 7 b l u e 3 8 0 g e bl e h db e c e 88 blue 360 bleached beoebleached gel fim 89 blue 255 bleached bleached blue 205 bleached bleached 91 blue 246 bleached bleachedI 92 blue 267 partially bleached

I

bleached 93 blue 232 bleached- bleached 1 94 blue 240 bleached bleached 1 blue 220 bleached bleachedI 96 purple 164 bleached bleached 97 purple 193 bleached bleachedI 98 purple 196 bleached bleached 1 99 blue 278 bleached bleached I 100 blue 258 bleached bleached I 101 blue 287 bleached bleached 1 102 blue 320 bleached bleached 1 104 green 252 bleached before bleached

I

gel -77- SUBS1TTUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 _Table lb Dye Initial Color Gel time Color Change Solubility in Color .___(seconds) at 2xGT at 24 hours silicone Change 105 green 252 bleached before bleached

I

gel time 106 blue/green 370 bleached before bleached I ge time 107 green 600 bleached before bleached I gel time 108 blue 290 bleached before bleached I 8d time 109 purple 166 bleached bleached I 110 blue 582 bached bleached I 111 blue/green 368 bleached before bleached I Rd time 112 blue 278 bleached bleached I 113 orange 371 bleached bleached

I

114 orange 260 bleached bleached

I

115 green/blue 409 bleached bleached I 116 blue 955 bleached before bleached

I

gel time 117 magenta 337 bleached bleached

I

118 magenta 337 bleached bleached

I

119 magenta 283 bleached bleached

I

120 blue/green 155 bleached before bleached

I

gel time 121 blue 222 bleached before bleached

I

gel time 122 purple 204 bleached before bleached

I

gel time 123 purple 190 bleached before bleached

I

Sel time Footnotes for Tables la and Ib: The "dye and "identification" correspond to the formula depicted in the attached drawings of dye structures. For brevity, the "dye listed in Table la will be used throughout the examples to refer to specific dyes. Notably, the cationic dyes may comprise any suitable counter ion and are not limited to the specific counter ion(s) shown or depicted in the table or the attached drawings. Similarly, anionic dyes may comprise any suitable counter ion and are not limited to the specific counter ion(s) shown or depicted in the table or the attached drawings.

Cationic dyes 77, 78, 80, 85-88, 90-92, 94-95, 97-98, 100, 102, 104, 107, 109- -78- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTUS95/08383 111, 115-121, and 123 were tested as PECH Sulfonate salts, though the CAS or C. I. name or number listed in the table may describe the cation paired with a different anion.

2 soluble; insoluble; "SS" slightly soluble.

3 "2xGT" twice the time elapsed to gel time.

"PECH Sulfonate" 1,2,2,3,3,4,5,5,6,6-decafluoro.4(pentafluoroethy) cyclohexane sulfonate.

The data of Table lb show that neutral dyes I to 50 and 52 to 61, anionic dye 51, and cationic dyes 77 to 123 all exhibit a significant color change within 24 hours. Notably, dye 51 changed from being a fluorescent dye to a colorless nonfluorescent dye. In addition, many of these dyes exhibit a color change at some time less than two times the gel point Several dyes 16, 77, 79, 86, 88, 104-108, 111, 116, and 120-123) exhibited bleaching prior to gelation and may be suitable as working time indicators. Dyes potentially suitable as set time indicators include: neutral dyes 1-10, 12-13, 15, 17, 22, 23, 29-36, 39, 42, 44, 46, 47, 49-50, 52-60, anionic dye 51, and cationic dyes 78, 80-85, 87, 89-102, 109, 110, 112-115, and 117-119.

S"In contrast, comparison dyes A to E and G to Q comprising neutral azo and anthraquinone dyes fail to exhibit a significant color change during any stage of the curing process. Comparison dye F exhibited a gradual darkening over 24 hours that did not correlate to any particular curing state.

Example 2 A number of dyes were further examined for solubility in the solventless silicone formulations of Preparatory Example 2. Those dyes that exhibited a noticeable color change within two times the gel point (as observed in Example 1) were evaluated for silicone solubility by the following procedure. Approximately 500 .tg of the dye was transferred to a 1.5 dram (6 ml) glass vial. Approximately

I

ml of stock composition B I was transferred to the vial with a disposable dropper, the solution was mixed with a spatula for approximately 3 minutes, and the mixture -79- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 was examined visually for coloration of the silicone liquid. Coloration of the resin indicates that the dye was soluble or highly dispersed in the composition. Several dyes required 1 to 2 drops (-150 to 300 mg) ofdichloromethane to induce solubility and were classified as "slightly soluble". Those dyes that required additional solvent more than 1-2 drops) to color the composition were classified as "insoluble". The data is presented in Table lb. Neutral dyes 1-6, 8-9, 12, 15, 16, 21, 23, 29-35, 41, 42, 45-49, 52-55, 57-59, and 61, and anionic dye 51 were all at least slightly soluble in stock composition B1. None of the cationic dyes were soluble in stock composition B1, although it is believed presently that such solubility could be achieved by modifying the anion, by modifying the dye cation by incorporating a suitable solubilizing group), or perhaps by modifying the dye cation to provide an amphoteric dye.

A

Example 3 15 A variety of silicone soluble dyes were evaluated as "cure indicators" in solventless silicone formulations. Neutral dyes 1-6, 8-9, 12, 15, 16, 21, 23, 30-35, 41, 42, 45, 46, 48, 49, 52-58, and 61, and anionic dye 51 were independently evaluated in the following procedure. Approximately 500 gg of a dye was transferred to a 1.5 dram (6 ml) glass vial. To this was added approximately 1 ml of stock composition B1, using a disposable dropper, the solution was mixed with a spatula for approximately 3 minutes and the mixture was examined visually for coloration of the resin and general solubility of the dye. Dichloromethane was used sparingly (1-2 drops) to promote solubility of less-soluble dyes. Approximately 1 ml of stock composition Cl was transferred to the colored solution, a timer was started and the composition was mixed thoroughly with a mixing stick for seconds. The composition was placed against a white background and examined for the times at which gelation and visual color change occurred, and specifically if a color change occurred before the gel point, or within two times the gel point at room temperature. The data in Table lb shows that nearly all of these dyes examined exhibited a partial or total color change within two times the gel point.

SUBSTTUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 Example 4 A simple and effective method of selecting suitable cure-indicating dyes for compositions of this invention was developed and a variety of dyes were evaluated by this method. Dyes were evaluated according to the following "pentamethyldisiloxane test". Approximately 500 gg of dye was transferred to a dram (6 ml) clear-glass, screw cap vial. To this was added, in order, 500 l of dichloromethane, 100 pl of pentamethyldisiloxane, and either: 25 pl of a catalyst solution comprising 25% by weight of a commercially available catalyst (PC075, available from United Chemical Technology, Inc. Bristol, PA) in dichloromethane; or 10 pl of a commercially available catalyst solution (PC072, available from United Chemical Technology, Inc. Bristol, PA). The vial was capped, agitated for approximately 5 seconds at room temperature and the solution was observed for bleaching. Those dyes that exhibited bleaching within 5 minutes also exhibited a significant color change in the compositions of Example 1 and are 15 believed to be suitable for use in this invention. Set out below in Table 4a are the dye number, dye type, results of the reactivity test and corresponding color change results from Table lb. The data from Table 4a shows that dyes that fail to exhibit a significant color change in the reactivity test (indicated with a negative sign are unlikely to function as visible cure monitors for the compositions of this invention; 20 whereas, those dyes exhibiting a positive test response (indicated with a positive sign are likely to serve as effective cure monitors. Notably, of the neutral anthraquinone and azo dyes tested, all failed the reactivity test and were ineffective cure monitors in the formulations of Example 1.

Table 4a Comparison of Reactivity Test Results and Example 1 Results Table lb Color Change Dye Number Dye Type Reactivit Test Results Results 1 neutral 2 neutal 4 neutral 16 neutral 52 neutral 59 neutral neutral 77 cationic+ -81- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 *fl.

S

S

S

S.

*5

S

S

Table 4a Comparison of Reactivity Test Results and-Example 1 Results Dye umbr Dy TyTable lb Color Change Dy Nmbr Reactivity Test Results Rtesults 78 cationic 82 cationic 91 cationic 96 cationic 97 cationic 99 cationic 101 cationic B neutral___ C -neutr D neutral E neutral F neutral G neutral H neutral I neutral__ IJ neutral K neutral L neutral M neutral N neutral 0 neutral P neutral Example A stock hydride and dye Composition MR5) was prepared by combining and mixing in a glass container 0.0035 parts by weight of dye number 2 and 50 parts by 5 weight of the crosslinker compound of Preparatory Example 2 A stock vinyl and dye composition (V5) was prepared by combining and mixing in a glass container 0.003 5 parts by weight of dye number 2 and 50 parts by weight of the vinyl termiinated polydimethylsiloxane compound of Preparatory Example 2 A stock catalyst composition (C5) was prepared by combining and mixing in a glass container 5 parts by weight of the platinum catalyst solution described in Preparatory Example 2 and 5 parts by weight dichloromethane.

Five compositions comprising varying hydride/vinyl ratios were prepared according to the following procedure and evaluated for gelation and dye color bleaching. Ten grams of VS was transferred to each of five glass vials along with -82- SUBSMruT SHEET (RULE 26) WO 96/00560 PCT/US95/08383 0.20, 0.30, 0.40, 0.50, and 0.60 grams respectively of HS. The compositions were mixed thoroughly, 0.10 grams of C5 was added to each vial, and the compositions again mixed until homogeneous. The samples were examined after standing minutes and also after standing approximately 1 hour, and a determination of gelation and bleaching established. Set out below in Table 3 are the run number, proportions of H5, V5, and C5, approximate ratio of hydride to vinyl, and whether gelation and/or bleaching occurred following 5 and 60 minutes. The data shows that gelation occurs for all compositions (indicated as sign) whereas complete bleaching (indicated as sign) only occurs when the ratio of hydride to vinyl exceeds approximately one. Samples having a ratio of hydride to vinyl less than approximately one did not bleach (indicated as sign). This result indicates that under the conditions of this example excess unreacted) hydride is required to effect bleaching of the dye and that the reaction between hydride and vinyl occurs preferentially to the reaction between hydride and dye.

S

~Table 5a Run H5 V5 C5 Hydride: Gel Bleaching gms) (gms) viniy ratio tS min at 60 min 1 0.20 10.0 0.10 0.50 2 0.30 10.0 0.10 0.75 3 0.40 10.0 0.10 1.00 slight slight bleaching bleaching 4 0.50 10.0 0.10 1.25 5 0.60 10.0 0.10 1.50 Example 6 A filled molding or dental impression material composition was prepared according to the following procedure. A filled base composition (B6) was prepared by transferring 25 parts by weight each of stock composition B from Preparatory Example 2 and dichloromethane to a 225 ml Semco mixing tube (available from Technical Resin Packaging Inc., Brooklyn Park, MN) and agitated by shaking.

0.0034 grams of dye #77 was dissolved in 1.2 grams of dichloromethane, added to the Semco cartridge and mixed by shaking. Ten grams ofQuso WR-55 filler (available from Degussa Corp., Dublin, OH) was added to the cartridge and mixed -83- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 minutes on a Model 388 automatic Semkit Mixer (available from Technical Resin Packaging Inc., Brooklyn Park, MN). 50.0 grams oflmsil A-25 filler (available from Micronized Unimen Specialty Minerals, Cairo, IL as Imsil A-25 micro crystalline silica) was then added to the cartridge and mixed for 10 minutes. Finally, an additional 5 grams each of B1 and dichloromethane was added to the cartridge and mixed for 5 minutes yielding a light blue paste.

A filled catalyst composition (C6) was prepared by transferring 25 parts by weight each of stock composition Cl from Preparatory Example 2 and dichloromethane to a 225 ml Semco mixing tube and agitated by shaking. 8.3 grams ofQuso filler was added to the tube, mixed 5 minutes on a model 388 Semkit Mixer, followed by the addition of 41.7 grams of Imsil A-25 filler and 12 minutes mixing. This procedure yielded a white paste.

Approximately equal volumes of B6 and C6 were transferred to independent chambers of a dual barrel mixing cartridge which were sealed with inserts. The 15 cartridge was inserted into a hand held dispensing apparatus, a Kenics static mixing tip was placed on the cartridge, and the catalyst (Cl) and base (B1) mixed by coextrusion through the mixing tip. A Kenics static mixer consists of a circular pipe within which are fixed a series of short helical elements of alternating left- and righthand pitch. The helical design of the central element causes a transverse flow to 20 arise in the plane normal to the pipe axis. As a consequence, radial mixing of the two compositions is achieved. A complete description of the fluid mechanics of a Kenics static mixer may be found on pages 327 and 328 of Fundamentals of Polymer Processing, by Stanley Middleman. The silicone compound begins to react crosslink) upon mixing the two compositions together.

The mixed paste became rigid and exhibited a color change from light blue to pale blue within about 6 minutes.

Example 7 A solventless, filled, molding or dental impression material composition was prepared according to the following procedure. A filled base composition (B7) was prepared by transferring 200 grams of stock composition B from Preparatory -84- SUBSTTUTE SHEET (RULE 26) WO 96/00560 PCT/US95108383 Example 2, 2.8 grams Silwet L-77 (available from OSi Specialties, Inc., Lisle, IL), and 20 grams Quso WR-55 to a Ross double planetary mixer. The materials were mixed for 5 minutes at 40 rpm. 135 grams of Imsil A-25 filler were then added to the mixer pot and mixed for 5 minutes. Finally, 45.0 grams of Imsil A-25 were added to the mixer and mixed under vacuum for 35 minutes yielding a white paste.

A filled catalyst composition (C7) was prepared by dissolving in a Ross mixer approximately 0.0254 grams of dye #2 in 187 grams of stock composition

CI

from Preparatory Example 2. 2.62 grams Silwet L-77 and 18.7 grams Quso were added to the Ross mixer and mixed for 5 minutes at 40 rpm. A 126 gram aliquot of Imsil A-25 filler was added to the mixer, mixed for 5 minutes followed by the addition of an additional 42 grams of Imsil A-25 and mixing for 35 minutes under vacuum at 40 rpm. This process yielded a blue catalyst paste.

Approximately equal volumes ofB7 and C7 were transferred to independent o* a chambers of a dual-barrel mixing cartridge. The cartridge was inserted into a handheld dispensing apparatus, a static-mixing tip placed on the cartridge and the catalyst (C7) and base (B7) mixed by co-extrusion through the static-mixing tip.

The mixed paste stiffened, then became rigid and exhibited a color change from light blue to white at approximately the same time of 3 to 3.5 minutes.

Example 8 The effects of varying levels of hydride/vinyl ratio, vinyl/platinum ratio and dye concentration upon bleaching time and setting time were examined by utilizing a three-variable "central composite" design experiment. Experiments of this type are extremely useful in examining the effects of reactive ingredients and optimizing the composition formula to prepare practical, useful impression materials.

As shown in Table 8a, catalyst impression materials (C8) were individually prepared by adding the indicated parts by weight of platinum catalyst (a solution of 2.55% Pt by weight in vinyl-terminated polydimethylsiloxane as described in Preparatory Example vinyl-terminated polydimethylsiloxane ("LMWP" as described in Preparatory Example 2) and Aerosil R202 (a fumed silica available from Degussa Corp., Dublin, OH) to a 225 ml Semco tube and mixing by means of SUBS7TU SHEET (RULE 26) WO 96/00560 PCrIUS95/033 a model 388 Semkit mixer for 7 minutes. Base impression materials (C8) were prepared similarly by adding the indicated parts by weight of crosslinker ("XL1" as described in Preparatory Example vinyl-terminated polydimethylsiloxane "LMWP", dye 2 (added as a 0.05 w/w solution in CHCI 3 and Aerosil R202 to a 225 ml Semco tube and mixing by means of a model 388 Semkit mixer for 7 minutes.

Approximately equal volumes of C8 and B8 were added to independent chambers of a dual-barrel mixing cartridge and mixed by extruding through a staticmixing element. Curing parameters were determined on a Monsanto Model R100 oscillating disc rheometer and are presented in Table 8b. The rheometer measures torque as a function of time. "T5" is the amount of time it takes for the torque to reach 5% of maximum value. "T90" is the amount of time it takes for the torque to reach 90% of maximum value. These values approximate the working time and setting time of the composition, respectively.

15 Table 8b shows cure times (T90 and T5) and bleach time (BT) at 27*C for each sample. The SiH/Viyl ratio, Vmyl/Pt ratio, and dye concentration were all e found to be significant contributors to the bleach time. It is especially useful to examine the data with reference to the bleach time and BT/T90 ratio. The SiHinyl ratio was the most significant variable had the strongest effect on BT). Runs 20 1, 3, 5, 7, and 13 all have SH/Vinyl less than 1.0. Notably, bleaching was observed only for run #3 (which had low dye concentration and a high Vinyl/Pt ratio).

By examining selected pairs of runs one can determine the effect of individual variables. For example, comparing run #2 to run #6 to or run to #16 one can isolate the effect of changing the vinyl/Pt ratio. In general, increasing the amount of Pt decreases both BT and the BT/T90 ratio. By comparing run #2 to run #4 to or run #17 to #18 one can isolate the effect of dye concentration. In general, raising the dye concentration increases the BT and ratio.

The BT/T90 ratio is indicative of the relationship between setting time and bleaching time. Setting time indicator compositions may be generalized to those materials having a BT/T90 ratio of approximately 1.0. Compositions with -86- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCr/US95OS3S3 ratios greater than about 1.2 may have less utility in this application. Compositions with a BT/T5 ratio of approximately 1.-0 may be viable working time indicators.

Table Ba aaytPaste (parts) -Base Paste (parts)- a CAyst- Vyl: Aerosil Cross- Vinyl terminated De- #2 Aerosil' er...tminated.. R02 lner plydimethyl- R02 lydi_- sioxane ~ifoxane 1 .0148- 49.985 5 3.65 46.35 0.00061 .013 49.987 5 15.4 34.6 0.00061 0.0931 9.907 15 3.64 46.36 0.00061 .0819 9.918 5 15.39 34.61 0.00061 .0148 19.985 5 3.65 4.35 0.01020 __0.013 [9.987 5 15.4 34.6 0.01020 0.0931 k9.907 5 364 4636 0.01020 0.0819 49.918 5 15.39 34.61 0.01020 __0.0357 49.964 -5 766 42.34 .00250 0.0357 49.964 5 766 42.34 0.00250 11- 374.6 .6 23 12 0.0357 49.964 5 766 42.34 ;0.00250 13 P.0377 49.962 5 25 47.75 0.00250 14 0.0297 49.97 5 2303 26.97 0.00250 0.00795 49.99 5 1766 42.34 0.00250 16 0.1596 49.84 5 765 42.35 0.00250 17 357 .964 5 6 2 3 40.00 18 0.0357 49.964 5 766 42.34 0.0025 198 0.03 57 49.964 5 7.66 42.34 0.02500 0 0.035749.964 5 7.66 12.34 0.00250 1m 0.371994_ m.6:--23 .05 a a -87- SUBSTITE SHEET (RULE 26) WO 96/00560 PCT/US95/08383

S

*555

S

*5 S

S

S.

5.55

S

S. S S. S S

S.

S

S.

S

S

8b___ Run 7 SiH/Si-Vi Si-Vi/Pt Dye, grams leach T90 (sec) T5 (sec) Bleach Bleach e (sec) Time/rT90 1 0.82 112.4 0.00061 10,000 586 259 >20 2 3.95 112.4 0.00061 2 114 85 0.72 0.96 3 0.82 17.9 0.00061 160 371 164 0.43 0.98 4 3.95 17.9 0.00061 52 82 45 0.63 1.16 0.82 112.4 0.01020 >10,000 552 240 >20 6 3.95 112.4 0.01020 110 94 59 1.17 1.86 7 0.82 17.9 0.01020 >10,000 354 153 >30 8 3.95 17.9 0.01020 70 82 45 0.85 1.56 9 1.8 44.8 0.00250 174 178 109 0.98 1.60 10 1.8 44.8 0.00250 164 191 114 0.86 1.44 11 1.8 44.8 0.00250 167 178 110 0.94 1.52 12 1.8 44.8 0.00250 170 189 113 0.9 1.50 13 0.5 44.8 0.00250 >10,000 411 250 >25 14 6.5 44.8 0.00250 39 52 32 0.75 1.22 15 1.8 201 0.00250 272 273 147 1 1.85 16 1.8 10 0.00250 102 162 85 0.63 1.20 17 1.8 44.8 0.00025 136 175 108 0.78 1.26 18 1.8 -44.8 0.02500 232 180 111 1.29 2.09 19 1.8 44.8 0.00250 160 182 112 0.88 1.43 20 1.8 44.8 0.00250 187 176 109 1.06 1.72 Example 9 Several other dyes evaluated in Examples 1 and 4 were compounded into filled molding or dental impression material compositions according to the following procedure.

Filled catalyst compositions (C9) were prepared by adding 0.014 parts of dye dissolved in 0.7 ml of CHCI 3 to a stock catalyst solution containing 96.73 parts vinyl-terminated polydimethylsiloxane ("LMWP", from Preparatory Example 2), 0.76 parts Silwet L-77, and 2.51 parts platinum catalyst ("Karstedt" type Pt catalyst, 2 to 3 Pt in vinyldimethylsiloxy- terminated polydimethylsiloxane, prepared in a similar manner as described in Preparatory Example la and having a viscosity of 2.0 Pa in an 225 ml Semco tube. 10 parts Quso WR-55 were added -88- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 and mixed by means of a model 388 Semkit mixer for 5 minutes. 60 parts Imsil Awere added and mixed for 5 minutes followed by 30 parts Imsil A-25 and mixing for an additional 30 minutes to yield colored pastes.

Filled base compositions (B9a and B9b) were prepared by the following procedure. B9a: 178 parts crosslinker 620 parts vinyl terminated polydimethylsiloxane 11.2 parts Silwet L-77, and 80 parts Quso WRwere added to a 1 gallon Ross mixer and mixed for 5 minutes at 30 rpm. 480 parts Imsil A-25 were added and mixed for 5 minutes at 30 rpm. Finally, 240 parts Imsil A-25 were added and mixed under vacuum for 50 minutes at 30 rpm to yield an off-white paste. B9b: 66 parts crosslinker 231 parts vinyl terminated polydimethylsiloxane 4.2 parts Silwet L-77, and 30 parts Quso were added to a 1 quart Ross mixer and mixed 5 minutes at 40 rpm. 179 parts Imsil A-25 were added and mixed for 5 minutes at 40 rpm. Finally, 90 parts Imsil were added and mixed for 50 minutes under vacuum at 40 rpm to yield an off-white 15 paste.

Approximately equal volumes of C9 and B9a (runs 1, 2, and 6-10) or C9 and B9b (runs 3-5) were placed in the chambers of a dual-barrel mixing cartridge S' and mixed by extruding through a static-mixing element. The mixed pastes cured in .C.i approximately 3 to 3.5 minutes (cure time defined as T90 at 27 0 The bleach 20 times, defined as the amount of time it takes to bleach completely (as compared to a reference prepared without dye) are listed in Table 9a below.

-Table 9a Run Dye Initial Color Bleach Time ~(800F) I none off white

NA

2 #2 blue 4 minutes 3 #53 pink 5 minutes 4 #60 purple 6 minutes #56 pink 4 minutes 6 H pink

DNBC'

7 E pink

DNBC'

8 L purple DNB -89- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 Table 9a Run Dye Initial Color Bleach Time I _(80 0

F)

9 K blue DNB 2 M blue DNB 2 Footnotes for Table 9a: 'Approximately 80-90% bleaching occurred in 90-120 minutes; however, the sample did not bleach completely ("DNBC") even after 72 hours.

2 "DNB"=did not bleach.

Example Several other filled molding or dental impression compositions were prepared utilizing dye #2 and also a non-cure-indicating pigment to impart both a unique initial-mix and final-cure colors.

*5 10 Cure-indicating base impression material composition (B10) was prepared by adding 22.4 parts Silwet L-77, 356 parts crosslinker 1239 parts vinyl terminated polydimethylsiloxane and 0.23 parts dye #2 (added as a 0.05 w/w solution in CHC 3 to a Ross mixer and mixing 5 minutes at 30 rpm. 160 parts Quso WR-55 were then added and mixed for 5 minutes at 30 rpm. 960 parts Imsil 15 A-25 were added and mixed for 5 minutes at 30 rpm followed by 480 parts Imsil A- 25 and an additional 50 minutes mixing at 30 rpm under vacuum to yield a blue base impression paste.

Catalyst impression material compositions (C10) were prepared by adding 11.2 parts Silwet L-77, 783 parts vinyl terminated polydimethylsiloxane

("LMWP"),

16.4 parts Pt catalyst (as described in Preparatory Example la but diluted in "LMWP"), and either 8 parts of red pigment (available from Warner-Jenkinson, St.

Louis, MO as #K7183 D&C Red #7 Calcium Lake) or 16 parts of yellow pigment (available from Reed Spectrum, Inc., Minneapolis, MN as Yellow #1604404) to a Ross mixer and mixing for 5 minutes at 30 rpm. 80 parts Quso WR-55 was added and mixed 5 minutes at 30 rpm. 480 parts Imsil A-25 were added and mixed for minutes at 30 rpm followed by 240 parts Imsil A-25 and an additional 50 minutes SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 mixing at 30 rpm under vacuum to yield pinkish-red (ClOa) or yellow (ClOb) catalyst impression pastes.

Approximately equal volumes of C10 and B10 were placed in the chambers of a dual-barrel mixing cartridge and mixed by extruding through a static mixingelement. The mixed pastes cured in approximately 3 to 3.5 minutes (27 0 The initial color of the ClOa/B10 impression paste is purple and bleaches to a pinkishred color in approximately 3.5 minutes. The initial color of the C10b/B10 impression paste is green and bleaches to a yellow color in approximately minutes.

Example 11 The effect of the hydrosilation inhibitor diethyl maleate (DEM) on the gel time and bleaching time of curable compositions at 25 0 C and 85 0 C was examined.

A stock dye catalyst solution (SDC11) was prepared by transferring 0.0034 grams of dye 2 and approximately 0.10 grams of dichloromethane to glass jar.

Approximately 50.0 grams of stock composition C (from Preparatory Example 2) S was transferred to the glass jar and mixed with a wooden tongue blade until homogeneous. Similarly, a stock dye base solution (SDB 11) was prepared by transferring 0.0034 grams of dye 2, approximately 0.10 grams of dichloromethane and approximately 50.0 grams of stock composition B 1 (from Preparatory Example 2) to another glass jar and the components were mixed with a wooden tonguedepression blade until homogeneous. Three samples containing various amounts of diethyl maleate were prepared by transferring 0, 1, or 5 pl respectively of diethyl maleate to separate 1.5 dram glass vials. Approximately 0.50 grams of the stock solution SDC11 and 0.50 grams of the stock solution SDBl 1 were transferred to the respective vials, mixed thoroughly for 30 seconds with a mixing stick and examined for gel time and bleaching time at 25 0

C.

A second set of similar samples was evaluated for gel and bleaching time at 0 C. A glass microscope slide was placed on a hot plate heated to 85*C. Three samples containing various amounts of diethyl maleate were prepared by transferring 0, 1, or 5 pl respectively of diethyl maleate to separate 1.5 dram glass -91- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 vials. Approximately 0.50 grams of the stock solution SDC I and 0.50 grams of the stock solution SDB 11 were transferred to the respective vials, mixed thoroughly for 30 seconds with a mixing stick and one drop (-0.05 grams) of the mixture applied to the heated glass slide. These samples were probed and visually inspected both for gel time and for bleach time. Set out in Table 1 la are the amounts of diethyl maleate added and the gel and bleaching times at 25 and 85 0

C.

_____Table lla Run-# DEM Gel time Bleach time Gel time Bleach time (ml) (25 0 C) (25*C) (85 0 o) (85 0

C)

1 0 135 sec. 210 sec. 8 sec. 12 sec.

2 1 1.5 hrs. 8 hrs. 22 sec. 20 sec.

3 5 >>48 hrs Significant 81 sec. 15 sec.

bleaching at 48 hrs.

The data show that the addition of DEM to hydrosilation-curable compositions results in room-temperature-stable compositions that can be cured and cure-monitored at elevated temperatures. Increasing levels of DEM result in bleaching times that occur at shorter times relative to gel times at 85 0 C thus providing potential indicators for working time, gel time and setting time.

Example 12 The effect of two additional active-hydrogen (proton) sources on the gel time and bleaching time of curable compositions at room temperature was evaluated. Four samples containing various amounts of dodecanol were prepared by transferring 0, 5, 10 or 20 il respectively of DDL to separate 1.5 dram glass vials. Approximately 0.50 grams of the stock solution SDCI and 0.50 grams of the stock solution SDB I were transferred to the respective vials, mixed thoroughly for 30 seconds with a mixing stick and examined for gel time and bleach time at 25 0

C.

-92- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 A second set of samples containing various amounts of acetic acid were evaluated for gel and bleaching time at 25 0 C. Four samples containing various amounts of acetic acid were prepared by transferring 0, 1, 5 or 10 u respectively of AA to separate 1.5 dram glass vials. Approximately 0.50 grams of the stock solution SDC1 and 0.50 grams of the stock solution SDB1 were transferred to the respective vials, mixed thoroughly for 30 seconds with a mixing stick and examined for gel time and bleach time at Results for both experiments are shown in Table 12a.

Table 12a Run# Indicator (pli) Gel time (25 0 C) Bleach time 'adjuvent 1 DDL 0 158 sec. 244 sec.

2 DDL 5 160 sec. 244 sec.

3 DDL 10 167 sec. 250 sec.

4 DDL 20 190 sec. 310 sec.

5 AA 0 150 sec. 220 sec.

6 AA 1 154 sec. 150 sec.

7 AA 5 240 sec. 140 sec.

8 AA 10 600 sec. -150 sec. (slight blue tinge) The data show that the addition of DDL to hydrosilation-curable compositions results in minimal change to gel and bleach times. In contrast, the addition of AA results in longer gel times and shorter bleach times, respectively, at room temperature. Thus the addition of adjuvents to compositions of the present invention can be utilized to adjust the relationship between the color change and the cure reaction.

-93- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/08393 Example 13 Indication of cure inhibition is demonstrated in the following examples utilizing the cure-indicating dental impression materials previously exemplified in Examples 9 and 10. A commercially available "acrylate" type adhesive (Scotchbond Multipurpose Dental Adhesive "SBMP" available from 3M, St. Paul, MN was applied to approximately a 5 mm x 5 num section of a glass microscope slide.

Acrylate adhesives sometimes are observed to retard or inhibit the setting of dental ipeson materials that cure via a hydrosilation mechanism. A purple impression paste from Example 10 (C IOaIB 10) was extruded through a static mixer and applied over much of the slide including the section coated with the SBMP. The bulk of the impression material exhibited a color change from purple to red/pink in approximately 3.5 minutes. Notably, however, the area previously coated with *SBMP maintained a purplish coloring (indicating that this area was not fully cured).

similar results were obtained for compositions ClIOb/B 10 (from Example 10) and 15 Runm2of Examnple 9.

A two-part (blue catalyst and white base) cure-indicating impression putty :similar to that described in Example 17 was evaluated under two sets of mxng conditions. Approximately 5 gramns each of catalyst and base putties were mixed by hand, wearing vinyl gloves, until a homogeneous blue paste was obtained. The paste was rolled into a ball and allowed to set. A second comparable mix of the catalyst and base compositions was prepared using latex gloves. Latex gloves sometimes are known to retard or inhibit the setting of dental impression materials that cure via a hydrosilation mechanism. This ball of material also was allowed to set.

Both balls cured in bulk. The sample mixed with vinyl gloves bleached to a white homogeneous sample. However, the sample mixed with latex gloves exhibited blue and white striations. The striations are believed to be indicative of incomplete curing due to contamination by the latex gloves.

Example 14' A stock impression base paste (B 14) was formulated by mixing together 150 parts vinyl terminated polydimethylsiloxane having a viscosity of 2.0 Pa s -94- SUBSTITUT SHEET (RULE 26) WO 96/00560 PCT/US95/08383 4.1 parts organohydrosiloxane crosslinker (PS 122.5, available from United Chemical Technology, Inc., Bristol, PA), and 30 parts Imsil A-25 filler.

A stock solution of dye M was prepared by dissolving 0.05 parts dye in 0.87 parts toluene. A stock solution of dye #2 (DS14) was prepared by dissolving 0.05 parts dye #2 in 1.74 parts of toluene. Additionally, a stock paste of dye #2 (DP14) was prepared by dispersing 5 parts dye and 5 parts Aerosil R976 fumed silica (available from Degussa Corp., Dublin, OH) in 90 parts vinyldimethyl-terminated polydimethyl siloxane with a viscosity of 1.0 Pa s ("VLMWP" available from OSi Specialties Inc., Danbury, CT) using a three-roll mill. A stock solution of chloroplatinic acid (H2PtCI 6 x6H 2 0, "CPA") catalyst was prepared by dissolving 0.04 parts CPA in 0.79 parts isopropanol.

Cure-indicating formulations were prepared by adding sufficient amounts of dye and catalyst to 30.7 parts of base paste (B14) to give 100 ppm dye (based on LMWP) and 30 ppm Pt (based on LMWP), and mixing by hand. Formulations were monitored for gel point, cure point, and bleach point as shown in Table 14a.

Table 14a 1 Run Dye Gel Point Cure Point 1 M 7 0-80 min. 180-240 min.

2 #2 2 >300 min. <1200 min.

3 >300 min. <1200 min.

II

I

"DNB" did not bleach after 72 hours.

2 As a toluene solution (DS14).

3 "PB" partial bleaching occurred.

4As a dispersed paste (DP14).

Notably, comparison dye M did not exhibit bleaching over the 72 hour period after the curing reaction was begun, while dye #2 exhibited some partial bleaching in this non-preferred composition.

Example The above experiment was repeated with the following changes: 1) the dye concentration was increased to 200 ppm based on LMWP; 2) a CPA stock solution SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCITUS95/08383 was prepared by dissolving 0.10 parts CPA in 0.79 parts isopropanol; and 3) 0.15 parts Silwet L-77 surfactant per 15.3 parts impression paste was added to the indicated run numbers. Formulations were monitored for gel point, cure point, and bleach point as shown in Table i _____Table Run "Silwet Dye GelPoint Cure Point Bleach Point 1 No M 120 min. <1320 min. DNB' 2 Yes M >420 min. <1320 min.

DNB

3 No #22 >1440 min. <2880 min.

DNB

4 Yes #22 230 min. <1320 min. 230 min.

DNB did not bleach after 72 hours.

2 As a toluene solution (DS14).

S

S

The composition containing Silwet and Dye #2 (Run 4) exhibited bleaching, while the composition containing Silwet and comparison dye M (Run 2) did not 10 bleach.

Example 16 A stock catalyst solution (C16A) was prepared by combining 400 parts of vinyldimethyl-terminated poly(dimethylsiloxane) with a viscosity of 2.0 Pa s ("LMWP") with 11 parts of Pt catalyst (from Preparatory Example la). A stock catalyst solution (C16S) was prepared by combining 400 parts of vinyldimethylterminated poly(dimethylsiloxane) with a viscosity of 2.0 Pa s ("LMWP") with 11 parts of Pt catalyst (from Preparatory Example la) and 8 parts Silwet L-77 surfactant. A stock base solution (B16) was prepared by combining 12.5 parts organohydropolysiloxane crosslinker with 0.25 parts 1,1, 3 ,3-tetramethyl- 1, 3 -divinyldisiloxane inhibitor ("DVTMDS"). 0.04 parts DP14 was added to parts of catalyst solutions C16A or C16S. Synthetic or mineral fillers were added according to Table 16a to prepare impression material pastes. These pastes were cured by adding 2.55 parts of base stock solution B16 and mixing for 120 seconds.

The initial color, gel time, cure time, and bleach time for each run are listed in Table 16a.

-96- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIJS95/083S3

V

*V

2 "SAA uoW-5 Cabosil M5" re hympi.c fumiic avilbl frm Cabot CoTsclM, I Blue 4.5 I m i n 6.5 micn. .53 calium hyRus an esumsiliwi t a vcnail fomk cyrs Indutial MAin ernmeralIns Englewood, CO. "Alumina" =A208 hydrated aluminum oxide available from R. J.

Marshall, Inc., Southfield, M1.

0 In general, the inclusion of Silwet L-77 does not seem to affect cure time or bleach time. Notably, the inclusion of certain fillers appears to affect both the initial paste color and the bleach time. For fillers which affect color and bleach time, the effect can be reversed with Silwet L-77.

-97- SUBSTUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/09833 9@ a.

4* 9 S* a EXAMPLE 17 Cure-indicating putty catalyst and base impression materials were prepared by mixing the following ingredients in a I gallon Ross mixer: Table:17a Ingredient Catalyst .(parts) Base (parts) LMWP 5.80 5.00 HMWP' 13.60 11.70 Pt Catalyst 2 0.60 Cosi 3.10 Mineral Oil' 6.50 6.50 Vicron 45-3 36.75 36.75 Iisil A-25 36.75 36.75 Silwet L-77 0.35 DVTMDS -0.0067 Dye #2 006 Footnotes for Table 17a: "11MW?" vinyl-terminated poly(dimethyLsiloxane) with a viscosity of 60 Pa s and molecular weight approximately 60,000 g/mol.

2 FrmPreparatory Example Ia.

3 *"Crosslinicer" A methylhydrosloxane-dimnthylsioxane copolymer with a viscosity between about 50 and 70 mPa. s and having approximately 0. 13% active hydrogen 4 "Mineral Oil"' KaydoP'm white mineral oil, USP grade available from Witco, Chemical Corp., Conneborn Div., Chicago, IL.

Catalyst and base putty impression material pastes were mixed together to give a cure-indicating formulation with T5 127 sec.; T90 190 sec.; and Bleach time 292 sec. at 27*C.

-98- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 EXAMPLE 18 Preparation of a Silwet-free impression material. Impression material catalyst and base pastes were prepared by mixing the following ingredients: Table 18a ngredient lyst, Parts Base, Parts VLMWP 83.1 51.2 Pt Catalyst, 3.04 Crossinker2 34.12 DVTMDS 0.07 Vicron45-3 107.5 108.5 Quso WR-55 6.1 7.1 Dye #2 0.014 S.00.

Footnotes for Table 18a: 1 From Preparatory Example la.

2 "XL".

Catalyst and base pastes were placed in separate barrels of a dual-barrel syringe and extruded through a static-mixing element. The material had a T5 129 sec.; T90 160 sec.; and Bleach time 240 sec. 27C.

EXAMPLE 19 Preparation of size-reduced structural abrasive molds. Stock catalyst and base solutions were prepared for use in fabricating size-reduced molds by mixing the following: -99- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/S8393 Footnotes for Table 19a: From Preparatory Example la 2 2 "XL2" .5 Catalyst and base solutions were mixed and poured against a flat, structured die. The system was closed to prevent solvent evaporation. After three hours the material cured and a color change from blue to clear occurred over a period of about 15 min. At this point the cured sample was removed from the die and solvent 10 was allowed to evaporate to form a size-reduced mold 50% of the original die volume.

EXAMPLE

S

A stock catalyst resin solution (C20) was prepared by mixing 190 parts VLMWP, 4.72 parts platinum catalyst from Preparatory Example la, and 3.30 parts Silwet L-77. A stock base resin solution (B20) was prepared by mixing 193 parts VLMWP, 0.21 parts divinyltetramethyl disiloxane, 98.82 parts XL2, and 4.95 parts Silwet L-77. A stock dye paste (DP20) was prepared from 83 parts VLMWP, 12 parts Quso WR-55 and 5 parts dye #2 using a three-roll mill. Impression material catalyst pastes were prepared by mixing 90 parts C20, 10 parts Quso WR-55, 100 parts Imsil A-25 and optionally 0.30 parts DP20. Impression material base pastes were prepared by mixing 90 parts B20, 10 parts Quso WR-55, 100 parts Imsil and optionally 1.4 parts of pink or yellow fluorescent pigment (Aurora Pink AX-11 -100- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 or Saturn Yellow AX-17, available from DAY-GLO Color Corp., Cleveland, OH).

Curing impression pastes were prepared by placing catalyst and base pastes into separate barrels of a dual barrel syringe and extruding through a static mixer.

Initial and final colors were determined using a color computer/spectrophotometer instrument (a Milton Roy Diano Match Scan II double beam spectrophotometer with a diffuse lighting source). Measurements were taken using a sample area view of 25 mm diameter and with specular reflection included.

The surface colors of 3 mm thick slabs of impression pastes were measured and reported in the CIE L*A*B* color system (as described in "Principles of Color Technology", Billmeyer Saltzman, Second Edition, 1981). This system is based on a 3-dimensional color space with the positive X-axis representing red, the negative X-axis representing green, the positive Y-axis representing yellow, the negative Y-axis representing blue, and the Z-axis going from zero (black) to 100 (white) with the origin at ST able 20a SI:n' .C r f Comnpos iio after Run Dye "Pigment Composition curng 1 None None Off White OffWhite 2 None Blue OffWhite 3 None Pink Pink Pink 4 Pink Purple Pink None Yellow Yellow Yellow 6 Yellow Green Yellow -101- SUBSTTUTE SHEET (RULE 26) WO 96/00560 PCTIUS95108383 Table Color Final Color Difference difference (AE*)i between sample (AE*) Initial LA*B* having dye and control between un Color (immed. Final L*A*B* Color sample having no dye initial and Safter mixing) (after curing) final color 1 70.00/2.01/6.68 70.04/1.91/6.88 0.71 0.23 2 63.03/-6.52/-4.67 69.94/1.36/6.44 15.27 3 63.14/26.50/-0.65 63.11/26.31/-0.51 2.93 0.24 4 57.82/9.93/-9.80 62.80/23.63/-1.66 16.70 71.66/-3.71/20.73 71.70/-3.66/20.68 1.97 0.08 6 63.02/-13.17/8.13 70.17/-4.36/19.65 16.17 Footnotes for Tables 20a and I "AE f(L* L 2 2

A

2 2

B

2 2 1 2 where LI*A,*BI* and

L

2

*A

2

*B

2 are the colors of the samples being compared. As a general rule, colors which differ by less than about 3 AE* units cannot be distinguished readily by the human eye.

This experiment illustrates that complete bleaching of the dye occurs as the compositions react and cure. This is illustrated by comparison of the final colors of 10 the samples with dye #2 and without dye For example, the difference between the final post cure) colors of Run #1 and Run #2 is about 0.71 AE* units. This minor difference in color would be well below that level which could be detected by the human eye. Similarly, comparing Runs 3 and 4 and Runs 5 and 6 yields AE* values below the level which is detectable easily by the human eye.

This experiment also illustrates that readily-observable color changes occur in the samples containing cure indicating dye. Runs 1, 3 and 5 do not contain any cure-indicating dye and do not change color as a result of the curing process (AE* values for these runs are 0.23, 0.24, and 0.08, respectively). Runs 2, 4 and 6 each contain a cure-indicating dye. Notably, these runs also exhibit large color changes (15.27, 16.70, and 16.17, respectively) as the samples are cured. For dental -102- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTTUS95108383 impression materials (and similar compositions which are monitored by the human eye) the amount of color change exhibited by the dye need only be that amount of change that can be observed by the human eye. Preferably, the impression material exhibits a color change upon curing of at least 5 AE* units when tested as described above. More preferably, the impression material exhibits a color change upon curing of at least 10 AE* units. Most preferably, the impression material exhibits a color change upon curing of at least 15 AE* units.

Figure 1 illustrates AE* as a function of curing time graphically for runs 2, 4, and 6. To generate these plots the samples were mixed and placed in the spectrophotometer. An initial color scan was obtained (within less than 1.25 minutes) and used as the reference color. Additional scans were taken as the material- cured and were compared to the initial scan. The difference in color (AE*) was computed for each additional scan and plotted. Table 20c contains the raw data for these scans. As can be seen in Figure I the color change was very pronounced for these samples (initial color final color) and occurred over a very short time period. Notably, the color change for each sample coincided with the gel point of the material. Thus, the pronounced, rapid color change was a very good indicator of the set time of the material. T90 for Runs 2, 4, and 6 was 5.28, 5.37 and 5.20 minutes, respectively, the time at which the color has changed to within 3 AE* units of the final color. Additionally, the time at which the initial color changes 3 AE* units from the initial color corresponds approximately with the T5 for Runs 2, 4, and 6 of 3.8, 3.9, and 3.9 minutes, respectively. This demonstrates the effectiveness of indicating both the working time and setting time in a single formulation.

-103- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 *5 S S S S

S

Table Time (Minutes) Run 2 Run 4 Run 6 (AE*) 2.00 0.50 0.42 0.55 2.25 0.64 0.55 0.71 2.50 0.79 0.69 0.86 2.75 0.94 0.85 1.05 3.00 1.12 1.03 1.23 3.25 1.32 1.22 1.45 3.50 1.57 1.48 1.71 3.75 1.86 1.79 2.02 4.00 2.25 2.21 2.41 4.25 2.85 2.87 2.96 4.50 3.83 4.12 3.79 4.75 6.83 8.48 5.59 5.00 11.37 13.03 10.81 5.25 13.76 14.86 14.15 5.50 14.62 15.59 15.36 5.75 14.95 16.00 15.77 6.00 15.12 16.25 15.95 6.25 15.21 16.45 16.05 6.50 15.26 16.59 16.12 6.75 15.32 16.70 16.18 EXAMPLE 21 A stock catalyst resin solution (C21) was prepared by mixing 2928 parts LMWP with 72 parts of the catalyst from Preparatory Example Ia. Cureindicating catalyst pastes were prepared by mixing 295 parts.C21, 4.5 parts of surfactant or wetting agent according to Table 21, 30 parts Quso WR-55, 300 parts Imsil A-25, and 0.96 parts stock solution DP20 in a double planetary Ross mixer.

A base impression paste (B21) was prepared by mixing 465 parts VLMWP, 195 parts XL2, 1.0 parts DVTMDS, 60 parts Aerosil R976, and 780 parts Imsil A-25 in -104- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTfUS95/08383 *oo o a double planetary Ross mixer. The catalyst and base impression pastes were placed in separate barrels of a dual barrel syringe, extruded through a static-mixing tip and checked visually for color change upon curing. Results are given in Table 21.

Table:21 :Run :Wetting Agent Initial Color Cured Color 1 none Grey Grey 2 Neodol 1-9 2 Blue Off White 3 Carbowax 3 Blue OffWhite 4 Triton X1024 Blue Off White 5 Fluorad FC 70C 5 Blue Off White 6 Fluorad FC4305 Blue Off White 7 Dibasic ester 6 Blue OffWhite "Initial Color" is the color of the catalyst impression paste.

2 Available from Shell Chemical Co., Houston,

TX.

3 Sentry@ polyethylene glycol 400, available from Union Carbide Chemicals and Plastics Co., Inc., Danbury, CT.

4 Available from Rohm and Haas Co., Philadelphia,

PA.

Available from 3M Co., St. Paul, MN.

6 A mixture of dimethyl glutarate, dimethyl adipate, and dimethyl succinate and available from E. I. duPont deNemours, Wilmington, DE. This impression material paste was prepared using a Semkit 388 mixer as previously described.

The above example illustrates that a variety of surfactants or wetting agents can be employed in filled compositions of the present invention. The filled composition of Run #1 did not exhibit an initial "blue" color as did Runs 2-7 which contained a wetting agent. The compositions with a wetting agent all exhibited a readily observable color change upon curing.

-105- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 Example 22 Reduction Potential and Spectroscopic Data of Various Dyes Reduction potentials by Cyclic Voltammetry: For a discussion of the underlying theory of potentiometry in organic solvents, the preferred method of referencing voltage measurements by means of ferricenium and cobalticenium salts, and the use of Cyclic Voltammetry for making such measurements, we incorporate herein by reference "The Chemistry of Nonaqueous Solvents", Volumes I (1966) and IV (1976), edited by J. J. Lagowski, Academic Press, NY, and specifically the chapter in Volume I entitled "Electrode Potentials in Non-Aqueous Solvents" by H.

Strehlow, notably page 159, and the chapter in Volume IV entitled "Redox Systems in Nonaqueous Solvents" by M. Rumeau, notably pages 90 and 96.

Based on the foregoing, solutions were made having approximately 0.0100 molar dye in a 0.100 molar solution oftetrabutylammonium tetrafluoroborate in dry 99% acetonitrile 1% trifluoroethanol (by volume). The reduction potentials were 15 measured with respect to the saturated calomel electrode at a scan rate of 20 V per second toward more negative values, and are reported as the peak potential.

Conversion to other electrode/potential scales may be carried out by making use of the values measured for the reduction potentials of cobalticenium and ferricenium salts, as reported in Table 22. This procedure also is applicable when 20 correcting for reasonable modifications in the solvent system necessitated by S.experimental factors such as solubility. Reduction potentials thus obtained are reported in Table 22. Preferred cure-indicating dyes, for use in the present invention, have a reduction potential greater than -0.80. More preferred cureindicating dyes have a reduction potential between 0 and -0.80.

Spectroscopic measurements: The dye solutions prepared for Cyclic voltammetry were diluted to 0.000050 molar in dry spectro-grade acetonitrile, and their spectra were measured from 200 to 800 nm in 10 mm silica cells, by means of a Perkin-Elmer No. 330 spectrophotometer. In the event that the maximal absorbance exceeded 3.0, a further fivefold dilution to 0.000010 molar was performed. In Table 22 is listed the wavelengths of maximal absorption in nanometers (nm) and the wavelengths (short and long, respectively) at which the -106- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383

S

*5 S

S

*5S* absorbance had fallen to one-half its maximal value. The latter serve to indicate the peak breadth and shape. The "Molar Extinction Coefficient", also termed "Molar Absorbance", is the measured absorbance corrected for concentration of the dye. In cases of commercial dyes for which the structures have not been disclosed, a nominal molecular weight of 475 was used to calculate molarities. In some cases, notably Sample No. 55, lack of purity means that the true molar extinction coefficients will be proportionately larger than the reported values. As is conventional in spectrophotometry, the common logarithms of the molar extinction coefficients is also reported in Table 22.

Table 22 Wave- Wavelengths of l ength of Hlf-maximal Maximal; .Visible Absorption, C.V. Visible Molar (nm).

Redu ct- sop- extMcio... Sample. ion o* .:iffici ent No. Potential X(m,2. 3a o 2 -0.73 645 31,300 587 703 4.50 -1.01 607 14,700 536 667 4.17 6 -0.98 602 15,200 535 663 4.18 11 -0.97 532 9,200 464 593 3.97 14 -0.5 675 26,600 617 731 4.42 15 -0.55 687 32,000 630 740 4.51 16 -0.95 612 16,800 544 673 4.23 17 -0.87 660 3,800 591 724 3.57 19 -0.96 476 2,400 580 3.37 21 -0.29 525 1,700 641 3.22 23 -0.9 547 1,800 621 3.26 34 -0.99 374 3,600 338 418 3.56 43 -0.24 488 15,200 437 525 4.18 46 -0.86 479 27,000 438 512 4.43 48 -0.61 498 26,700 459 533 4.43 -107- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/09393

S

g.e.

S S *5 S. C C S

S.

*0 *5*e a e.g.

'S a

S..

g S S. C .5 S

SC

g 4 a.

S a Cs. a a 555...

S

Table 22 Wave- Wavelengths of length of Half-maximal Maximal, Visible Absorption, CV. Visible Molar (rim) Redct- Absorp- extinction Sample :ion: w tion Coefficient N. otential z Vin_ 51 -1.26 588' 178,200 570 605 5.25 52 -0.49 638 113,900 593 667 5.06 53 -0.78 532 125,800 498 552 5.10 54 -0.67 560 54,800 509 586 4.74 55 661 >5,000 600 703 >3.7 56 -0.71 542 114,200 508 562 5.06 58 -0.61 627 73,700 583 65_5 4.87 59 -0.63 543 68,900 509 566 4.84 60 -0.97 527 112,200 472 576 5.05 61 54 1,900 621 3.27 77 -0.50 639 .176,000 609 635.25 A -1.20 391 16,100 331 443 4.21 B -1.04 472 13,800 375 515 4.14 D -1.09 483 15,600 383 30 4.19 E -0.93, 514 15,300 432 562 4.19 -1.35_ F -0.89, 501 21,100 434 545 4.33 -1.4 G -0.88, 508 25,300 449 553 4.40 -1.23 1 -1.15 593, 11,900, 555 658 4.08, 13,900 ___4.14 K -1.19 590, 15,800, 555 653 4.20, 18,600 4.27 L -0.82 581 7,000 509 635 3.85 Cobalt- -0.93 9 iceniurn Hexafluoro- 1phos I_ -108- SUBSTIU= SHEET (RULE 26) WO 96/00560 PCT/US95/08383 Table 22 Wave- Wavelengths of length of Half-maximal Maximal Visible Absorption, CV. Visible Molar (nm) Reduct- Absorp- extinction Sample ion tion Coefficient No. Potential (nm) 8 '12 Log s phate Ferri- +0.453 cenium Hexafluorophosphate (Ref) I oo *o Example 23 A stock catalyst paste was prepared by combining in a Ross mixer 33 parts 5 platinum catalyst (Preparatory Example la), 1449 parts vinyl-terminated polydimethylsiloxane having a viscosity of 2.0 Pa-s "LMWP"), and 18 0 parts Quso and mixing 10 minutes at 30 rpm. 1320 parts of Imsil A-25 was added and mixed 70 minutes at rpm. 1320 parts of Imsil A-25 was added and mixed minutes at 30 rpm under vacuum. 18 parts of Silwet L-77 was added and mixed minutes at 30 rpm under vacuum to make catalyst paste C23.

Base pastes were prepared by adding the indicated number of parts of dye to 3.3 parts Silwet L-77, see Table 23. The Silwet/dye mixture was added to a mixture of 136 parts LMWP, 54 parts oforganohydrogenpolysiloxane, XL2, and 0.17 parts 1,3-divinyl-, 1, 3 3 -tetramethyldisiloxne and shaken vigorously. 180 parts of this mixture and 22.5 parts of Quso WR-55 were added to a Ross mixer and mixed for 10 minutes at 40 rpm. 173 parts of Imsil A-25 was added and mixed minutes at 40 rpm under vacuum to form blue base pastes BXX. These pastes were placed in separate barrels of a dual barrel syringe and evaluated for bleaching and curing properties.

-109- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTfUS95/0383

S

*5 S

S.

*5*S

*SS*

S

S

*S

S *SS Table.23 Run Dye Dye, parts Cure Indicator Result 1CMDI-TNM 0.042 bleaches at cure point 2 CMDDI 0.038 bleaches at cure point 3 CMDI-CI 0.090 bleaches at cure point 4 CDHI 0.080 bleaches at cure point CMDI-OH 0.024 not soluble in formulation 6 CDI 0.022 bleaches at cure point 7 CMDI-TMSether 0.043 bleaches at cure point 8TC-Bu2 0.040 bleaches before cure point 9 TC-Et3 0.040 bleaches before cure point 10 SN-compound 0.040 not soluble in formulation 11 CMdDI-PIv*' 0.040 bleaches at cure point *Silbond® 3000MST-M filter (available from Quarzwerke GmbHL Freschen, Gennany) was substituted for lImsil in the base paste for run #11.

Compounds 3-11 were tested according to the procedure of Example 4.

They bleached according to the description defined in Example 4.

The chemical structures of these dyes are as follows:

CMI-TM[HE

Exmle 23 #1 2-hor 1-onebl-N-hl--2(355 -110- SUBSTMTUT SHEE (RULE 26) WO 96/00560 WO 9600560PCTIUS95/09393 CMDI-TMSether Example 23 #7 2 -Chloro-4-[[2-methyl-.N-ethyl.N-(3,, 5-dioxa-7- I -one CMDI-TMSether Example 23 #2 2 -Chloro-4-[[4-(N-dodecyl-N-metihyanXio)pheny] imino]-2,5-cyclohexandien- I one n-C 12

H

25

CDHI

Example 23 #4 2-hoo4[4(ieyaiopenliin]25ccoeain 1-one SUBSTITUTE SKEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/08383

CMDI-PIV

Example 23 #11 2-Chloro-4-[[2-methyl-(N-ethyl-N..(2- 1 -one

CMDI-OH

Example 23 2-Choro4-[2-methyl(NethyN(2hyroythy) cyclohexadien- I -one CMDI-Cl Example 23 #3 2 -Chloro-4-[[2-methyl.4-{N-ethyl-N(2.cloroethyl) cyclohexadien- 1 -one -112- SUBSTITE SHEET (RULE 26) WO 96/00560 PCT71US95/09383

CDI

Example 23 #6 2 -Chloro- 4 -114-diethylanlino)phenyl]imrino]-2,5-cyclohexadien. 1-one

CH

3

CH,

a. a a a.

a a a Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention is not limnited to the illustrative embodiments set forth herein.

-113- SUBSTIUT SHEET (RULE 26) WO 96/00560 (Dye 1) (Dye #2) (Dye #3) (Dye #4) PCT1US95/08383 cH 3 ChN QN=c'o

(HSC

2 2 N N2-

C

CC..

C.

(Dye -114- SUBSTITMT SHEET (RULE 26) WO 96/00560 PCr[US9s5o03

CH

3

OCH

3 (HsC 2 Q N (Dye #6) (Dye #7) (Dye #8) (Dye a.

a cl (Dye #11) -115- SUBSTTUTE SHEET (RULE 26) WO 96/00560 (Dye 12) (Dye 13) (Dye #14) (Dye PCIUS95/09383 (HCA)N-0QN: a a a.

,CH

3 a. a a.

a a.

a a a -NH-K0 (Dye 16)

(H

5 CA)N-O

-N

-116- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95/08383 (Dye 17) (Dye #18) a (Dye 19) (Dye a.

a a

CH

3 HO- N C 3 (Dye #2 1) -117- SUBSTrrUT SHEET (RULE 26) WO 96/00560 (Dye #22) (Dye #23) PCTIUS95/08383 0-CH2,O

N-

OCH

3 cI

H

3 CQO N Nc cI (Dye #24)

H

5

C

2 (Dye #26) (Dye #27) -118- SUBSTITUT SHEET (RULE 26) WO 96/00560 (Dye #29) (Dye (Dye #31) (Dye #34) PCT/US95/08383 0~o

QN

KO>NJ$

(Dye #37) -119- SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS9S/08383 (Dye #39) CiQ N- =0 CI CI

(H

3

C)

2

N

(Dye #40) 0C -N

*N

I .CI

HO

(Dy #4 1)

O

.0 SUBSTTTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTIUS95IOS383

OCH

3 (Dye #42)

-N

0 -N

OCH

3

CH

3

,CH

3

C

(Dye #43) N CH 3 9 0 -N

CH

3

CH

3

"CE

3 (Dy #44) (Dye #46) .9 9 N &3 .9..1 SUBSTTUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/OS33

H

3 C N CH 3

CI

(Dye #47) 0

H

3 C CIA 3

CI

(Dye #48) SC S S.N S* S 01000O 3 C CH 3 CI (Dye #49)- N- 0 0 0.

y 6C 0 Dye #5)0 0 r-122 SUBSTnr SHEET (RULE 26) WO 96/00560 WO 9600560PCrtIUS95/08383 (Dye #5 1) (Dye #52) (Dye #53) (Dye #54) (Hi 3

C)

2 N OC=H-HC-E* 2F @0e9 S. S S. S S S

S.

S.

SeeS *5S5*4

S

5555

S.

55 S S 55 S 55 5 S S

OS

55..

S

5S 5 S 000 S ,OCH2 iCH3

SQ.CF

3

<SO

2

CF

3

SO

2

CF

3 <SO2 CF3

H

3

CO'

(Dye -123- SUBSTITE SHEET (RULE 26) WO 96/00560 (Dye #56) PCTIUS95/09383 ,CH 3 (Hi 3 Ch2N

-CH

3 (Dye #57)

SO

2

CF

3

<SO

2

CF

3 (Dye #58)

(H

3

C',

(Dye #59)

SOCF

3

(H

3

C)

2 N Q Kk

H-H=CSO

2

CF

3 -124- SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCr/US95/08383 (Dye (Dye #6 1) 0OH I I

H

3 CC -N- (Dye #77) (Dye #78)

CH

2

CH

2

CI

.N

CH

2

CH

2

CI

H

3 00' -125- SUBSTPTE-j SHEET (RULE 26) WO 96/00560 PTU9188 PCTfUS95/09393

H

5

C

2 Q0.

(Dye #79) -N(CH 5 2 (Dye

H

5

C

2 0- (Dye

H

3

C,

N

H 3

C/

(Dye #86) (Dye #87)

(H

3

C)

2

N*

-126- SUBSTITUTE SHEET (RULE 26) WO 96/00560 (Dye #88) (Dye #89) PCTIUS95IO8383

S.

S S

S

S

(Dye (Dye #91) -127- SUBSTITUT SHEE (RULE 26)

S

0 S. 0 WO 96/00560 (Dye #92) (Dye #93) (Dye #94) PCrIUS95MO83%3 (ONCH R

ON(CH

3 2

S

S

SS S S S

SS

(Dye #96) (Dye #97)

OCN

CH

2

CHIOH

CH3 -128- SUBSrrM SHEET (RULE 23) WO 96/00560 PCIUS95/08393 (Dye 100) ci CH3 CH3 CH3

N

I CH3 0 a 0 0000 00 0S (Dye #102) (Dye 104)

GN

CH3 (Dye #105)

N

2

H

k(CH3)2

ST

-129- SUBS1TrLTE SHEET (RULE 26) WO 96/00560 PCr[US95/08383 (Dye 107) 0

S

S S 0 0

S.

SO S 0@ 0@ 00 0 *50

S

0 600050 0

S

0000 0 see...

0 (Dye #108) (Dye 109) 0'

/CH

3 CH3 0 1

N

li3C- I CH-CH=C-CH=.CH No-CH3 CH3 CH 3 CH3 CH 3 013 (n4 3 "3 CH3 S0. S 0 00C (Dye #11i0) -130- SUBSTITUT SHEET (RULE 26) WO 96/00560 PCTIUS95/09S3 (Dye #111)

GN

N(C 2

S

S

0e 0e 0O *0 S S S 5S 0

S.

0 0 (Dye #112) (Dye #113) O N(CH 3 R3

S

00@0 5000

S

OSSeOS

S

cH 3

S

S

(Dye #1 14) fa' 3 -13 1- SUBSTITUTE SHEET (RULE 26) WO 96/00560 .(Dye 115) PCT/US95108383

N(CH

3 2 0SO*OS 0 0 S 0O S0 S.

SS

S.

S

*50 0

S

(Dye #121)

-N(CH)

(Dye #122) *5SS

S

S

S

S

S

S. S 5@

S.

(Dye 123)

N

Cl! 3

III

c 013

N\

01C3 -132- SUBSTTUTE SHEET (RULE 26) P:\WPDOCS\CRN\7I8295.3m.do-26/10/00 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers or steps but not the exclusion of any other integer or group of integers 5 or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge in Australia.

*550 oo -132a-

Claims (34)

1. A dental impression material in the form of a single-part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst; a crosslinker compound containing at least two SiH groups; a hydrosilation catalyst comprising a complex of platinum and an unsaturated organosilicon material; and one or more cure-indicating dyes, wherein said dye exhibits a color change within about 10 minutes at 25 *C when 500 tg of said dye, 500 pl of dichloromethane, 100 Pl ofpentamethyldisiloxane and 10 pl of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together and wherein said impression material exhibits a color change upon curing.

2. A dental impression material according to claim 1, wherein said impression material is in the form of a two-part composition, provided to the user as two separate mixtures, wherein a first mixture comprises said catalyst and a second mixture comprises said crosslinker compound.

3. A dental impression material according to claim 1, wherein said hydrosilation catalyst comprises a complex of platinum, and a complexing material in the form of an unsaturated organosilicon material selected from the group consisting of: unsaturated silanes having the empirical formula, RR'bSiX, where R is free of aliphatic unsaturation and selected from monovalent hydrocarbon radicals, R' is selected from monovalent aliphatically unsaturated hydrocarbon radicals, X is a hydrolyzable radical, c is an integer having a value of at least 1, b is an integer having a value greater than or equal to 2 and the sum of a, b and z equals 133 SUBSTITUTE SHEET (RULE 26) IPAWPOCSCRNMSPECI\718295.3 m.dmo- 9/03)01 the sum of 2 and two times c for a linear or branched silane and wherein c is an integer having a value from 4 to 18 and the sum of a, b and z equals two times c: for a cyclic silane; 133a WO 96/00560 PCTIUS95/08383 unsaturated linear or branched siloxanes of the empirical formula, RdR'.SiO(r.J) where R and R' are as defined above, f is an integer having a value of between 2 and 10,000, e is an integer having a value greater than or equal to 2 and the sum of d and e equals the sum of2 and two times f; and unsaturated cyclic siloxanes of the empirical formula, Ra.SiIOr where R and R' are as defined above, e is an integer having a value greater than or equal to 2, fis an integer having a value from 3 to 18, and the sum ofd and e equals two times f.

4. A dental impression material according to claim 3, wherein said catalyst complex is formed using a platinum halide selected from the group consisting of H 2 PtCI 6 nH 2 0, NaHPtC6nH20, KHPtCI 6 nH 2 0, Na 2 PtClknH 2 0, K 2 PtCJ 6 nH 2 0, 15 PtCL*nH 2 0, PtCI 2 Na 2 PtCi 4 nH 2 0, H 2 PtCI 4 nH 2 0, NaHPtCL*nH 2 0, KHPtCLsnH 2 0, K 2 PtBr 4 ((CHCH 2 )PtCl 2 2 (PtC12C 3 H6)2, and the reaction product of chloroplatinic acid hexahydrate and octyl alcohol. S. 5. A dental impression material according to claim 2, wherein said catalyst is a 20 Karstedt catalyst and has available inorganic halogen of less than 0.1 gram atoms of halogen per gram atom of platinum.

6. A dental impression material according to claim 3, wherein R' is selected from the group consisting of ethynyl, 1-propynyl, vinyl, allyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl.

7. A dental impression material according to claim 6, wherein R is selected from the group consisting of methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, cyclohexyl, cycloheptyl, phenyl, naphthyl, tolyl, xylyl, benzyl, phenylethyl, and phenylpropyl. 134 SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCIT.J59510383

8. A dental impression material according to claim 3, wherein said unsaturated organosilicon material is an unsaturated silane selected from the group consisting of tetra-vinylsilane, triallylmethylsilane, divinyldimethylsilane, trivinyiphenylsilane, divinylmethylphenylsilane, divinylmethylethoxysilane, divinylmethylacetoxysilane.

9. A dental impression material according to claim 7, wherein said unsaturated organosilicon material is an unsaturated linear or branched siloxane selected from the group consisting of disiloxanes of the formula, RR'ISiOSiRh.R 1 where h and h' are integers with a value of at least one, the sum of g and h is equal a to 3, and the sum of g! and hW is equal to 3. a *10. A dental impression material according to claim 7, wherein said unsaturated organosilicon material is selected from the group consisting of 1, 1 -divinyl- tetramethyldisiloxane, 1,3 divinyltetramethyldisiloxane, hexavinyldisiloxane, 1, 1,3- trivinyltriethyldisiloxane, 1,1 3 3 -tetravinyldimethydisiloxane, 1,1 ,3,5,5-pentamethyltrisiloxane, and I ,3-divinyl,-1I,3-dimethyl,- 1,3- diphenyidisiloxane. 0*S 20 11. A dental impression material according to claim 2, wherein said unsaturated organosilicon material is an unsaturated siloxane selected from the group consisting of I ,3,5-trivnyl- 1, 3 ,5-trimethylcyclotrisiloxane, I,3,5,7-tetraalyL, 1,3,5,7- tetraphenylcyclotetrasiloxane, 1 3 -divinyloctaniethylcyclopentasiloxane, and 1 3 ,5,7-tetravinyl- 1,3 ,5, 7 -tetraxnethylcyclotetrasilone.

12. A dental impression material according to claim 2, wherein said cure- indicating dye changes color to indicate the gel point of said impression material.

13. A curable composition according to claimn 2, wherein said cure-indicating dye changes color to indicate the set time of said impression material. 135 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383

14. A dental impression material according to claim 1, wherein said cure- indicating dye is present in an amount between 0.0003 and 0.03 weight percent. A dental impression material according to claim 1, wherein said cure- indicating dye has a molar extinction coefficient of at least 10,000 M'cm

16. A dental impression material according to claim 3, wherein said cure- indicating dye exhibits a loss of 90% in absorbance within about 10 minutes at 25 0 C when 500 pg of said dye, 500 pl ofdichloromethane, 100 pl of pentamethyldisiloxane and 10 pt of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together, as compared to an identical solution that does not contain a hydrosilation catalyst. S17. A dental impression material according to claim 1, wherein said cure- indicating dye exhibits a loss of 99% in absorbance within about 10 minutes at 25 0 C when 500 pg of said dye, 500 pl ofdichloromethane, 100 pl of S. pentamethyldisiloxane and 10 p of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together, as compared to an *e identical solution that does not contain a hydrosilation catalyst.

18. A dental impression material according to claim 1, wherein said impression material exhibits a transition time between the onset of color change and the effective completion of the color change of less than three minutes at 32°C.

19. A dental impression material according to claim 1, wherein said cure- indicating dye is selected from the group consisting ofindoaniline dyes, indophenol dyes, quinone monoimine dyes, quinone diimine dyes, cyanine dyes, merocyanine dyes, cyclohexadienone dyes, iminocyclohexadienone dyes, imidazolylidinecyclohexadienone dyes, dihydronaphthalenone dyes, iminodihydronaphthalenone dyes, imidazolylidinedihydronaphthalenone dyes, cyclohexadienimine dyes, aryl substituted bis (trifluoromethylsulfonyl)hexatrienyl 136 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 dyes, aryl substituted bis (trifluoromethylsulfonyl)butadienyl dyes, aryl substituted bis (fluorosulfonyl)hexatrienyl dyes, aryl substituted bis (fluorosulfonyl)butadienyl dyes, oxazolone dyes, cationic dyes, anionic dyes and amphoteric dyes.

20. A dental impression material according to claim 1, wherein said cure- indicating dye is selected from the group consisting of neutral dyes represented by the following general formula: wherein: each R R and R 4 group is independently hydrogen, halogen, a O hydrocarbyl-containing group, or a heterocyclic group, and wherein R1 and R 2 or R 3 and R may be connected to form a saturated or unsaturated ring; A is O, S, or NR, wherein *Rn is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic S. group; and B is any group capable of providing extended conjugation thereby rendering the dye capable of absorbing visible, near-UV, or near-infrared radiation and includes groups of formula D, E, F, H, or J, wheiein D is represented by formula: R* R1 R 137 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 wherein: each R 5 R 6 R 7 and R 9 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two adjacent R 5 R 6 R 7 R 8 and R 9 groups may be connected to form a ring; E is represented by formula: R 1 0 R X 3X=N-N wherein: XI is C(R") 2 S, NR 1 2 or 0; X 2 is C(R 2 2 S, NR 1 2 or 0; and each R 1 0 R" and R 2 group is independently hydrogen, a hydrocarbyl- 10 containing group, or a heterocycic group and wherein R 1 0 and R 1 may be connected to form a ring; F is represented by formula: *13 R 0 wherein: X 3 is N or CR' 6 and each R 1 3 R 1 4 R 1 5 and R 1 6 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two adjacent R 13 R 1 4 R 1 5 and R 1 6 groups may be connected to form a ring; 138 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 H is represented by formula: R 2 C R21. a wherein: each R and R 2 1 group is independently hydrogen, halogen, a hydrocarbyl- containing group, or a heterocyclic group and wherein R 2 and R 21 may be connected to form a ring; and J is represented by formula: R6 R R23-N= wherein: each R 5 R7 Rand R 8 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two R 5 R 6 10 R 7 and R 8 groups may be connected to form a ring; and R is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group; sulfonyl dyes represented by the following general formula: S0 2 R 2 6 R24 S02 R 27 139 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 wherein: each R 24 and R 2 group is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group with the proviso that at least one of R 24 and R" is or contains a substituted aryl, aminoaryl or heterocyclic group; each R 26 and R 2 group is independently a -(CF2)F group wherein m is a number between 0 and 20; and n is an integer less than neutral dyes represented by the following general formula: R 29 wherein: each R 2 R 3 R 4 and R 9 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein any two adjacent R 2 R 3 or R groups may be connected to form a ring; and R 3 is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic 15 group and n is an integer less than anionic dyes having the following general formula: R 2 8. R 2 8 ,z wherein: Z represents the non-metallic atoms necessary to complete a substituted or unsubstituted nitrogen-containing heterocyclic ring; 140 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCr[US95108383 each R 21is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group; n is an integer less than 5; and wherein M+ is selected from any suitable cation; cationic dyes having the following general formula: a C wherein: each R 31 W 32 W 33 and R34 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein any two adjacen W I, R 32 W 33 Or R 34 groups may be connected to form a ring; RW' and e~ are as defined above for e 3 and R' is 0, S, or f" is N or CR; W" and R 3 are as defined above for W? 3 and wherein M- is any suitable anion; cationic dyes having the following general formula: 141 SUBSTITE SHEET (RULE 26) J 96/00560 PCT/US95108383 wherein: *00000 :1:6 each R 32 R 33 R' and R' group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein any two i1) adjacent RI, R, R 3 or R groups may be connected to fonn a ring R is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group; X is C=R, C(R) 2 O, S, or NR7, wherein R- is as defined above fbr R-7, 5 R- is as defined above for R' R is an oxo group, a divalent hydrocarbyl-containing group or a divalent 0000 heterocyclic group, and wherein R" and R may be connected to form an **unsaturated ring, and Rn and R may be connected to form a ring; and wherein M- is any suitable anion; and .:2 cationic dyes having the following general formula: 0 A R R41-- 43 wherein: each R 4 2 to R 45 group is independently hydrogen, halogen, or a hydrocarbyl- containing group, or a heterocyclic group; each R, R, R, and R 7 group is independently hydrogen, a hydrocarbyl- containing group, or a heterocyclic group and wherein any two adjacent R" 1 to R 142 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT1US95/08393 groups may be connected to form a ring and wherein R44 and R 45 may be connected to form a ring; n is an integer less than 5; and wherein M_ is any suitable anion.

21. A dental impression material according to claim 2, wherein said cure- indicating dye is a neutral dye.

22. A dental impression material according to claim 1, wherein said cure- indicating dye is selected from the group consisting of 4-[j4- -one; 2 -Chloro-4-[[2_methyl..4. (deh*iopeylnio-,-coeain I 1-one; 4-II4- (Diethylinoey]im no]-,4-ydonahtale- -one; 4-[4 (Dieth~kn r.J)juenuaiAinJ 1,4-dhydronaphtl.al- I -one; 4 -[[2-methyl-4. 1dehlmn)hn]iio-,-Yrnptae-I-one; 3-Methoxy..4.{[2_ OV. ethl-4(dith~amin)Phn~linlnol2,5-yclhexdie- I-one; 3-Chloro-4-[[2- -one;. 2-Methyl-4[[4-{4-. -one; 2,6-Dicbworo..4.[[4.{4_ mOrPhOliny)phenl o]25 dohaie-I -one; 2,6-Dimethy morpholiny)phenyl]i o]25cohain 2 ~-iho_4.4- (dethlamno)pheyl~nliol-,5-yclhexdie- I-one; 3 -Metboxy-4[[3.metioxy. 4-dehlaln~hnliio-,-~lhxde-I-n, 2 6 -Dichloro-4[[2-meth. *1-dehlniopey~rnnl25ccoeain -one; 3-[[4-U(iethylaxnino)-2- methylpheylJo]6oxoN-phenyl-l, 4 -cclohexadiene l-carboxamicie; (Diethylaniino)2methypheny]i~no]g{ H-uiofno 2,5-Dicbloro4{[2. mehl-dehlmn)pey~nio-,-ylhxde- -one; 2,6-Dichloro-4. 4 -(acetamido)pheny1inino]2,5.<,clohexadien- -one; 2 6 -Dichioro_-[4-ethox, 1-one; 2 6 -Dichloro-4(2-methyA..ethoxy 1 -one; 2 6 -Dimethyl-4..4hydrox, phenyl)ixnino]- 2 ,5-cyclohexadien.. 1-one; 2 6 -Dichloro..4.{(4-.methoxy- 1-naphthyI)imiino]-2,5-yclo. hexadien- 1 -one; 2 6 -Dichloro4[4.bezylo)phenyl]no 2 5 loheainI 143 sUBSrrr SHEET (RULE 26) WO 96/00560 PCTIUS95/09393 one; 2,-ihoo4[24dmtoyhey~mnj25ccoeain 1 -one; 2,6- Dichloro-4-[(4-methoxyphenyi)iwjno]-25-cycohexa 8 dien- I -one; 4-(phenylixnino)- 2 5 -cyclohexadien- 1 -one; 4-(lI -naphthylinino)-2,5-cycohexadien-1 -one; 4-(2- 1 -one; 2 5 -Bis(phenyamino)-4(phnyhiio) 2 5 -cyclohexadien.. I -one; 2 5 -Dibromo-[(2,4dibromophenyl)imino 1 cyclohexadien-lI-one; 2 3 5 -Trichloro4(2,4,6-tdchloropheny)inwno]..2,5 cyclohexadien-1 -one; 2,-i~r4[-4(iehlniopey]5pey-2) inidazol-2-ylidine]-2,5-cyciohexadien- 1-one; 2 6 -DichloroA-[4,5-bis(4.hydroxy. phenyI)-(2H in idazoI-2-yhdine]2,5..ycohen- I~ -one; 2,6-Dimethoxy-4-{4,5.. bi(-irl-2)iiao-2yiie-,-coeain I -one; 2,6-Bis[ 1, 1 one; 4 -(phenylimino)-2,5-cyclohexadie. 1 -imine; Mono,[(3-methyI-2-{3H)..bezo cyclhocaien--ylidine)-amino]- 1,2-dihydro-1,-iehl2pey-3)pmi 15 3-one; 4 3 5 -Dich~oro-4-oxo-2,5-cyclohexadien. I-ylidine)amino]- 1,2-dihydro- l,5-dimethy..2.pheny[-(3H..pyrazo..3.on; 3 3 ,5-Dicbloro-4-oxo-2,5-cydo. nexadien- 1 1yiieain]25dhdo,4ehl -phenylpyrrol-2-one; 4- (Phenylsulfonyl)inino.. 4 -(henysulfonyl)imino]-2,5.cyclohexadien.. I-ylidenyl]- 2 ,5-cycloheaudiene; 4 6 6 -Bis[(trfluoromethy)sfonyl].1,3,5.hextienyl].NN- 20 diniethylbenzenanine; 4 4 4 -Bis[(tfluoromety)ony]3bujjdienJ 2 etoyNNdiehle eaie 4 4 4 -Bis[(trifluoromethyl)sulfonyI]-1,3-buta- 9 -[4,4-Bis[(trifluoro- S methyl)sulfonyl]- 1 3 butadienyI]-2,3,6,7tetrahydro-( lHH)-benzo[ij]quinojzine; benzenarnine; 4 -[5,5-Bis[(trifluoromethyl)sulfonyI].24..pentadenyljidfle]-1,4- dihydro.. 1 -methylquinoline; 6 6 -Bis[4-(dimethylaniino)phenyJ 1 3 ,5-hexatriene- 1, 1 bis(sulfonylfluoride); 4 4 4 -Bis[(trifluoronmethyl)sufonyl]-.1 ,3-butadienyl]-NN- dimethylbenzenarnine; and 4 3 4 -(Dmethyamino)phenyI]-2propenylidene-2- phenyl-5(4H)..oxazolone; anionic dyes having the following anions: Diethylhexahydro..2,4,6-troxo-5..pyriTdiny)24pentadienyliden]1 ,3-diethyl- 2 4 6 (lH, 3 H5H)-pyrirnjdenetrjone; and cationic dyes having the following cations 144 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/09383 or having the cations of the following cationic dyes: 3H-Indolium, (diznethylaxino)phenyl]2propenylidene] I -methyl-2-phenyl; Benzothiazolium 3-' Benzothiazoliun, 3 3 -amiino-3-oxopropyl).2[[4..diethylnno)pheny]zo]-6 ethoxy-; Benzothiazoliwn, 3-3aio3oorpl-2[4(ityaio-- methylphenyl]azo]-6&etioxy.; CAS 12221-40-8; CAS 12270-14-3; CAS 12221-

31-7; CAS 12221-34-0; Benzo[a]phenoxazin.7iwp., 9 -(dimethylaznino)-; bis[4mdimethylamino)phenyl]- 1 ,3-butadienyl]- I -ethyl qumnolinium; 4-(4,4,-bis[4. (dimethylaiino)phenyl]. 1 ,3-butadienyl] 1 -ethyl quinoliniuin; Naphtho[2, I1- dlthiazoiuxn, 2 4 A4-bis[4-(dimethylamiino)phenyl]..1 ,3-butadienyl]-3-ethyl.; 2-[2- 4 -(dimethylazino)phenyl]etheyl]-.1 -phenyl-3-methyl quinoxaliniuin; Quinolinurn, 2 3 -(5-chloro-1I,3-dihydro- 1, 3 3 -trimethyl-(2H)-ndol.2.ylideie). I-propenyl]-lI- methyl-; Benzothiazolimn, 2 4 -(dimethylarnio)phenyl]azo].6..etho-3-methyl-; Benz~cdlindolium, 2 4 dethyhlarino)-2-ethoyphenyJ.-I1-ethyl-; 2-[p- 15 (Dunethylaxnino)styryl]- I, 3 -dimnethylquinoxaliniuni; 2 -[3-(5-chloro- 1,3-dihydro,- l, 3 3 -trimethyl(2)idol2ylidene). 1-propenyl]-lI-methylquinoxafirinum C. I. Basc Bue 0; enzthizolum, 2 4 -[ethyl(2-hydroxyethyl)anuno phenyl]azo]-6- *0*methoxy-3-meth yl-; Benzothiazoliurn, 2 4 -[ethyl(2-hydroxyethyl)aino]phn yl]azo]-6-methoxy-3-met1hyl-; C. 1. Basic Blue 42; C. 1. Basic Blue 53; 3H- 20 Indoljim, 5-chloro-2-[5-(5.cljoro-.1 ,3-dihydro- I, 3 3 -trimethyl-2H-indol.2-yldene)- 1, 3 -pentadienyl]-1,3,3-trimtyl-; C. 1. Basic Blue 142; Benzfcd]indolium, (dimethylamino)phenyl]-2phenylethenyl]-1-methyl-; Benz[cd]indoliur, 2-[2,2- bis[4-(dimethylaniino)phenyl]ethenyl]-l 1-methyl-; Benz[cd]indolium dihydro-lI-methyl-2-phenyl- lH-indol-3-yl)-2..(2..methylphenyl)ethelyl]-l -methyl-; Pyrimidinium, 4-[5-(2,3-dihydro- 1, 3 -dimnethyl-2-oxo-; 4 (1H)-pyrimidinylidene). ,3- pentadienyI]-2,3-dihydro- 1,3-dimethyl-2-oxo-; 3H-Indolium, ,3-dihydro- 1,3 3 -trimethyl-2H-indo[2-ylidene)methyl]-5,S-dimethyl-2-cyclohexen- ylidenejmethyl].. I,3,3-trimethyl-; Benz[cd]indoliurm, 2 2 -[4-(diethylaniino).2. methylphenyl]ethenyl]j.. -methyl-; 3H-Indolium, 3 3 -[4-[(dimethyla mino)phenyl]-2 propenylidene]- I-methyl-2-(4-methoxyphenyl)-; 3 H-Indolium, 3-[(2,5-dimethyl- 1- 145 SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCIUS95/08383 phenyl-(I H)-pyrrol-3-yl)methylene]- 1 ,2-dixnethyl-; 3H-Indolium, 3-[2,5-dimethyl- I1- phenyl-( lH)-pyrrol-3-yl)methylene]-l1-methyl-2-phenyl-; 2-[2-[2-chloro-4- (dimethylamino)phenyl]ethenyl]mehylbez[cd]indolium C. I. Basic Violet 22; C. I. Basic Red 15; Benzfcd]indolium, 2 2 4 -(dimethylamino)phenyl]ethenyl]..I.. methyl-; Bezclnoun2[4-dmtyain)2ehxpey~tey] methyl-; and 3H-Indolium, I-cyano44-bis[4(dimethylamino)pheny].1,3- butadienyl]- 1,3,3-trimethyl-. 23. A dental impression nmaterial according to claim 1, wherein said cure- indicating dye is selected fr-om the group consisting of (Dimethylanflino)phenyl]imino]-2,s.cyclohexan-je. 1 -one; 2-Chloro-4-[[2-methyl-4- (diethylamino)phenyl]inmino]-2,..yclohomdjen. 1 -one; (DiethylaninO)phenyllinlino]-1I,4-dhydronaphthalen- 1 -one; (DimethyainoW)phenyl~imino]- 1 ,4-aiydronaphthalen- 1 -one; -[[2-methyl-4- (diethyiaznino)phenYllinlinO].1 ,4-dihydronaphthalen- 1 -one; 3-Methoxy-4-[[2- I-dit~mnOPe~liinl2,-y 1hde--one; 2-Methyl-4-[[4-(4- mOrPholiny1)phenyI]imino]-2,5.cycohem jen. 1-one; 2,5-Dichloro-4-[[4- .(diethylamino)phenyl]iiino]2,s.cycloheadie- 1-one; 3-[[4-(Diethylamino)-2- -xo-N-phenyl-l ,4-clohexadiene-l1-carboxamnide; n)--e~pey~iin]--5)-unfioe 2,6-Dichloro-4-[[4- 20 (aeaiopey~nio-,-ylhiin oe 4-(I-naphthylmio)-2,5- cyclohexadien- 1 -one; 4 2 -naphthyimino)-2,5-cyclohxadieuI.. -one; Bi*hnkio4pa nio-,-coeain I -one; 4-[5,5- Bis[(trifluoromethyl)sulfonyl]-2,4..pentadienylidee].1 ,4-dihydro- I-methylquinoline; 6 6 -Bis[4-(dimethylaxniino)phenyl] I ,3,5-hexatriene- 1, 1 -bis(sulfonylfluoride); 4-[4,4- Bis[(trifluoromethyl)sulforyl]-1 3 -butadienyl]-N,N.dinetkylezen ne; and 4-[3- [4(iehlmn~hnl--rpnyiee--hnl54)oaooe 24. A dental impression material according to claim 2, wherein said impression material comprises between 20 and 90 weight percent filler. 146 SUBSTTUT SHEET (RULE 26) WO 96/00560 PCT/US95/08383 A dental impression material according to claim 19, wherein said impression material further comprises an indicator adjuvent comprising an active proton. 26. A dental impression material according to claim 5, further comprising a non- cure-indicating dye or pigment. 27. A dental impression material in the form of a single-part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst; a crosslinker compound containing at least two SiH groups; a hydrosilation catalyst comprising a complex of platinum and a complexing material in the form of an unsaturated organosilicon material selected from the group consisting of: *15 unsaturated silanes having the empirical formula, *S RRbSiX where R is free of aliphatic unsaturation and selected from monovalent hydrocarbon radicals, R' is selected from monovalent aliphatically unsaturated hydrocarbon radicals, X is a hydrolyzable radical, c is an integer having a value of at least 1, b is 20 an integer having a value greater than or equal to 2 and the sum of a, b and z equals the sum of 2 and two times c for a linear or branched silane and wherein c is an .integer having a value from 4 to 18 and the sum of a, b and z equals two times c for a cyclic silane; unsaturated linear or branched siloxanes of the empirical formula, Rd RSiWO(f) where R and R' are as defined above, fis an integer having a value of between 2 and 10,000, e is an integer having a value greater than or equal to 2 and the sum ofd and e equals the sum of 2 and two times f; and unsaturated cyclic siloxanes of the empirical formula, RdR'eSijOf where R and R' are as defined above, e is an integer having a value greater than or equal to 2, f is an integer having a value from 3 to 18, and the sum of d and e equals 147 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/0838 two times f and wherein said catalyst complex is formed using a platinum halide selected from the group consisting of HPtCknH 2 0, NaHPtC 6 nH 2 0, KHPtCk nH 2 0, Na 2 PtCI 6 nH20, K 2 PtClInH20, PtCl 4 nH 2 0, PtCl2, Na 2 PtCI 4 nH 2 0, H 2 PtClnH 2 0, NaHPtCl'nH20, KHPtCI4nH20, K 2 PtBr4, ((CH 2 =CH 2 )PtC 2 2 (PtCl 2 C 3 and the reaction product of chloroplatinic acid hexahydrate and octyl alcohol; and one or more cure-indicating dyes, wherein said impression material exhibits a color change upon curing, wherein said dye exhibits a color change within about minutes at 25 0 C when 500 pg of said dye, 500 pl ofdichloromethane, 100 ul of pentamethyldisiloxane and 10 ul of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together, and wherein said cure- indicating dye is present in an amount between 0.0003 and 0.03 weight percent. 28. A dental impression material in the form of a single-part or multiple-part 15 composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst; I a crosslinker compound containing at least two SiR groups; a hydrosilation catalyst comprising a complex of platinum and a complexing 20 material in the form of an unsaturated organosilicon material selected from the unsaturated silanes having the empirical formula, RR'bSi X. where R is free of aliphatic unsaturation and selected from monovalent hydrocarbon radicals, R' is selected from monovalent aliphatically unsaturated hydrocarbon radicals, X is a hydrolyzable radical, c is an integer having a value of at least 1, b is an integer having a value greater than or equal to 2 and the sum of a, b and z equals the sum of 2 and two times c for a linear or branched silane and wherein c is an integer having a value from 4 to 18 and the sum of a, b and z equals two times c for a cyclic silane; unsaturated linear or branched siloxanes of the empirical formula, RR'.SiO(f.l) S148 SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PC7Is9s/oS3S where R and RW are as defined above, f is an integer having a value of between 2 and 10,000, e is an integer having a value greater than or equal to 2 and the sum of d and e equals the sum of 2 and two times and unsaturated cyclic siloxanes of the empirical formula, RdR.SiA~ where Rand R!are as defined above, ecis aninteger having avalue greater than or equal to 2, fisanmiteger having avalue from 3to18, and the sum of dand eequals two times t and wherein said catalyst complex is formed using a platinum halide selected fr-om the group consisting of H 2 PtCI 4 nH 2 O, NaHPtCI 6 .nH 2 O, KHIPtC4*nH 2 O, Na 2 PtCL6*nHzO, K 2 PtCI 6 'nH 2 O, PtCI 4 nH 2 O, PtCl 2 Na 2 PtCljnH 2 O, H 2 PtC1.*nH 2 O, NaHPtCinH 2 O, KHPtCL'nH 2 O, K 2 PtBr4. ((CH 2 -=CH 2 )PtCl), (PtCbjC 3 H 4 2 and the reaction product of chioroplatinic acid hexcahydrate and octyl alcohol, and wherein said catalyst is a Karstedt catalyst and has available inorganic halogen of less than about 0. 1 gram atoms of halogen per gram atom of platinusm; and one or more cure-indicating dyes having a molar extinction coefficient of at least 10o,000 MT'cmf 1 wherein said impression material exhibits a color change upon curing of at least 10 AE* units. 29. A dental impression material in the form of a single- part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SOH group in the presence of a catalyst; a crosslinker compound containing at least two Sill groups; a hydrosilation, catalyst; and. one or more cureindicating dyes selected f-rm the group consisting of neutral dyes represented by the folowing general formula: 0.*0* 149 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 wherein: each R 2 R 3 and R 4 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein R 1 and R 2 or R 3 and R 4 may be connected to form a saturated or unsaturated ring; A is O, S, or NR 2 wherein R is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group; and B is any group capable of providing extended conjugation thereby rendering the dye capable of absorbing visible, near-UV, or near-infrared radiation and 0 0 includes groups of formula D, E, F, H, or J, wherein D is represented by formula: *e 0 R7 N wherein: each R 5 R 7 and R' group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two '1 adjacent R 5 R6, R 7 and R9 groups may be connected to form a ring; E is represented by formula: R o 10 \X I X ==N-N R 1 wherein: X' is C(R) 2 S, NR 12 or O; X 2 is C(R 1 2)2, S, NR' 2 or 0; and 150 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PTU9188 PCT/US95/08383 each R1 0 R 1 and R. 2 group is independently hydrogen, a hydrocarbyl- containing group, or a heterocyclic group and wherein W' 0 and may be connected to form a ring; F is represented by formula: wherein: X' is Nor CR; and each R3, R1 4 R 15 and R"1 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two adjacent R1 3 R1 4 R1 5 and R 1 6 groups may be connected to form a ring; H is represented by formula: wherein: each R2' and R 2 group is independently hydrogen, halogen, a hydrocarbyl- containing group, or a heterocyclic group and wherein R1 5 and R1 6 groups may be connected to form a ring; and J is represented by formula: 151 SUBSTIUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 wherein: each R s R 6 R 7 and R' group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and wherein any two R 5 R 6 R 7 and R" groups may be connected to form a ring; and R 2 is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group; sulfonyl dyes represented by the following general formula: S0 2 R 26 SO2R R 25 n wherein: each R 2 and R 2 5 group is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group with the proviso that at least one of R 2 4 and R 2 is or contains a substituted aryl, aminoaryl or heterocyclic group; each R 2 and R 27 group is independently a -(CF 2 group wherein m is a .o number between 0 and 20; and n is an integer less than neutral dyes represented by the following general formula: R R R wherein: each R1, R 2 R 3 R 4 and R 2 group is independently hydrogen, halogen, a 2 0 hydrocarbyl-containing group, or a heterocyclic group, and wherein any two adjacent R 2 R 3 R 4 or R 2 groups may be connected to form a ring; and 152 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 R 3 is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group and n is an integer less than anionic dyes having the following general formula: R 2 i R 28 U Z represents the non-metallic atoms necessary to complete a substituted or unsubstituted nitrogen-containing heterocyclic ring; each e~ is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group; n is an integer M+ is selected from any suitable cation; cationic dyes having the following general formula: wherein: each R 31 R 32 R 33 and R 3 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein any two adjacent R 31 R 32 W 33 or R3groups may be connected to form a ring; R 35 and R 3 are as defined above for R 33 and R 3; is 0, S, or NR 37 is N or CR 38 W 37 and R 3 1 are as defined above for 3 and wherein 153 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/US95/08383 M- is any suitable anion; cationic dyes having the following general formula: R 39 wherein: each R 3 R 32 R 3 R and R 4 group is independently hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclic group, and wherein any two adjacent R 31 R 32 R 33 or R groups may be connected to form a ring; R 9 is independently hydrogen, a hydrocarbyl-containing group, or a heterocyclic group; X is C=R 4 C(R)2, O, S, or NR 3 wherein R 37 is as defined above for R 3 9 R 38 is as defined above for R 4 R is an oxo group, a divalent hydrocarbyl-containing group or a divalent 2 0 heterocyclic group, and wherein R 4 and R 4 may be connected to form an unsaturated ring, and R 37 and R 3 may be connected to form a ring; and wherein M- is any suitable anion; and cationic dyes having the following general formula: 0 R 4 0 0 R 4 1 N 46 R4225 wherein: wherein: 154 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 each R 42 to R 45 group is independently hydrogen, halogen, or a hydrocarbyl- containing group, or a heterocyclic group; each R, and R 47 group is independently hydrogen, a hydrocarbyl- containing group, or a heterocyclic group and wherein any two adjacent R 4 to R 4 groups may be connected to form a ring and wherein R 4 and R 45 may be connected to form a ring; n is an integer less than 5; and wherein M- is any suitable anion, and wherein said dental impression material exhibits a color change upon curing of at least 10 AE* units. 30. A method of monitoring the curing of a dental impression material, comprising the steps of: placing against the teeth of a patient an impression material comprising a curable silicone polymer containing at least two functional groups capable of 15 reacting with a SiH group in the presence of a hydrosilation catalyst, a crosslinker compound containing at least two SiH groups, a hydrosilation catalyst comprising a complex of platinum and an unsaturated organosilicon material, and one or more cure-indicating dyes; and visually observing said impression material, wherein said impression material 20 has a first color before the cure reaction is effected and a second color after the cure reaction has been effected to an indication point, and wherein said first and second colors differ by at least 5 AE* units. 31. A method of monitoring the curing of a dental impression material according to claim 30, wherein the second color of said dental impression material is compared to a reference color standard and wherein the color difference between the reference color standard and the second color of said dental impression material is less than 3 AE* units.

32. A method of monitoring the curing of a curable composition according to claim 30, wherein the first color of said dental impression material is compared to a SZ155 S SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCr1US95/0S383 reference color standard and wherein the color difference between the reference color standard and the first color of said dental impression material is less than 3 AE* unts

33. A method of monitoring the curing of a dental impression material according to claim 3 1, wherein said reference color standard is selected from the group consisting of printed cards, printed labels, colored plastic parts, painted parts, colored ceramic parts, and colored dental impression materials.

34. A method of monitoring the curing of a dental impression material to 00.:according to claim 30, wherein said first and second colors difer by at least 10 AE* units. A method of monitoring the curing of a dental impression material according to claim 30, wherein said firs andisecond colors diffger byithilasot 150A

36. A method of monitoring the curing of a dental impression material according to claim 30, wherein said dyre exiitsn ay colo idang wihiaiouth muefs atd imrsso atraln whenei 500 cogo of said dy,50i fdclrmetess00iof paetaeldisoaet a 10ernc olof r hyrsatndr sctlys srouton hagr bewee consisting of printed cards, printed labels, colored plastic parts, painted parts, colored ceramic parts, and colored curable composition's and wherein the color difference between the reference color standard and the second color of said impression material is less than 3 AE* units. 156 SUBSTITUT SKEET (RULE 26) WO 96/00560 PCTIUS95/09333

38. A method of monitoring the curing of a curable Composition according to claim 36, tirther comprising the step of. placing said dental impression material against the teeth of a patient and allowing said impression material to cure.

39. A method of monitoring the curing of a curable composition according to claim 38, further comprising the step of: removing said impression material from the mouth of said patient, and then visually observing the surface of said impression material for the presence of any regions which exhibit less color change than the bulk of the impression. *0@e40. A method of monitoring the curing of a curable composition according to claim 38, fiurther comprising the step of- removing said impression material from the mouth of said patient, and then visually observing the surfa~ce of said impression material for the presence of any regions which after 30 seconds exhibit less color change than the bulk of the impression. 20 41. A method of monitoring the curing of a curable composition according to claim 32, wherein the time at which the color difference between said impression material and said reference color standard is greater than 3 AE* units corresponds to just bfere the gel point of the impression material.

43. A dental impression material in the form or a single-part of multiple-part composition, comprising: 157 \A SUBSnTMT SHEET (RULE 26) WO 96/00560 WO 9600560PCT/US9SIOS3S3 a curable silicone polymer containing at least two functional groups capable of reacting with a SOH group in the presence of a catalyst; a crosslinker compound containing at least two SOH groups; a hydrosilation catalyst; between 20 and 90 weight percent filler, a surfactant; and one or more cure-indicating dyes selected from the group consisting of indoaniline dyes, indophenol dyes, quinone monoirnine dyes, quinone diimine dyes, cyanine dyes, merocyanine dyes, cydlohexadienone dyes, -iminocydohexadienone dyes, inidazolylidinecyclohexadienone dyes. dihydronaphthalenone dyes, iminodihydronaphthalenone dyes, imidazolylidkiihydironaphthalenone dyes, cyclohexadieninune dyes, aryl substituted bis (trifluoromethyLsufobnyl)hexatrienyI dyes, aryl substituted bis (trifluoromethylsulfonyl)butadienyl dyes, aryl substituted 0 15 bis (fluorosulonyl)heaztrienyl dyes, aryl substituted bis (fluorosulfonyl)butadienyl dyes, oxazolone dys cationic dyes, anionic dyes and amphoteric dyes, wherein said impression material exhibits a color change upon curing of at least 10 AE* units. .44. A dental impression material in the form of a single-part or multiple-part composition, comprising: 20a curable silicone polymer containing at least two functional groups capable: of reacting with a SiO group in the presence of a hydrosilaton catalyst; 04 0: a. a crosslinker compound containing at least two SOH groups; a catalyst capable of catalyzing a hydrosilauion reaction, and one or more cure-indicating dyes, wherein said dye exhibits a color change within about 10 minutes at 25 *C when 500 jpg of said dye, 500 pi of dichloromethane, 100 p1 of pentamethyidisiloxane and 10 p1 of a hydrosilation catalyst-solutionauving bctwecn about 2 an e-3-eight Pe cent pltiuu, at mixed together, 158 SUBSTITUITE SHEET (RULE 26) WO 96/00560 WO 9600560PCrfUS95/08383 wherein said dye is represented by the formula R4 R52 R 5 1 R 5 \C/ R56 7 \R54 Cl wherein each of R" 4 ,and is independently. selected from the group consisting of: hydrogen, halogen and an acydic, alicyclic or aromatic hydrocarbyl optionally interrupted with one or more heteroatoms, each of R51, R 52 R 53 R 5 4, R 55 and R 5 6 is independently selected from the *0 0 group consisting of hydrogen and an acyclic, alicyclic or aromatic hydrocarbyl group optionally interrupted with one or more heteroatoms, and optionally, any two ofR, R 53 e, ei, and R56 may together form an alicyclic or aromatic ring. gets** S.159 SUBSTITUT SKEET (RULE 26) WO 96/00560 PCTIUS95/08383 The composition of claim 44, wherein each of R, R, and Ris independently selected from the group consisting of hydrogen, alkyl and halogen; and each of R' 2 R1 3 R" 4 and R" is independently selected from the group consisting of hydrogen and alkyl that is optionally substituted by one or more cyano, alkoxy, hydroxy, alkylsiloxy, alkylsilyl, acyl, aryl, halo, arylsiloxy, arylsilyl, amino, and mono or dialkyl amino groups.

46. The composition of claim 44, wherein at least one of R 2 R 3 R", and Ru is selected from the group consisting of CH 2 OSi(CH 3 )2 C(CH 3 3 CH 2 OC(O)CH2CH(CH 3 )CH2C(CH 3 )3 CH 2 OC(O)C(CH) 3 CH OCH2 OCH2CH2 Si(CH). CH 2 CI CH20C()NHCH 2 CH 2 CH 2 CH 3 ,and CH20C(O)NHCH 2 CH 2 CH 2 Si(OCH2H 3

47. A dental impression material in the form of a single-part or multiple-part 20 composition, comprising: Got* a curable silicone polymer containing at least two functional groups capable S of reacting with a SiH group in the presence ofa hydrosilation catalyst; a crosslinker compound containing at least two SiH groups; A~ 160 SUBSTiTUTE SHEET (RULE 26) WO 96/00560 PCTIUS95/08383 a catalyst capable of catalyzing a hydrosilation reaction; and one or more cure-indicating dyes, wherein said dye exhibits a color change within about minutes at 25 *C when 500 pg of said dye, 500 pi of dichloromethajie, 100 W1 of pentamethyldisiloxane and 10 p1 of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together, wherein said dye is represented by the formula a a. a a. a a. a a. a a a a 161 SUBSTITUTE SHEET (RULE 26) WO 96/00560 PCT/IUS950833 wherein X 4 is N-R 67 O-R6, S-R0 or CR 7 R7R2 and wherein each of Rs, R' 9 R6 0 R6', R6 R R, R' 5 R66", is independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl group optionally interrupted with one or more heteroatoms and an acyclic, alicyclic or aromatic heterocyclic group, and each of R, R 7 and Rn is independently selected from the group consisting of hydrogen, a hydrocarbyl group optionally interrupted with one or more heteroatoms and an acyclic, alicyclic or aromatic heterocyclic group. 15 2 0 *006

48. The composition of claim 47, wherein each of R, R, R, R, R 7 R, and R' is independently selected from the group consisting of hydrogen and alkyl that is optionally substituted by one or more cyano, alkoxy, hydroxy, alkylsiloxy, alkylsilyl, acyl, aryl, halo, arylsiloxy, arylsilyl, amino, and mono or dialkyl amino groups.

49. The composition of claim 47, wherein at least one of Re, R 0 R R7, Rn, and R' is selected from the group consiting of CH2CH 2 OSi(CH 3 2 C(CH 3 3 CH 2 CH 2 OC(O)CH2CH(CH 3 )CH 2 C(CH 3 b CH 2 CH 2 OC(O)C(CH) 3 CH 2 CH 2 OCH2 OCH 2 CH 2 Si(CH 3 3 CH 2 CH 2 CI CH2CH20C(O)NHCH2CH2CH2CH 3 and CH2CH20C(O)NHCHCH2CH 2 Si(OCH 2 CH) 3

50. A dental impression material, in the form of a single-part or multiple-part composition, comprising: a curable silicone polymer containing at least two functional groups capable of reacting with a SiH group in the presence of a hydrosilation catalyst; a crosslinker compound containing at least two SiH groups; a catalyst capable of catalyzing a hydrosilation reaction; and one or more cure-indicating dyes, wherein said dye exhibits a color change within about 10 minutes at 25 C when 500 pg of said dye, 500 pid of 162 SUBSTITUTE SHEET (RULE 26) WO 96/00560 WO 9600560PCTfUS95IOS383 dichloromethane, 100 jpd of pentainethyldisiloxane and 10 jil of a hydrosilation catalyst solution having between about 2 and 3 weight percent platinum are mixed together, wherein said dye is selected from compounds of the formula NC and a. *aaa.. a. a a a. a a a a. a 163 SUBSTITUTE SHEET (RULE 26) -164-

51. A dental impression material of claim 44, wherein said catalyst is a hydrosilation catalyst comprising a complex of platinum and an unsaturated organosilicon material.

52. A dental impression material of claim 50, wherein said catalyst is a hydrosilation catalyst comprising a complex of platinum and an unsaturated organosilicon material.

53. A dental impression material of claim 47, wherein said catalyst is a hydrosilation catalyst comprising a complex of platinum and an unsaturated organosilicon material.

54. A dental impression material substantially as hereinbefore described with reference to the examples. A method of monitoring the curing of a dental impression material substantially as hereinbefore described with reference to the examples. 0 DATED this 27th day of October 2000 MINNESOTA MINING AND MANUFACTURING COMPANY by its Patent Attorneys DAVIES COLLISON CAVE 961 119P-WpA \ca\wsCLAJBiS.,14