ZA200508713B - Highly compatible and non-migratory polymeric UV-absorber - Google Patents

Description

Highly compatible and non-migratory polymeric: UV-Absorber

The present invention relates to highly compatible hydroxyphenyitriazine UV- absorbers and to organic polymer material, especially thermoplastic polymer films, containing them. The polymer material thus obtained may be used as packaging films, protecting packed foodstuffs, beverages, pharmaceuticals, cosmetics, personal care products, shampoos and the like from the dele-terious effects of ultraviolet radiation. it is further useful in protecting plants in greenhous-es. The invention further pertains to a method of preventing photooxidation of packed! food by combined use of a UV absorber and an oxygen scavenger. It has been found that certain fris-aryl-s-triazines are especially effective when incorporated in the containers o r films in which such materials are stored.

Compounds of present invention are further effective in cosmetic formulations for the protection of human (or animal) skin or hair against UV radiation.

Also many packaged products such as certain fruit juices, soft drinks, beer, wines, food products, dairy products, cosmetics, shampoos , vitamins and pharmaceuticals are deleteriously affected, i.e. degraded, by the effects of ultraviolet (UV) light when packaged in plastic containers which allow the transmission of such light.

The use of UV absorbers towards protecting bo-tte and film contents is well known.

However there is a trend towards the use of cleaar or lightly colored containers. More aesthetically pleasing containers may be formed from clear plastics, which also allow one to view the contents. Unfortunately, clear and lightly colored containers and films allow the : transmission of significant portions of ultraviolet light, i.e. light in the range of about 280 to : about 400 nm. Further, there is a trend towardss more light-weight and hence thinner walled containers. Thin-walled containers, by virtue of & shorter path length, will allow more UV light to pass. Due to these trends in packaging there is a need for more efficient UV absorbers for use In this area.

Many cooking oils and salad oils are now offered in clear PET [poly(ethylene terephthalate)] packaging. Practically all vegetable or seed-bassed oils such as soybean, olive, safflower, cottonseed and com oils contain varying levels of unsaturated olefinic acids or esters (e.g. linoleates), which are susceptible to light-induced degradation. Most plant-based oils also contain natural chiorophyll or other pigment photosensitizers. Pascall et al., J. Food Sci., 60 (5). 1116 (1995), discuss tha UV protection of soybean oll with the use of Tinuvin® 326 incorporated into coextruded, mullti-layered, polypropylene-based containers. Tinuvin® 326 is a benzotriazole UV absorber, 5 -chioro-2-(2-hydroxy-3-tert-butyl-5-methyiphenyl)-2H- benzotriazole, available from Ciba Specialty Chemicals Corp.

WO 03/004557 describes some hydroxyphenyltriazine UV absorbers having good persistency in polyoiefin films. Plastic containers or films containing durable UV absorbers are also mentioned in WO 01/57124.

Present hydroxyphenyl triazine UV absorbers show excellent compatibility and persistence in a variety of plastic materials and protect these materials from the harmful effects of UV radiation. The same time, these UW absorbers provide efficient and selective UV shielding in greenhouse films, window sheets and packaging materials. Due to extremely long alkyl moieties they are highly compatible with many polymers, allowing thus to incorporate higher amounts of UVA. They are thermally stable and do not exude from the polymer, which is important when in contact with food or beverages.

The praesent invention relates to a oligo- or polyester formula (I) -[A-O-D-0}~ [()) in which x is a number from 1 to 50;

A is a group of the formula (ll)

R 10 (in)

Ra

Ris

R, N° ON ! 7

N

9 jog “0. 0 —C—L—0 R; o—L-C— or has one of the meanings given for T;

Dis C4-Cy2 alkylene or said alkylerae substituted by OH or interrupted by O or both substituted by OH and interrupted by O;

L is C1~Cygalkylene; Cs-Cyocycloalkwiene; Cs-Cigalkenylene; or one of said residues substituted by phenyl, C;-Cialkylp henyl, Cs-Ci cycloalkyl, OH, halogen, Ci-Cisalkoxy, Cs-

Ciz2cycloalkoxy, Cs-C,galkenyloxy, COOH; the R, are independently of each oither H, OR; or OH, with the proviso that at least one of

Ry; or Ry; is OH; the Ry are independently of each oEher hydrogen, C4-Cs.alkyl or a radical of formula -L-CO-O-Rg;

Ro is H, C4-Cisalkyl, C-Cihydroxyelkyl;

Rio is hydrogen, C4-Caalkyl, Ci, phemyl or a group -ORy;

Ry is hydrogen or methyl;

Rs is hydrogen, methyl, OH or OR7z and

T is the divalent acyl residue of an amliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms; and which contains at least one moiety of formula (II) and at least one moiety T.

In a preferred compound, L is C,-C;alkylene, especially C,-Calkylidene or methylene.

D is advantageously C,-Cralkylene or C,-Ciealkyiene interrupted by O.

T as the divalent acy! residus of an aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms includes, for example, aliphatic diacyls wherein the 2 carbonyl groups are interconnected by C4,-Cssalkylene or —alkenylene or alkylene interrupted by cycloalkylene or cycloalkenylene, each of which is unssubstituted or substituted by alkyl, and containing 11 to 58 carbon atoms in total, preferably 240 to 50 carbon atoms. Alkylene or alkenylena may be branched or unbranched, or, preferably not adjacent to an ethylenic double bond, interrupted by oxygen. In preferred co mpounds, T is ~-CO-T'-CO-, wherein T is Cx-

Csoalkylene or Cx-Csoalkylene interrupted by one or more oxygen atoms; especially preferred is unbranched Cz-Cssalkylere. In further preferred compounds, T is —CO-~T-CO-, wherein T' is alkylene interrupted by C _¢Cizcycloalkylene or Cs-Cicycloalkenylene or said cycloalkylene or cycloalkenylene substituted by alkyl and containing 11 to 58 carbon atoms, especially 20-50 carbon atoms, in total ; especially preferred cycloalkylene is cyclohexylene; especially preferred cycloalkenylene is cyclohexenylene. Valuable spacer groups T' are, for example, of the formula IX ed -

R

\ 23

H,)

Ph R 2 (IX) —QR

R 21 . wherein Ry is {CyHop)- and Ry is (CHa) and

Raz, Rs and Ry are -((CqHz)-H, (CeHz)-H, and (CHy)-H, respectively, where a is from the range 0 — 7, and each of the indices b - f is from the range 0 - 20, with the condition that -the sum a+b+c+d +e +f is from the range 15 — 45, or of the formula X

Ro R 2s

R of 2 0 27 09

Rx RE— wherein

R2s and Ry each are C 4-Cisalkylene and each of Ry, Ra, Ras and Ry, independently, are H or C4+-Cygalkyl, and Rxs &and Rs, together may also be a chemical bond, with the cosndition that the total number of carbon atoms in formula X ranges from 20 to 50.

Of special technical imp ortance are spacer groups T' of the formula X wherein Rzs and Rag independently ars alkylexne of 4 — 12 carbon atoms, each of Ro; and Ra, independently, ara

C4-Cizalkyl, while Rog an-d Ra, are hydrogen.

Suitable diacids may be obtained, for example, by dimerization of a mono- with a «di- unsaturated fatty acid; thee product containing a cycloaikenyl structure may be used as such or is, preferably, hydrogeanated before use in the preparation of the present compounds; in the latter case, the hydrasgenated diacld often is a mixture of open chain (“alkylenes”) type and cycloalkylene-interrapted compounds. An example for the preparation of a dia«cid from fatty acids A and 8B is given in the following scheme:

A oo I \ ent OH mwt=280

B wo, cute! carom mwt=282 0 / Rt-1 orca {y-on OH Compd I mwt = 562

HON ot CsHia—CHj 0 [Fu] x Compd II ( cyclic dimer acid ) nme yon OH mwt = 564

HO Ceti CeHjz—CH3 hi 0 \ a : x

CHi3— CsHl; CoH; Be oy Compl * ’ fi ( linear dimer acid )

HO.__CeHn2 CsHiz~—CHa mwt = 566 hd 0

In the compounds of~ present formula |, most preferably, the R4 are OH; the R; are hydrogen or methyi;

Ryo is hydrogen, methyl or a group -ORy;

R;4 is hydrogen;

Rqs is hydrogen, OH or methyi.

Terminal groups of ttme oligomer or polymer of formula (I) usually are -0-D-OR;,, or -OR, if bonded to A (left side of formula I),

or —A-ORys, such as —-T-COOR, or ~{formula l{-OR¢2, or —R12 if bonded to O (right side of formula 1), where Rq2 is H or C4-Cgalkyl.

For example, the ester of formula (I) may conform to the fosrmula (lil)

R 10

Ri

Ris

R, NN

Rs Rg

R opi R; |g] f-o-0Ho-ooreoo—r 2

Ry Ry } 4 in ity which x is a number from 1 to 20; the number y is at least 1 and ranges from (x +z — 1) to (x * z + 1);

Zz is a number from 1 to 20; and

Regis hydrogen, C-Cr.alkyl; Cs-Crocycloalkyl; C-Cioalkenyl; phenyl; C;-Cqialkylphenyl; Cs-

C 1-alkyl substituted by phenyl, OH, halogen; C-Csalkoxy, (Cs-Cscycloalkoxy, Cs-

C qsalkenyloxy or COOH; especially hydrogen or C,-C,alkyi;

R +2 is hydrogen or C-Cgalkyl;

Rs is hydrogen or C:-C,alkyl;

D is C-Cgalkylene or C4-Cioalkylene interrupted by O; and T~' is Cx-Csoalkylene or Cx-

Csoalkylene interrupted by one or more oxygen atoms; ard all other symbols are as defined for formula | above.

T' may also be alkylene interrupted by Cs-Ci.cycloalkylene o.r said cycloalkylene, especially cyxclohexylene, substituted by alkyl and containing 20-50 carbon atoms in total.

in the oligo- or polyester of formula (lil), each of the divalent structural units identified by the indices x and z bond to the structural unit -O-D- identifised by the index y, and/or to an end group R¢2 or ORqa. in compounds of the formula (1), x is preferably from the range 2-50, more preferably from the range 2-20, especially 4-12; the number of triazine smoieties of the formula Il to diacid residues T preferably ranges from about 1 : 3 to about ~10:1, more preferably from about 1 : 1 to about 5: 1. In compounds of the formula (Ill), each of x and z are preferably from the range 1-16; more preferably, x is from the range 4-10 amd z is ranging from 2-12,

Oligomeric or polymeric esters of the invention such as #hose of formula | or lil usually have a molecular weight within the range 1000 to 50000 g/mol, more preferably 1500 to 20000 g/mol, most preferably 2000 to 10000 g/mol (number average Mn as determined by gel permeation chromatography GPC).

Alkyiphenyl is alkyl-substituted phenyl; C;-Cialkylphenyl embraces examples such as methylphenyl (tolyl), dimethylphenyl (xyiyl), timethylphery (mesityl), ethylphenyl, propyiphenyl, butylphenyi, dibutyiphenyl, pentylphenyl, lmexylphenyl, heptyiphenyi and «<Octylphenyl.

Phenylalky! is phenyl-substituted alkyl; CC phenylalkyl embraces examples such as

Benzyl, a-methyibenzyl, a-ethylbenzyl, a,o~dimethyibenzwyl, phenylethyi, phenylpropyl, phenylbutyl and phenylpentyl.

Alkyl interrupted by O can generally comprise one or mor-e nonadjacent oxygen atom(s).

Preferably, a carbon atom of an alkylene chain such as D# or T' bonds to not more than 1 . heteroatom.

VWWithin the scope of the stated definitions, the alkyl radicals are branched or unbranched alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethyibutyl, n--pentyl, isopentyl, 1-methylpentyl, 1,3-dimsthylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, is-oheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-mettwylheptyl, n-octyl, 2-ethylhexyl,

1,1,3-trimathythexyi, 1,1,3,3-tetramexthyipentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexcyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.

Alkylene such as of L or D derives from such alkyls by abstraction of an hydrogen atom.

Within the scope of the stated definitions, the alkenyl radicals include allyl, isopropenyi, 2- butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl; n-oct-2-enyl, n- dodec-2-enyl, isododecenyl, n-octaciec-2-enyl and n-octadec-4-enyl.

The heavy chains of T, e.g. alkylene groups of T', may have a certain molecular distribution around their main component. Ranges may be, for example, from 22-26, 28-32 or 34-38 C- atoms. It is however also possible that broader ranges are used such as for example from to 40, from 30 to 50 or from 30 to 40 carbon atoms, each for T" in total.

Since the educts for preparing a cormpound of formula (I) or (lil) are commercial products, they may vary within certain specifications. This is particularly the case for high molecular weight diacids from which the T growips are derived, when T is Cx-Cgalkylene (which may be interrupted as described above).

Commercially available diacids or diacid esters may also contain small amounts of chains below Cz. Therefore mixtures of cornpounds wherein T is a mixture containing up to 10% of diacyl chains below 20 carbon atom.s and 90 to 100% of diacyl chains between 20 and 60, particularly between 20 and 40 carbon atoms are also subject of the invention. Percentage is weight percent, based on the totall mixture.

The compounds of formula (1) and (1 Il) or precursors thereof can be prepared in analogy to methods described in WO 03/00455 7 or publications mentioned therein (e.g. EP-A-434 608, H. Brunetti and C.E. Lithi, Helw. Chim. Acta 55, 1566 (1972), US-3118887, EP-A- 165608). (Poly)esters of formula (I) or (lll) are advantageously prepared starting from tris-aryl- triazines containing 2 carboxylic acid groups or suitable derivatives thereof such as acid chloride, anhydride or especially ester groups. Such educts or their homologues are

~g- described, inter alia, in US-4826978, US-5736597 (see e.g. columns 11-13), US-5686233,

US-5959008 (see e.g. col. 30, line 35, until col. 31, line 11) and a further educt of the same type, e.g. aliphatic, cycloaliphatic or aromatic: dicarboxylic acid or derivative thereof containing the group T. For esterification, the dicarboxylic educts are preferably reacted according to methods known in the art with suitable amounts, e.g. 0.9 — 1.1 mol per mol dicarboxy! or equimolar amounts, of a diol HO-D-OH; preferred diols include glycol, glycerine, various polyethylene glycoles, or ox,o-dihydroxyalkanes of various chain lengths such as butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, tricdlecanediol, pentadecanediol, octadecanediol, eicosanediol, and mixtures thereof. Reactions can be carried out with or without addition of further components such as solvents (e.g. aliphatic alcohols, ethers, aromatic hydrocarbons or halogenated hydrocarbons such as chlorobenzene, or solvent mixtures) or catalysts, e.g. transesterification catalysts such as mineral or organic (Lewis or Broensted-type) acids or bases. In case that no additional solvent is used, an educt such as the diol or a suitable ester of a dicarboxylic acid may be used in excess and serve simultaneously as a solvent.

Temperature and pressure are usually not critical, thus, the reaction often is carried out at temperatures in the range -5°C to 200°C, e.g. between 10 and 170°C, and pressure close to 1 atmosphere, e.g. 10* to about 10° Pa, with or without presence of oxygen, e.g. under nitrogen or argon. . Present invention also pertains to an oligoester ar polyester which is obtained by reacting a tris-aryl-triazine of the formula V }

R 10

Ra Vv)

Rea

R i SN

R —0-Y—|—0 R, o—}v—o—r 12

Rs Re and a compound of the formula R2~0-T-O-R2, where Y is CO and all other all symbols are as defined above, with a diol HO-D-OH.

Claims (17)

Claims

1. An oligoester or polyester formula (I) -[A-O-D-O}, 0 in which x is a number from 1 to 50; A is a group of the formula (ll) R 10 (in Ri Ris © R, NTN I N ? jon 1 ; —C—1—0 R; o-L-C— or has one of the meanings given for T; D is C4-C+2 alkyle=ne or said alkylene substituted by OH or interrupted by O ar both substituted by OH and interrupted by O; L is C4-Cysalkylerne; Cs-Ciacycloalkylene; Cs-Cisalkenylene; or one of said re sidues substituted by ph enyl, C~-Cqsalkylphenyl, Cs-C.cycloalkyl, OH, halogen, Ci—Cigalkoxy, Cs- C2cycloalkaxy, Cs-Cysalkenyloxy, COOH; the R, are independently of each other H, OR; or OH, with the proviso that &xt least one of R;orRyzis OH; the R; are independently of each other hydrogen, C-C+zalkyl or a radical of formula -L-CO-0O-Rg; Ry is H, C4-Cysalkcyl, C-Cyzhydroxyalkyl; Ryo is hydrogen, €,-C,alkyl, Cl, phenyl or a group -OR;; Ry is hydrogen or methyl; Ry; is hydrogen, methyl, OH or ORy; and T is the divalent axcyi residue of an aliphatic or cycloaliphatic dicarboxylic actd of 13 to 60 carbon atoms; and which contains at least one moiety of formula (I) and at least one moiety T.

2. Oligoester or polyester of claim -1, wherein D is C4-Cyoalkylene or C4-Cyoaltkyleme interrupted by O; L is C4-C alkylene; T is the divalent acyl residue CO-T-CO, wherein T' is Cz-Csoalkylene or Cx-Cxoalkylene interrupted by one or more oxygen atoms; or alkylene interrupted by Cs-Cr.cycloalkylene or by Cs-Ciocycloalkenylene, each of which is unsubstituted or substituted by alkyl, and T contains 20-50 carbon atoms in total; the R; are hydrogen or methyl; Ryo is hydrogen, methyl! or a group -OR;; R44 is hydrogen; Rua is hydrogen, OH or methyl.

3. Oligoester or polyester of claim 1 conforming to the formula (ill) R 10 Ra J rrfoy Fo R of yTto-o-Ho-oomcoko— 2 Ry = Ix (1) in which x is a number from 1 to 20; the number y is at least 1 and ranges from (x + z— 1) to (x + z + 1); z is a number from 1 to 20; and Rs is hydrogen, C-Ci,alkyl; Cs-Ci2-cycloalkyl; C-Ci.alkenyl; phenyl; C;-Cyqalkylphenyi; C;- Cizalkyl substituted by phenyl, OH halogen; C-Cisalkoxy, Cs-Ci2cycloalkoxy, Cs- Cisalkenyloxy or COOH; especiallys hydrogen ar C+-Caalkyl; Ry2 Is hydrogen or C;-Cgalkyl; Rs is hydrogen or C,-C,alkyl;

D is C4-Calkylene or C,-Cyealkylene interrupted by O; and T' is Cx-Csoalkylene or Cxo-Cssalkylene interrupted by ore or more oxygen atoms; or alkylene interrupted by Cs-Ci.cycloalkylene or by Cs-Ci=cycloalkenylene, each of which is unsubstituted or substituted by alkyl, while T" containing 20-50 carbon atoms in total; and all other symbols are as defined for formula | of claim 1.

4. Oligoester or polyester of claim 1, wherein x is from the range 2-50, and the number of triazine moieties of the formula [1 to divalent acid residues T is between 1 to 3 and 10to 1.

5. Oligoester or polyester which is obtained by reacting a tris-aryl-triazine of the formula (V) R 10 Ri ) Ris R, N7SN Rg Rs R j—O—Y—}—0 R; o—v—o—r 2 Rs Ry and a compound of the formula R;-O-OC-T"-CO-0-R+2 with a diol of the formula HO-D-OH, where Y Is CO and all other all symbols are as defined For formula (lll) of claim 2.

6. Composition protected against the permeation of ultraviolet radiation comprising (a) an arganic polymer material and (b) at least one oligoester or polyester of formula (I) of claim 1 or a mixture thereof.

7. Composition of claim 6, which is a transparent plastic: container or film or multilayer film.

8. Composition of claim 8 wherein the organic polymer material is a thermoplastic polymer, especially a polyolefin, a polyester, a polyvinylalcohol, aa polyvinylacetate, a polylactone or a polycarbonate.

9. Composition of clairn 6 wherein the organic polymer material is a film of 10 p to 200 pn thickness or a plastic container of 200 pu to 1000 p wall thickness, and containing the compound of formula €l) in an amount of from 0.005 % to 10 %, based on the weight of the organic polymer material.

10. Composition of claim 6 containing a further component selected from phenolic antioxidants, sterically hindered amines, further UV absorbers, phosphites and phosphonites, alkali metal salts and alkaline earth metal salts of higher fatty acids, fillers, metal oxides, hydrotal«ites, oxygen scavengers, acetaldehyde scavengers, plasticisers, clarifiers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, processing aids, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

11. A method of protecting a transparent plastic container or film and its contents against the deleterious effects: of ultraviolet radiation, which method comprises incorporation of zan oligoester or polyester of claim 1 into said plastic container or film.

12. Use of an oligoesteer or polyester of claim 1 for protecting a transparent plastic contai ner or film and its contents against the deleterious effects of ultraviolet radiation.

13. A method of prevesnting photooxidation of packed food, characterized in that the food is sealed in a transparent plastic container or film or multilayer film of claim 7, especially a package or container &omprising a transparent sheet or film, and the package further contains an oxygen scavenger.

14. A method of preve=nting photooxidation of packed food, characterized in that the food is sealed in a package ow container comprising a transparent sheet or film made from plastic material, wherein the plastic material contains a UV absorber selected from the hydroxyphenyl-s-triazimes, 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenoness, and mixtures thereof, and the package further cantains an oxygen scavenger.

15. Method of claim 14, wherein the plastic material comprises a polyolefin, a polyester, a polyvinylaicohol, a polwvinylacetate or a polycarbonate.

16. Method of claim 14, wherein the UV absorber is used in an amount from 0.01 gto 10g per square meter of transparent sheet or film.

17. Method of claim 14, wherein and the oxygen scavenger is an additive based on an oxidizable iron or iron compound.