# US 4,396,735 A · Synergistic light stabilizer compositions for synthetic resins and resin compositions containing the same

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- Number: US 4,396,735 A
- Document ID: US4396735A
- Status: Granted
- Kind: A
- Application number: 06/193,551
- Filed: 1980-10-03
- Granted: 1983-08-02
- Earliest claimed: 1977-11-21
- Assignees: Adeka Argus Chemical Co., Ltd.
- Inventors: Motonobu Minagawa; Naohiro Kubota; Toshihiro Shibata
- Web page: https://patentgrep.com/patent/US4396735A

## CPC

- C08K 5/3462: Six-membered rings
- C08K 5/3435: Piperidines
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

Light stabilizers for synthetic resin compositions and synthetic resin compositions containing such stabilizers are provided, comprising (1) at least one hindered heterocyclic amine having the formula: ##STR1## wherein: X is a bivalent linking radical forming with the ring structure ##STR2## a nitrogen-containing heterocyclic ring having from five to seven ring atoms, preferably piperidine; R.sub.1 and R.sub.2 are each selected from the group consisting of lower alkyl, preferably methyl, and R.sub.1 and R.sub.2 taken together as pentylene (CH.sub.2).sub.5 ; R.sub.3 and R.sub.4 are each selected from the group consisting of lower alkyl, and R.sub.3 and R.sub.4 taken together as one of butylene--(CH.sub.2).sub.4, pentylene--(CH.sub.2).sub.5, and CH.sub.2 --C(CH.sub.3).sub.2 --NH--C(CH.sub.3).sub.2 --CH.sub.2 --; n is 1 or 2; and when n is 1, Y.sub.1 is selected from the group consisting of hydrogen, O.sup..cndot., OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and when n is 2, Y.sub.1 is selected from the group consisting of alkylene, alkenylene, alkynylene, cycloalkylene and aralkylene having from one to about thirty carbon atoms; together with (2) at least one heterocyclic acid hydrazide having the formula: ##STR3## wherein: R is selected from the group consisting of hydrogen, alkyl, aryl and such groups having hydroxyl, carboxylic acid ester, oxyether and carbonyl groups having from one to about thirty carbon atoms; ##STR4## is the residue of a dicarboxylic or tetracarboxylic acid, wherein Z is selected from the group consisting of alkylene, alkenylene, cycloalkylene, alkylcycloalkylene, arylene and alkylarylene having from one to about thirty carbon atoms, and such radicals bearing free carboxylic acid or carboxylic acid ester groups; and m is 1 or 2. In such combinations, the heterocyclic acid hydrazide, which alone is not a light-stabilizer, synergizes the stabilizing effectiveness of the hindered heterocyclic amine.

## Claims

### Claim 1

A light stabilizer composition for organic polymeric materials comprising:
(1) at least one hindered heterocyclic amine having the formula: ##STR241## wherein: X is a bivalent linking radical including at least one up to four ring carbon atoms completing the ring structure: ##STR242## as a heterocyclic ring having from five to seven ring atoms of which at least one is nitrogen and from three to six are carbon; and a substituent selected from the group consisting of Z; O--Z; NH--Z; ##STR243## wherein Z is the residue of an acid selected from the group consisting of carboxylic acids having from one to thirty carbon atoms, carbonic acid and inorganic oxyacids of phosphorus, silicon and boron and R" is hydrogen or lower alkyl; and
.dbd.Z.sub.4 wherein Z.sub.4 is a bivalent group selected from the group consisting of: ##STR244## wherein X.sub.4 is hydrogen or methyl; and
B is selected from the group consisting of alkyl, epoxy alkyl, alkenyl and cycloalkyl having from one to about eighteen carbon atoms, and ##STR245## in which the alkylene has from one to about ten carbon atoms; R.sub.1 and R.sub.2 are each selected from the group consisting of lower alkyl and R.sub.1 and R.sub.2 taken together as pentylene (CH.sub.2).sub.5 ;
R.sub.3 and R.sub.4 are each selected from the group consisting of lower alkyl, and R.sub.3 and R.sub.4 taken together as one of butylene--(CH.sub.2).sub.4, pentylene--(CH.sub.2).sub.5, and CH.sub.2 --C(CH.sub.3).sub.2 --NH--C(CH.sub.3).sub.2 --CH.sub.2 --;
n is 1 or 2; and
when n is 1, Y.sub.1 is selected from the group consisting of hydrogen; O.sup..cndot., OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and
when n is 2, Y.sub.1 is selected from the group consisting of alkylene, alkenylene, alkynylene, cycloalkylene and aralkylene having from one to about thirty carbon atoms; and p1 (2) at least one heterocyclic acid hydrazide having the formula: ##STR246## wherein: R is selected from the group consisting of hydrogen, alkyl, aryl and such groups having hydroxyl, carboxylic acid ester, oxyether and carbonyl groups having from one to about thirty carbon atoms; ##STR247## is the residue of a dicarboxylic or tetracarboxylic acid, wherein Z.sub.1 is selected from the group consisting of alkylene, alkenylene, cycloalkylene, alkylcycloalkylene, arylene and alkylarylene having from one to about thirty carbon atoms, and such radicals bearing free carboxylic acid or carboxylic acid ester groups; and
m is 1 or 2,
the heterocyclic acid hydrazide being in an amount synergizing the stabilizing effectiveness of the hindered heterocyclic amine.

### Claim 2

A light stabilizer composition comprising:
(1) at least one hindered heterocyclic amine which is a 2,2,6,6-tetrasubsituted piperidine having one of the formulae: ##STR248## wherein: R.sub.1 and R.sub.2 are each selected from the group consisting of lower alkyl, and R.sub.1 and R.sub.2 taken together as pentylene (CH.sub.2).sub.5 ;
R.sub.3 and R.sub.4 are each selected from the group consisting of lower alkyl and R.sub.3 and R.sub.4 taken together or as one of butylene--(CH.sub.2).sub.4, pentylene--(CH.sub.2).sub.5, and--CH.sub.2 --C(CH.sub.3).sub.2 --NH--C(CH.sub.3).sub.2 --CH.sub.2 --;
R.sub.5 and R.sub.6 are selected from the group consisting of hydrogen and lower alkyl;
A is ##STR249## wherein R.sub.7 is lower alkyl; n.sub.1 is a number from 1 to 6;
Y.sub.2 is selected from the group consisting of hydrogen, O.sup..cndot., OH, alkyl, alkenyl, alkynyl, aralkyl and acryl having from one to about thirty carbon atoms; and
Z.sub.2 is the residue of an acid selected from the group consisting of carboxylic acids having from one to about thirty carbon atoms, and inorganic oxyacids of phosphorus, silicon and boron; together with
(2) at least one heterocyclic acid hydrazide having the formula: ##STR250## wherein: R is selected from the group consisting of hydrogen, alkyl, aryl and such groups having hydroxyl, carboxylic acid ester, oxyether and carbonyl groups having from one to about thirty carbon atoms; ##STR251## is the residue of a dicarboxylic or tetracarboxylic acid, wherein Z.sub.1 is selected from the group consisting of alkylene, alkenylene, cycloalkylene, alkylcycloalkylene, arylene and alkylarylene having from one to about thirty carbon atoms, and such radicals bearing free carboxylic acid or carboxylic acid ester groups; and
m is 1 or 2,
the heterocyclic acid hydrazide being in an amount synergizing the stabilizing effectiveness of the hindered heterocyclic amine.

### Claim 3

A light stabilizer composition
(1) comprising at least one hindered heterocyclic amine having the formula: ##STR252## in which Y.sub.3 is selected from the group consisting of hydrogen, O.sup..cndot., OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and
Z.sub.3 is the residue of a carboxylic acid having from one to about thirty carbon atoms or an inorganic oxyacid of phosphorus, silicon, or boron; together with
(2) at least one heterocyclic acid hydrazide having the formula: ##STR253## wherein: R is selected from the group consisting of hydrogen, alkyl, aryl and such groups having hydroxyl, carboxylic acid ester, oxyether and carbonyl groups having from one to about thirty carbon atoms; ##STR254## is the residue of a dicarboxylic or tetracarboxylic acid, wherein Z.sub.1 is selected from the group consisting of alkylene, alkenylene, cycloalkylene, alkylcycloalkylene, arylene and alkylarylene having from one to about thirty carbon atoms, and such radicals bearing free carboxylic acid or carboxylic acid ester groups; and
m is 1 or 2,
the heterocyclic acid hydrazide being in an amount synerigizing the stabilizing effectiveness of the hindered heterocyclic amine.

### Claim 4

A light stabilizer composition comprising
(1) at least one hindered heterocyclic amine having the formula: ##STR255## wherein Z.sub.4 is a bivalent group selected from the group consisting of ##STR256## together with (2) at least one heterocyclic acid hydrazide having the formula: ##STR257## wherein: R is selected from the group consisting of hydrogen, alkyl, aryl and such groups having hydroxyl, carboxylic acid ester, oxyether and carbonyl groups having from one to about thirty carbon atoms; ##STR258## is the residue of a dicarboxylic or tetracarboxylic acid, wherein Z.sub.1 is selected from the group consisting of alkylene, alkenylene, cycloalkylene, alkylcycloalkylene, arylene and alkylarylene having from one to about thirty carbon atoms, and such radicals bearing free carboxylic acid or carboxylic acid ester groups; and
m is 1 or 2,
the heterocyclic acid hydrazide being in an amount synergizing the stabilizing effectiveness of the hindered heterocyclic amine.

### Claim 5

A light stabilizer composition comprising
(1) at least one hindered heterocyclic amine having the formula: ##STR259## in which Y.sub.4 is hydrogen or methyl;
X.sub.4 is hydrogen or methyl; and
B is selected from the group consisting of alkyl, epoxy alkyl, alkenyl and cycloalkyl having from one to about eighteen carbon atoms, and ##STR260## in which the alkylene has from one to about ten carbon atoms; together with
(2) at least one heterocyclic acid hydrazide having the formula: ##STR261## wherein: R is selected from the group consisting of hydrogen, alkyl, aryl and such groups having hydroxyl, carboxylic acid ester, oxyether and carbonyl groups having from one to about thirty carbon atoms; ##STR262## is the residue of a dicarboxylic or tetracarboxylic acid, wherein Z.sub.1 is selected from the group consisting of alkylene, alkenylene, cycloalkylene, alkylcycloalkylene, arylene and alkylarylene having from one to about thirty carbon atoms, and such radicals bearing free carboxylic acid or carboxylic acid ester groups; and
m is 1 or 2,
the heterocyclic acid hydrazide being in an amount synergizing the stabilizing effectiveness of the hindered heterocyclic amine.

### Claim 6

A light stabilizer composition comprising
(1) at least one hindered heterocyclic amine having the formula: ##STR263## in which R.sub.8 is hydrogen or alkyl having from one to about six carbon atoms;
p is an even number from 2 to 6; and
Z.sub.5 is the residue of a carboxylic acid having from one to about thirty carbon atoms or an inorganic oxyacid of phosphorus, silicon, or boron; together with
(2) at least one heterocyclic acid hydrazide having the formula: ##STR264## wherein: R is selected from the group consisting of hydrogen, alkyl, aryl and such groups having hydroxyl, carboxylic acid ester, oxyether and carbonyl groups having from one to about thirty carbon atoms; ##STR265## is the residue of a dicarboxylic or tetracarboxylic acid, wherein Z.sub.1 is selected from the group consisting of alkylene, alkenylene, cycloalkylene, alkylcycloalkylene, arylene and alkylarylene having from one to about thirty carbon atoms, and such radicals bearing free carboxylic acid or carboxylic acid ester groups; and
m is 1 or 2,
the heterocyclic acid hydrazide being in an amount synergizing the stabilizing effectiveness of the hindered heterocyclic amine.

### Claim 7 (depends on 1)

A light stabilizer composition according to claim 1 in which X is alkylene having from two to four carbon atoms.

### Claim 8 (depends on 1)

A light stabilizer composition according to claim 1 in which X is alkylene having from two to four carbon atoms substituted with a carboxylic acid ester group.

### Claim 9 (depends on 1)

A light stabilizer composition according to claim 1 in which X is alkylene substituted with a carboxylic acid ester group and a phenolic group.

### Claim 10 (depends on 1)

A light stabilizer composition according to claim 1 in which X is alkylene substituted with an amide group.

### Claim 11 (depends on 1)

A light stabilizer composition according to claim 1 in which X is alkylene substituted with a phenolic group.

### Claim 12

A light stabilizer composition
comprising
(1) at least one hindered heterocyclic amine having the formula: ##STR266## wherein A is alkylene completing the ring structure; X is a bivalent linking radical including at least one up to four ring carbon atoms completing the ring structure ##STR267## as a heterocyclic ring having from five to seven ring atoms of which at least one is nitrogen and from three to six are carbon;
R.sub.1 and R.sub.2 are each selected from the group consisting of lower alkyl, and R.sub.1 and R.sub.2 taken together as pentylene (CH.sub.2).sub.5 ;
R.sub.3 and R.sub.4 are each selected from the group consisting of lower alkyl and R.sub.3 and R.sub.4 taken together as one of butylene--(CH.sub.2).sub.4, pentylene--(CH.sub.2).sub.5, and --CH.sub.2 --C(CH.sub.3).sub.2 --NH--C(CH.sub.3).sub.2 --CH.sub.2 --;
n is 1 or 2; and
Y.sub.1 is selected from the group consisting of hydrogen, O.sup..cndot., OH, alkyl, alkenyl, alkynyl, aralkyl and acyl having from one to about thirty carbon atoms; and
when n is 1, Y.sub.2 is selected from the group consisting of bivalent alkylene, alkenylene, alkynylene, cycloalkylene and arylkylene having from one to about thirty carbon atoms;
and when n is 2, Y.sub.2 is selected from the group consisting of trivalent alkylene, alkenylene, alkynylene, cycloalkylene and aralkylene having from one to about thirty carbon atoms;
together with
(2) at least one heterocyclic acid hydrazide having the formula: ##STR268## wherein: R is selected from the group consisting of hydrogen, alkyl, aryl and such groups having hydroxyl, carboxylic acid ester, oxyether and carbonyl groups having from one to about thirty carbon atoms; ##STR269## is the residue of a dicarboxylic or tetracarboxylic acid, wherein Z.sub.1 is selected from the group consisting of alkylene, alkenylene, cycloalkylene, alkylcycloalkylene, arylene and alkylarylene having from one to about thirty carbon atoms, and such radicals bearing free carboxylic acid or carboxylic acid ester groups; and
m is 1 or 2,
the heterocyclic acid hydrazide being in an amount synergizing the stabilizing effectiveness of the hindered heterocyclic amine.

### Claim 13 (depends on 1)

A light stabilizer composition according to claim 1 in which X is alkylene substituted with a phosphite ester group.

### Claim 14 (depends on 1)

A light stabilizer composition according to claim 1 in which Z.sub.1 is alkylene.

### Claim 15 (depends on 1)

A light stabilizer composition according to claim 1 in which Z.sub.1 is aralkylene.

### Claim 16 (depends on 1)

A light stabilizer composition according to claim 1 in which Z.sub.1 is arylene.

### Claim 17 (depends on 1)

A light stabilizer composition according to claim 1 in which Z.sub.1 is cycloalkylene.

### Claim 18 (depends on 1)

A light stabilizer composition according to claim 1 in which Z.sub.1 includes a second ##STR270## group.

### Claim 19 (depends on 1)

A light stabilizer composition according to claim 1 in which R is hydrogen.

### Claim 20 (depends on 1)

A polyvinyl chloride resin composition having improved resistance to deterioration when heated at 350.degree. F., comprising a polyvinyl chloride resin and a compound in accordance with claim 1.

### Claim 21 (depends on 20)

A polyvinyl chloride resin composition in accordance with claim 20, in which the polyvinyl chloride resin is polyvinyl chloride homopolymer.

### Claim 22 (depends on 20)

A polyvinyl chloride resin composition in accordance with claim 20, in which the polyvinyl chloride resin is a copolymer of vinyl chloride and vinyl acetate.

### Claim 23 (depends on 1)

An olefin polymer composition having improved resistance to deterioration comprising an olefin polymer selected from the group consisting of polymers of alpha-olefins having from two to six carbon atoms and polystyrene, and a compound in accordance with claim 1.

### Claim 24 (depends on 23)

An olefin polymer composition in accordance with claim 23 wherein the polyolefin is polypropylene.

### Claim 25 (depends on 23)

An olefin polymer composition in accordance with claim 23 wherein the polyolefin is polyethylene.

### Claim 26 (depends on 1)

An acrylonitrile-butadiene-styrene polymer having its resistance to deterioration when heated at 300.degree. F. and above enhanced by a compound in accordance with claim 1.

### Claim 27 (depends on 1)

A polyester polymer composition having improved resistance to deterioration comprising a polyester polymer and a compound in accordance with claim 1.

### Claim 28 (depends on 1)

A polyurethane resin composition having improved resistance to deterioration comprising a polyurethane resin and a compound in accordance with claim 1.

### Claim 29 (depends on 1)

An ethylene-vinyl acetate copolymer composition having improved resistance to deterioration comprising an ethylene-vinyl acetate copolymer and a compound in accordance with claim 1.