US4376685A
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US
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Acid copper electroplating baths containing brightening and leveling additives
Assignee: M& T CHEMICALS INC A CORP OF
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Filing: 1981-06-24
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Granted: 1983-03-15
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Expires: 2001-06-24
Abstract
Abstract The invention is concerned with the electrodeposition of copper from an aqueous acidic bath containing the following additives: a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula : H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent; an organic sulfo sulfonate; a polyether; and optionally a thioorganic compound.
Inventors
- 👤 Angus Watson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 19:53
CPC Classifications
C; C25; C25D; C25D3/00; C25D3/02; C25D3/38
Claims Analysis
Total Claims: 51
Claim 1
Independent Claim
47 words
An aqueous acid copper electroplating bath containing an alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6, with an epihalohydrin and an alkylating agent.
Claim 2
Dependent Claim
47 words
An aqueous acid copper electroplating bath containing an alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6, with an epihalohydrin and an alkylating agent.
Claim 3
Dependent Claim
26 words
The acid copper bath of claim 1 wherein said polyalkyleneimine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.
Claim 4
Dependent Claim
52 words
The acid copper bath of claim 1 wherein said alkylating agent is selected from the group consisting of an alkyl halide having from 1 to 3 carbon atoms, an alkylene halide having from 3 to 6 carbon atoms, an alkynyl halide having from 3 to 6 carbon atoms, and an aralkyl halide.
Claim 5
Dependent Claim
14 words
The acid copper bath of claim 3 wherein said aralkyl halide is benzyl chloride.
Claim 6
Dependent Claim
121 words
The acid copper electroplating bath of claim 1 which further comprises an organic sulfo sulfonate represented by the formula: R.sub.1 --(S).sub.n --RSO.sub.3 M wherein M is an alkali metal or ammonium ion; n is from 1 to 6; R is selected from the group consisting of an alkylene group having from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group consisting of the group MO 3 SR, where M & R are as described above, ##STR31## wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR32## wherein r is from 2 to 6.
Claim 7
Dependent Claim
88 words
The acid copper electroplating bath of claim 1 which further comprises a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl and benzyl.
Claim 8
Dependent Claim
140 words
The acid copper electroplating bath of claim 1 which further comprises a thioorganic compound represented by the formula: ##STR33## wherein the bond between C and S and N and C is a single or a double bond, R 1 or R 2 may be hydrogen or R 1 taken together with R 2 forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or carbon atoms and at least one heteroatom selected from the group consisting of S, N and N-substituted atom, R 3 is selected from the group consisting of hydrogen, alkyl and aralkyl, and R 4 is ##STR34## wherein R 5 and R 6 are each selected from the group consisting of hydrogen, alkyl and aralkyl groups.
Claim 9
Dependent Claim
13 words
The acid copper electroplating bath of claim 1 wherein said epihalohydrin is epichlorohydrin.
Claim 10
Dependent Claim
236 words
An aqueous acid copper electroplating bath containing a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent; b. An organic sulfo sulfonate represented by the formula: R.sub.1 --(S).sub.n --RSO.sub.3 M wherein M is an alkali metal or ammonium ion; n is from 1 to 6; R is selected from the group consisting of an alkylene group having from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group consisting of MO 3 SR, wherein M & R are as described above, ##STR35## wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR36## wherein r is from 2 to 6; and c. a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl and benzyl.
Claim 11
Dependent Claim
236 words
An aqueous acid copper electroplating bath containing a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent; b. An organic sulfo sulfonate represented by the formula: R.sub.1 --(S).sub.n --RSO.sub.3 M wherein M is an alkali metal or ammonium ion; n is from 1 to 6; R is selected from the group consisting of an alkylene group having from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group consisting of MO 3 SR, wherein M & R are as described above, ##STR35## wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR36## wherein r is from 2 to 6; and c. a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl and benzyl.
Claim 12
Dependent Claim
140 words
The acid copper electroplating bath of claim 9 which further comprise a thioorganic compound represented by the formula: ##STR37## wherein the bond between C and S and N and C is a single or a double bond, R 1 or R 2 may be hydrogen or R 1 taken together with R 2 forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or carbon atoms and at least one heteroatom selected from the group consisting of S, N and N-substituted atom, R 3 is selected from the group consisting of hydrogen alkyl and aralkyl, and R 4 is ##STR38## wherein R 5 and R 6 are each selected from the group consisting of hydrogen, alkyl and aralkyl groups.
Claim 13
Dependent Claim
34 words
The acid copper electroplating bath of claim 10 wherein said thioorganic compound is selected from the group consisting of thiourea, N-alkyl and aryl substituted thioureas, 2-thiazolidinethione, 1-(2-hydroxyethyl)-2-imidazolidine thione, 2-aminothiazole, 2-imidazoline thione, 2-mercaptopyridine and benzothiazolethione.
Claim 14
Dependent Claim
26 words
The acid copper bath of claim 9 wherein said polyalklyene imine is selected from the group consisting of ethylenediamine, propylene diamine, diethylene triamine and dipropylene triamine.
Claim 15
Dependent Claim
13 words
The acid copper electroplating bath of claim 9 wherein said epihalohydrin is epichlorohydrin.
Claim 16
Dependent Claim
23 words
The acid copper electroplating bath of claim 9 wherein said alkylated polyalkyleneimine is formed from substantially equimolar amounts of polyalkyleneimine and alkylating agent.
Claim 17
Dependent Claim
35 words
The acid copper electroplating bath of claim 9 wherein said organic sulfo sulfonate is a disulfo sulfonate represented by the formula: MO.sub.3 S (CH.sub.2).sub.a S--S (CH.sub.2).sub.a SO.sub.3 M wherein a is from 2 to 6.
Claim 18
Dependent Claim
51 words
The acid copper electroplating bath of claim 9 wherein said organic sulfo sulfonate is a sulfonated dialkyl dithiocarbamate represented by the formula: ##STR39## wherein R may be each an alkyl group of from 1 to 3 carbon atoms or a cycloaliphatic hydrocarbon and b is a number from 2 to 6.
Claim 19
Dependent Claim
15 words
The acid copper electroplating bath of claim 9 wherein said organic sulfo sulfonate is ##STR40##
Claim 20
Dependent Claim
15 words
The acid copper electroplating bath of claim 9 wherein said organic sulfo sulfonate is: ##STR41##
Claim 21
Dependent Claim
367 words
An aqueous acid copper electroplating bath containing: a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N(CH.sub.2).sub.n NH R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent; b. An organic sulfo sulfonate represented by the formula: R.sub.1 --(S).sub.n --RSO.sub.3 M wherein M is an alkali metal or ammonium ion; n is from 1 to 6; R is selected from the group consisting of an alkylene group of from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group consisting of MO 3 SR, wherein M & R are as described above, ##STR42## wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR43## wherein r is from 2 to 6; c. a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl and benzyl and d. A thioorganic compound represented by the formula: ##STR44## wherein the bond between C and S and N and C is a single or a double bond, R 1 or R 2 may be hydrogen or R 1 taken together with R 2 forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or carbon atoms and at least one heteroatom selected from the group consisting of S, N and N-substituted atom, R 3 is selected from the group consisting of hydrogen alkyl and aralkyl, and R 4 is ##STR45## wherein R 5 and R 6 are each selected from the group consisting of hydrogen, alkyl and aralkyl groups.
Claim 22
Dependent Claim
367 words
An aqueous acid copper electroplating bath containing: a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N(CH.sub.2).sub.n NH R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent; b. An organic sulfo sulfonate represented by the formula: R.sub.1 --(S).sub.n --RSO.sub.3 M wherein M is an alkali metal or ammonium ion; n is from 1 to 6; R is selected from the group consisting of an alkylene group of from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group consisting of MO 3 SR, wherein M & R are as described above, ##STR42## wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR43## wherein r is from 2 to 6; c. a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl and benzyl and d. A thioorganic compound represented by the formula: ##STR44## wherein the bond between C and S and N and C is a single or a double bond, R 1 or R 2 may be hydrogen or R 1 taken together with R 2 forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or carbon atoms and at least one heteroatom selected from the group consisting of S, N and N-substituted atom, R 3 is selected from the group consisting of hydrogen alkyl and aralkyl, and R 4 is ##STR45## wherein R 5 and R 6 are each selected from the group consisting of hydrogen, alkyl and aralkyl groups.
Claim 23
Dependent Claim
52 words
The acid copper bath of claim 19 wherein said alkylating agent is selected from the group consisting of an alkyl halide having from 1 to 3 carbon atoms, an alkylene halide having from 3 to 6 carbon atoms, an alkynyl halide having from 3 to 6 carbon atoms and an aralkyl halide.
Claim 24
Dependent Claim
14 words
The acid copper bath of claim 20 wherein said aralkyl halide is benzyl chloride.
Claim 25
Dependent Claim
13 words
The acid copper electroplating bath of claim 19 wherein said epihalohydrin is epichlorohydrin.
Claim 26
Dependent Claim
23 words
The acid copper electroplating bath of claim 19 wherein said alkylated polyalkyleneimine is formed from substantially equimolar amounts of polyalkyleneimine and alkylating agent.
Claim 27
Dependent Claim
32 words
The acid copper electroplating bath of claim 19 wherein said organic sulfo sulfonate is a disulfosulfonate represented by the formula: MO.sub.3 S(CH.sub.2).sub.a S--S(CH.sub.2).sub.a SO.sub.3 M wherein a is from 2 to 6.
Claim 28
Dependent Claim
51 words
The acid copper electroplating bath of claim 19 wherein said organic sulfo sulfonate is a sulfonated dialkyl dithiocarbamate represented by the formula: ##STR46## wherein R may be each an alkyl group of from 1 to 3 carbon atoms or a cycloaliphatic hydrocarbon and b is a number from 2 to 6.
Claim 29
Dependent Claim
15 words
The acid copper electroplating bath of claim 19 wherein said organic sulfo sulfonate is ##STR47##
Claim 30
Dependent Claim
15 words
The acid copper electroplating bath of claim 19 wherein said organic sulfo sulfonate is: ##STR48##
Claim 31
Dependent Claim
166 words
An aqueous acid copper electroplating bath containing: a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6, with epichlorohydrin and benzyl chloride, the molar amounts of polyalkyleneimine, epichlorohydrin and benzyl chloride being substantially equal; b. an organic sulfo sulfonate represented by the formula: MO.sub.3 S(CH.sub.2).sub.a S--S(CH.sub.2).sub.a SO.sub.3 M wherein a is from 2 to 6; c. a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl and benzyl; and d. an equimolar combination of 2-thiazolidinethione and 1-(2-hydroxyethyl)-2-imidazolidinethione.
Claim 32
Dependent Claim
166 words
An aqueous acid copper electroplating bath containing: a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6, with epichlorohydrin and benzyl chloride, the molar amounts of polyalkyleneimine, epichlorohydrin and benzyl chloride being substantially equal; b. an organic sulfo sulfonate represented by the formula: MO.sub.3 S(CH.sub.2).sub.a S--S(CH.sub.2).sub.a SO.sub.3 M wherein a is from 2 to 6; c. a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl and benzyl; and d. an equimolar combination of 2-thiazolidinethione and 1-(2-hydroxyethyl)-2-imidazolidinethione.
Claim 33
Dependent Claim
52 words
A process for producing copper deposits which comprises electrodepositing copper from an aqueous acidic copper bath containing the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent.
Claim 34
Dependent Claim
52 words
A process for producing copper deposits which comprises electrodepositing copper from an aqueous acidic copper bath containing the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent.
Claim 35
Dependent Claim
119 words
The process of claim 29 in which said bath further comprises an organic sulfo sulfonate represented by the formula: R.sub.1 --(S).sub.n --RSO.sub.3 M wherein M is an alkali metal or ammonium ion; n is from 1 to 6; R is selected from the group consisting of an alkylene group having from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group consisting of MO 3 SR, wherein M & R are as described above, ##STR49## wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR50## wherein r is from 2 to 6.
Claim 36
Dependent Claim
88 words
The process of claim 29 in which said bath further comprises a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl and benzyl.
Claim 37
Dependent Claim
140 words
The process of claim 29 in which said bath further comprises a thioorganic compound represented by the formula: ##STR51## wherein the bond between C and S and N and C is a single or a double bond, R 1 or R 2 may be hydrogen or R 1 taken together with R 2 forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or carbon atoms and at least one heteroatom selected from the group consisting of S, N and N-substituted atom, R 3 is selected from the group consisting of hydrogen, alkyl and aralkyl, and R 4 is ##STR52## wherein R 5 and R 6 are each selected from the group consisting of hydrogen, alkyl and aralkyl groups.
Claim 38
Dependent Claim
249 words
A process for producing bright and leveled copper deposits which comprises electrodepositing copper from an aqueous acidic copper bath containing: a. an alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent; b. an organic sulfo sulfonate represented by the formula: R.sub.1 --(S).sub.n --RSO.sub.3 M wherein M is an alkali metal or ammonium ion; n is from 1 to 6; R is selected from the group consisting of an alkylene group of from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group consisting of MO 3 SR, wherein M & R are as described above, ##STR53## wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR54## wherein r is from 2 to 6; and c. a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkyryl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl or benzyl.
Claim 39
Dependent Claim
249 words
A process for producing bright and leveled copper deposits which comprises electrodepositing copper from an aqueous acidic copper bath containing: a. an alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula: H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH 2 ) n NH 2 and n=1 to 6 with an epihalohydrin and an alkylating agent; b. an organic sulfo sulfonate represented by the formula: R.sub.1 --(S).sub.n --RSO.sub.3 M wherein M is an alkali metal or ammonium ion; n is from 1 to 6; R is selected from the group consisting of an alkylene group of from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group consisting of MO 3 SR, wherein M & R are as described above, ##STR53## wherein R 2 & R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR54## wherein r is from 2 to 6; and c. a polyether represented by the formula: R(OZ).sub.m wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkyryl, alkylaryl and arylalkyl; m is 5 to 100; and Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T wherein u and v=0 to 4 but at least one of u or v must be greater than 0, r+s=6 to 200,000; r=0 when u=0; s=0 when v=0; and T is selected from the group consisting of hydrogen, alkyl or benzyl.
Claim 40
Dependent Claim
140 words
The process of claim 33 wherein said bath which further comprises a thioorganic compound represented by the formula: ##STR55## wherein the bond between C and S and N and C is a single or a double bond, R 1 or R 2 may be hydrogen or R 1 taken together with R 2 forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or carbon atoms and at least one heteroatom selected from the group consisting of S, N and N-substituted atom, R 3 is selected from the group consisting of hydrogen alkyl and aralkyl, and R 4 is ##STR56## wherein R 5 and R 6 are each selected from the group consisting of hydrogen, alkyl and aralkyl groups.
Claim 41
Dependent Claim
30 words
The process of claim 34 wherein said organic sulfo sulfonate is a disulfo sulfonate represented by the formula: MO.sub.3 S(CH.sub.2).sub.a S--S(CH.sub.2).sub.2 SO.sub.3 M wherein a is from 2 to 6.
Claim 42
Dependent Claim
48 words
The process of claim 34 wherein said organic sulfo sulfonate is a sulfonated dialkyl dithiocarbamate represented by the formula: ##STR57## wherein R may be each an alkyl group of from 1 to 3 carbon atoms or a cycloaliphatic hydrocarbon and b is a number from 2 to 6.
Claim 43
Dependent Claim
12 words
The process of claim 34 wherein said organic sulfo sulfonate is ##STR58##
Claim 44
Dependent Claim
12 words
The process of claim 34 wherein said organic sulfo sulfonate is ##STR59##
Claim 45
Dependent Claim
29 words
The process of claim 34 wherein said thioorganic compound is selected from the group consisting of thiourea, N-alkyl and aryl substituted thioureas, 2-thiazolidinethione, 1-(2-hydroxyethyl)-2-imidazolidinethione, 2-aminothiazole, 2-imidazolinethione, 2-mercaptopyridine, and benzothiazolethione.
Claim 46
Dependent Claim
30 words
The process of claim 33 wherein said organic sulfo sulfonate is a disulfo sulfonate represented by the formula: MO.sub.3 S(CH.sub.2).sub.a S--S(CH.sub.2).sub.a SO.sub.3 M wherein a is from 2 to 6.
Claim 47
Dependent Claim
48 words
The process of claim 33 wherein said organic sulfo sulfonate is as sulfonated dialkyl dithiocarbamate represented by the formula: ##STR60## wherein R may be each an alkyl group of from 1 to 3 carbon atoms or a cycloaliphatic hydrocarbon and b is a number from 2 to 6.
Claim 48
Dependent Claim
12 words
The process of claim 33 wherein said organic sulfo sulfonate is ##STR61##
Claim 49
Dependent Claim
12 words
The process of claim 33 wherein said organic sulfo sulfonate is ##STR62##
Claim 50
Dependent Claim
29 words
The process of claim 33 wherein said thioorganic compound is selected from the group consisting of thiourea, N-alkyl and aryl substituted thioureas, 2-thiazolidinethione, 1-(2-hydroxyethyl)-2-imidazolidinethione, 2-aminothiazole, 2-imidazolinethione, 2-mercaptopyridine, and benzothiazolethione.
Claim 51
Dependent Claim
24 words
The process of claim 33 wherein said bath further comprises a thioorganic compound which consists of an equimolar mixture of 2-thiazolidinethione and 1-(2-hydroxyethyl)-2-imidazolidine thione.
References Cited (Backward Citations)
US2733198A
Cited
USRE24582E
Cited
US2296225A
Cited
US2272489A
Cited
US2355070A
Cited
US2563360A
Cited
US2366737A
Cited
US2391289A
Cited
US2424887A
Cited
US2462870A
Cited
US2609339A
Cited
US2660554A
Cited
US2700019A
Cited
US2707166A
Cited
US2707167A
Cited
US2700020A
Cited
US2663684A
Cited
US2737485A
Cited
US2758076A
Cited
US2773022A
Cited
US2849351A
Cited
US2837472A
Cited
US2903403A
Cited
US2799634A
Cited
US2986498A
Cited
US2830014A
Cited
US3023150A
Cited
US2842488A
Cited
US2738318A
Cited
US2910413A
Cited
US2805193A
Cited
US2805194A
Cited
US2853444A
Cited
US2848394A
Cited
US2849352A
Cited
US3000800A
Cited
US2882209A
Cited
US3021266A
Cited
US2931760A
Cited
US3051634A
Cited
US2950235A
Cited
US3075899A
Cited
US3018232A
Cited
US2954331A
Cited
US2999767A
Cited
US3081240A
Cited
US2967135A
Cited
US3037918A
Cited
US3203878A
Cited
US3179578A
Cited
US3030282A
Cited
US3227638A
Cited
US3122549A
Cited
US3359297A
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-03-14 | 1986-09-13 | 1987-03-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-03-14 | 1990-09-13 | 1991-03-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-03-14 | 1994-09-13 | 1995-03-15 | $7700.00 | Window Closed / Lapsed |