DE2309105A1 - MEANS FOR IMPROVING THE GAS RESISTANCE AND THE POLYMERIZED COMPOSITIONS CONTAINING THIS - Google Patents

Description

"Agents for improving the gas resistance and polymer compositions containing the same"

The invention relates to a means for increasing the gas resistance of polymers, i.e. an agent with which the decomposition by gases is inhibited, the polyurethanes and Cellulose acetates imparts lasting superior gas resistance without sacrificing the desirable properties these polymers are adversely affected, as well as gas-resistant polymer compositions containing a polyurethane or contain a cellulose acetate and the agent for increasing the gas resistance.

The invention particularly relates to an enhancement agent

309836/1189

ORIGINAL INSPECTED

the gas resistance of polyurethanes and cellulose acetates, which is a triazine derivative of the general formula I.

A-X if 1 Tl Y-B

• I ⁶ 2 Il ·

(I)

NH-R

includes where

X and Y, which can be identical or different, denote nitrogen, sulfur or oxygen atoms, where
when X represents a nitrogen, η represents 1, η represents zero be-sulfur atom or an oxygen atom, η represents zero, when Y represents a nitrogen atom, m represents 1
and when Y represents a sulfur atom or an oxygen atom, m represents zero,

A, B and R are alkyl groups with 1 to 18 carbon atoms,
Alkenyl groups with 3 to 18 carbon atoms, cycloalkyl groups with 3 to 6 carbon atoms, benzyl groups, substituted benzyl groups, cyanoalkyl groups with 3 to 5
Carbon atoms, dialkylamino groups with 2 to 8 carbon atoms, phenylamino groups, phenyl groups and / or substituted phenyl groups, with the proviso that A, B and R do not simultaneously denote phenyl groups or substituted phenyl groups and R when X and Y represent oxygen or sulfur atoms, denotes no phenyl group or substituted phenyl group, and

D and E are hydrogen atoms or groups for the substituents A, B and R represent the meaning given, where the

309836/1189

Groups A and E or groups B and D together with X and Y can form a heterocyclic ring with 2 to 5 carbon atoms, where v / enn the groups E and D of hydrogen are different groups, the group R does not represent a phenyl group or substituted phenyl group, if only the group E represents a hydrogen atom, both the group A and the group R are not phenyl groups or substituted phenyl groups and where, if only the group D represents a hydrogen atom, both the group B and the group R do not represent phenyl groups or substituted phenyl groups and where the sum of the carbon atoms contained in groups A, B, D, E and R is at least 10..

The invention also relates to a gas-resistant polymer composition, which is a polyurethane or a cellulose acetate and not more than 10 wt .- # of the triazine derivative defined above, based on the weight of the polymer contains.

It is known that the increased concentrations of nitrogen monoxide present in the air (referred to as nitrogen oxide gas will) pose an air pollution problem. Recently, it has been found that nitrogen oxide gas gradually and leads to yellowing of polyurethanes or deteriorates the physical properties of this material or causes discoloration or fading of colored polyurethanes or cellulose acetates. This phenomenon is referred to as "gas-fading".

The agent according to the invention for increasing the gas resistance, i.e. the agent with which the decomposition by the action of gas is inhibited, makes it possible to avoid the undesirable "gas decomposition" phenomenon caused by in Nitrogen oxide gas present in the air is to be prevented.

309836/1189

Some of the compounds encompassed by the general formula I have already been used as active ingredients for in agriculture and fungicidal or bactericidal agents used in horticulture. Some other materials of this Kinds are known as effective ingredients of herbicides, while other substances of this kind are known as agents for improvement the dyeability of polyolefins are known. However, it has not yet been suggested to those defined above To use triazine derivatives of the general formula I for polyurethanes and cellulose acetates, which are related to Their chemical structure is very different from that of polyolefins. Furthermore, there is an improvement in gas resistance poses no problem in the development of the polyolefins, so that the excellent ones increase the gas resistance Effects of the compounds of general formula I on polyurethanes and cellulose acetates are not to be expected was.

Various means have been proposed by which the gas decomposition of polyurethanes and cellulose acetates produced by nitrogen oxide gas are said to be inhibited, but none of these materials was well compatible with these polymers and led to a long-term, superior gas resistance, without the desirable properties of these polymers being adversely affected.

For example, in order to prevent the yellowing or bleaching of polyurethanes by nitrogen oxide gas, high molecular weight fatty acids such as stearic acid or eehenic acid (see Japanese Patent Publication No. 22626/69), higher alcohols such as n-decyl alcohol or stearyl alcohol (see U.S. Pat published Japanese Patent No. 31804/69), sulfur-containing, higher-molecular fatty acid esters, such as lauryl thioethyl alcohol, dilauryl thiodipropionate or distearyl thiodipropionate (cf. the published Japanese patent

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note 25909/69), higher molecular weight fatty acid amides such as stearic acid amide or palmitic acid amide (see published Japanese patent application 27874/69), ureas such as phenylurea or phenylthiourea (see published Japanese patent application 19190/67), adipic acid dihydrazide or 2,4-bis-hydrazino-6-dimethylamino-s-triazine (see. Japanese published Patentanm. 25828/68), hydrazides such as adipic acid-bis-N, N-dimethyl (see. Japanese published Patentanm. 27348 / 65), semicarbazides such as 1,1-dimethylstearyl-semicarbazide (cf. the published Japanese patent application 16793/66), phosphite esters such as tridecyl phosphite or trilauryl thiophosphite, either as such or together with 2,4,6-tris-ethyleneimino- 8-triazine or 2-phenyl-4,6-diamino-2-triazine (see Published Japanese Patent Nos. 9828/69, 29672/68 and 28625/68), hydroxyphenyl compounds such as 1,3,5-trimethyl-2 , 4,6-tris- (3 »5-di-tert-butyl-4-hydroxybenzyl) -benzene (cf. published Japanese patent application 16856/68) and polymeric compounds such as poly (di-isopropylaminoethyl methacrylate) or poly (diethylaminoethyl methacrylate) (cf. the published Japanese patent application no. 2904/71) used. However, all these connec tions lead to the disadvantages indicated above and are not suitable means for increasing the gas resistance of polyurethanes.

On the other hand , to inhibit the discoloration or fading of cellulose acetates, in particular colored materials of this type, in particular primary, secondary or tertiary amines, hydroxylamines such as triethanolamine, heterocyclic compounds such as phenylmorpholine, 1,4-dibenzylmorpholine or N, IJ ¹ -diphenylpiperazine and Compounds such as thiourea, melamine, N-acetylmelamine, N-phenylmelamine, 2,4-bis-anilino-6-amino-s-triazine or triphenylmelamine are used. These cellulose acetate inhibitors are generally water-soluble, have a low affinity for

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Fibers and in most cases reduce the wet fastness or the lightfastness of the dyeings. So so far no inhibitor of practical fourth has become known. Furthermore, the melamines containing NH 4 groups are generally difficult to use in organic solvents, such as acetone or methylene dichloride and also have a strong affinity for water. As a result, before the Processing are not mixed with the polymer and result if they are used in the aftertreatment, not to have a lasting effect.

When these agents are used to increase the gas resistance of cellulose acetates for polyurethanes, the durability and the poor durability result Compatibility and in certain cases unwanted reactions with isocyanates arise or it stalls (especially in the case of the tertiary amines) does not increase the gas resistance. Certain other materials of this Type reduce the light resistance of the polymers and worsen the physical properties of the processed polymer.

Tetrakis [methylene-3- (3 ', 5'-tert-butyl-4 ^f -hydroxyphenyl) propionate! Methane (Irganox 1010, CIBA GEIGY AG) or 2- (2', which is known as an ultraviolet light absorber) is known as an antioxidant. -Hydroxy-3 ^l , 5'-diisoamlyphenyl) -benztriazole (Tinuvin-328, CIBA GEIGY AG) are also used for polyurethanes, but these compounds do not cause an increase in the gas resistance , but rather are detrimental. The triazine antioxidants such as 6- (4 ^f -hydroxy-3 ', 5 ^l -di-tert-butylanilino) -2,' 4-bisoctadecylthio-1 _f 3,5-triazine (irganox 565, CIBY GSIGY AG) has no effect on the decomposition through the action of gas.

It is believed that the higher molecular weight fatty acids that

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The higher-molecular alcohols, the higher-molecular fatty acid amides and the higher-molecular fatty acid esters, which have been given above , have no positive effect against the yellowing or bleaching of polyurethane due to the action of nitrogen oxide gas due to their chemical structure. However, as can be seen from the examples given below, they then have an inhibiting effect when they are incorporated into a polyurethane and processed into a film . This is possibly due to the fact that these compounds bleed out of the surface of the film because of their poor compatibility with the polyurethane and thereby seal off the polymer from the surrounding atmosphere. However, if such a compound is incorporated into a polyurethane and the polymer is spun into fibers or dyed, an effect of this kind is not shown. Furthermore, these compounds are largely ineffective with respect to cellulose acetates.

It has now been found that the triazine derivatives of the general formula I are polyurethanes and cellulose acetates can impart increased, permanent gas resistance without the desirable properties of these polymers be affected. It was also found that the triazine derivatives of the general formula I to any Point in time between the manufacture of the polyurethanes and the final treatment of the molded polyurethane articles, e.g. before, during or after the production of the polyurethanes or during or after the molding of the polyurethanes or may be incorporated during or after the dyeing of the molded articles. It was also found that this Triazine derivatives give these polymers excellent gas resistance and good affinity for these polymers show, can be incorporated into the polymers in a variety of ways and with the improved properties have better durability.

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It is therefore an object of the invention to provide an agent for increasing the gas resistance of polyurethanes and cellulose acetates or to provide a means for inhibiting the gas-induced decomposition of these materials, which gives them excellent long-term gas resistance and that with any equipment can be incorporated into these polymers at any desired time.

Another object of the invention is to provide gas resistant polymer compositions provide a polyurethane or a cellulose acetate and one incorporated therein Contain inhibitor of the type mentioned.

The agent according to the invention for increasing the gas resistance comprises the triazine derivative of the general formula I and contains at least one, preferably two, more preferably three or more —NH groups in the molecule. Analogous triazine derivatives, which do not contain an -NH bond, such as 2,4,6-tris-dibutylamino-s-triazine, 2,4,6-tris-morpholino-s-triazine, 2,4,6-trisdiallylamino-s-triazine or Z-diethylamino- ^ dipropylamino-6-dibutylamino-2-triazine are hardly able to achieve the effects of the present invention in terms of increasing the gas resistance to unfold.

The groups X and Y of the general formula I are identical or different and represent nitrogen, sulfur or As can be seen from the general formula I, η is 1 when X represents a nitrogen atom and zero when X is a sulfur atom or an oxygen atom, while m is 1 when Y is a nitrogen atom represents and represents zero when Y represents a sulfur atom or an oxygen atom.

The groups A, B and R of the general formula I have the meanings given above. Examples of the sub-

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substituents of the substituted benzyl groups A, B or R the general formula I are chlorine atoms and methyl groups. Examples for the substituents of the substituted phenyl groups A, B and R are halogen atoms, such as chlorine or bromine atoms, Methyl groups, ethyl groups, nitro groups, methoxy groups and ethoxy groups.

The groups D and E of the general formula I represent hydrogen atoms or groups as defined for groups A, B and R, with groups A and E or the Groups B and D together with groups X and Y form a heterocyclic ring with 2 to 5 carbon atoms can.

As already mentioned above, the compounds of general formula I are subject to the restrictions indicated below Are defined:

a) A, B and R should not mean phenyl groups or substituted phenyl groups at the same time,

b) R should not represent a phenyl group or substituted phenyl group if X and Y are oxygen atoms or sulfur atoms (i.e. when both X and Y are oxygen atoms or sulfur atoms when X is a Sulfur atom and Y is an oxygen atom or if Y is an oxygen atom and Y is a sulfur atom),

c) R should not represent a phenyl group or substituted phenyl group if the groups E and D are different from hydrogen are,

d) the groups A and R should not represent any phenyl groups or substituted phenyl groups at the same time, if only the group E represents a hydrogen atom, the

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Group D is different from hydrogen,

e) the groups B and R should not have any phenyl groups at the same time or substituted phenyl groups when only the group D represents a hydrogen atom (i.e. the group E is other than hydrogen) and

f) the sum of the carbon atoms of groups A, B, D, E and R at least 10 (usually 10 to 50, preferably 12 to 40, more preferably 14 to 30).

Examples of compounds that do not correspond to the o _#-lived provisos are:

Connections that do not meet requirement a):

2,4,6-tris-phenylamino-s-triazine, 2 _{tons of} 4,6-tris- (p-anisidino) -s-triazine and 2,4,6-tris- (o-anisidino) -s-triazine.

Connections that do not meet requirement b):

2,6-bis-phenoxy-4-phenylamino-2-triazine and 2,6-bis-phenylthio-4-phenylamino-s-triazine.

Connections that do not meet requirement c):

2,6-bis-dibutylaraino-4-phenylamino-s-triazine, 2,6-bis-morpholino-4-phenylamino-s-triazine, 2,6-bis-ethyleneimino-4-phenylamino-s-triazine, 2,6-bis-dibenzylamino-4- (o-anisidino) -s-triazine and 2,6-bis-diallylamino-4- (p-chlorophenylamino) -s-triazine. ■

Connections that do not meet the requirements d) or e):

2,4-bis-phenylamino-6-dibutylamino-s-triazine, 2 _t 4-bis- (p-chlorophenylamino) -6-diallylamino-s-triazine,

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2,4-bis (p-toluidino) -6-morpholino-s-triazine and 2, ^ - bis-phenylamino-e-piperidino-s-triazine.

Connections that do not comply with requirement f):

2,4,6-tris-methylamino-s-triazine, 2,4,6-tris-ethylamino-s-triazine, 2, ^ -Bis-methylamino-ö-butoxy- s-triazine, 2, A-bis-ethylamino-e-methoxy-s-triazine, 2,4-bis-allylamino-6-methoxy-s ~ triazine, 2,4-bis-propylamino-6-methylthio-s-triazine and 2-methylamino-4-propylamino-6-methylthio-s-triazine.

The compounds given above, which represent only a few examples, do not show the outstanding ones Gas resistance increases the effects of the agents according to the invention or do not show this effect at all. In particular show the compounds which do not meet requirement f), i.e. have low molecular weights, extremely poor durability.

Of the compounds of general formula I are the compounds of the following general formula Ia

AX <T 1 Γ ^ N - B

(Ia)

preferred, wherein

X represents a nitrogen, sulfur or oxygen atom, where n, when X is a nitrogen atom, is 1 or zero,

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when X represents a sulfur atom or an oxygen atom,

A, B and R are alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 3 to 18 carbon atoms, cycloalkyl groups with 3 to 6 carbon atoms, benzyl groups, represent substituted benzyl groups, cyanoalkyl groups with 3 to 5 carbon atoms, dialkylamino groups with 2 to 8 carbon atoms, phenylamino groups, phenyl groups or substituted phenyl groups, with the proviso that the groups A, B and R are not simultaneously a phenyl group or a substituted phenyl group,

and D and E represent hydrogen atoms or groups of the type specified for A, B and R, where the groups A and E or the groups B and D together with the group X and the nitrogen atom can form a heterocyclic ring having 2 to 5 carbon atoms, where the group D is different from hydrogen and the group R is not a phenyl group or substituted phenyl group when X is a sulfur atom or an oxygen atom, the group D is a hydrogen atom and the groups B and R are not simultaneously phenyl groups or substituted phenyl groups when X is Represents a sulfur atom or an oxygen atom, the groups E and D are different from hydrogen and the group R does not represent a phenyl group or substituted phenyl group, if X represents a nitrogen atom, the groups A and R do not simultaneously represent phenyl groups or substituted phenyl groups if only the group E represents a hydrogen atom and the groups B and R are not Ph represent enyl groups or substituted phenyl groups, and only the group D denotes a hydrogen atom, the sum of the number of carbon atoms of the groups A,

B, D, E and R is at least 10.

Of the compounds represented by the general formula Ia, those represented by the following general formula Ib

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(Ib)

NH-R

compounds shown new compounds, wherein

X represents a nitrogen, sulfur or oxygen atom, where n, "when X represents a nitrogen atom 1 and when X represents represents a sulfur atom or an oxygen atom means zero,

A is an alkyl group having 1 to 18 carbon atoms, a Alkenyl group having 3 to 18 carbon atoms means a cycloalkyl group having 3 to 6 carbon atoms, a benzyl group, a substituted benzyl group, a cyanoalkyl group having 3 to 5 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a phenyl group or represents a substituted phenyl group,

R represents a group of the formula -N (R) ~, wherein the two Groups R, which can be identical or different, denote alkyl groups with 1 to 4 carbon atoms,

E is a hydrogen atom or one with respect to the group A represents a defined group, where the groups A and E together with X form a heterocyclic ring with 2 to 5 Carbon atoms and v / orin denote the sum of the carbon atoms contained in groups A, E and R at least 10 is.

The compounds of the general formula Ib can easily be prepared by methods known per se. she can e.g. be prepared as follows:

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Starting from cyanuric chloride or cyanuric bromide, the group of the formula is carried out first

A-X- (E)

whereupon the -NHR group is introduced. If you first carries out the introduction of the -NHR group, the desired compounds cannot be obtained. It is therefore necessary first the group of the formula

A-X-

to introduce. In particular, one mole of cyanuric chloride is dispersed in a medium such as acetone, methyl ethyl ketone or dioxane at a temperature of not more than 5 ^° C. and a fine dispersion of cyanuric chloride is produced by adding ice water. One mole of a primary or secondary amine (e.g. octylamine, laurylamine, stearylamine, cyclohexylamine, benzylamine, p-chloroaniline, 2,5-dichloroaniline, p-toluidine, o-toluidine, dibenzylamine, diphenylamine or dicyclohexylamine) is then added to this mixture, a compound containing hydroxyl groups (for example pentachlorophenol, p-tert-butylphenol, o-cresol, phenol, 2,4-dichlorophenol or lauryl alcohol) or a compound containing a mercapto group (for example octyl mercaptan, lauryl mercaptan, stearyl mercaptan, benzyl mercaptan or phenyl mercaptan) and leads the reaction at a temperature of not more than 5 ⁰ C by using as acid binding agent IJatriumhydroxyd, sodium carbonate, ITatriumbicarbonat or a water soluble organic tertiary Arain used. The reaction product is filtered off and washed with water, a mono-

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substituted 4,6-dichloro-s-triazine is obtained. Since it is desirable for practical use to obtain this mono-substituted product in the form of crystals, it is suitably rings containing compounds instead of aliphatic Verbinungen as amines, hydroxyl groups and mercapto compounds containing a · One mol of the resulting mono-substituted 4,6-W.chlor- s- triazines is nioht more dispersed in a low molecular weight alcohol such as methanol or ethanol at a temperature of 5 ⁰ C (wherein the amount of alcohols preferably about 5 to 7 times as large as the 1st of triazines). 2.5 times the molar amount of a dialkylhydrazine, such as asym-dimethylhydrazine or asym-diethylhydrazine, is added dropwise with stirring and the mixture is kept at a temperature of not more than 15 ° C. Since a considerable amount of heat develops, the addition should be carried out with caution, whereupon, after the addition is complete, 2 moles of sodium hydroxide or sodium carbonate in the form of an approx. 10 subsequent aqueous solution are added dropwise as an acid-binding agent. In the course of the reaction, the reaction mixture becomes cloudy, which indicates the progress of the reaction. After finishing the alkali addition, the mixture is heated to approximately 40 ⁰ C and stir for 1 hour. While the low molecular weight alcohol is stripped off under reduced pressure, water is added. The reaction product is then obtained in the form of crystals. By cooling, filtering off and washing with water, a pure product is obtained in a yield of 75 to 90% , which can be used directly as an agent for increasing the gas resistance. If necessary, the product is reprecipitated or recrystallized for further purification. A compound of the general formula Ib can easily be prepared in this way.

If you first 2 moles of the dialkyl hydrazine with 1 mole of cyanuric chloride converts, it is not possible to use a triazine derivative that has reacted with two dialkylhydrazine residues with good

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Produce yields, which is possibly due to the fact that the hydrolysis of the cyanuric chloride is facilitated.

The compound of the general formula Ia can easily be prepared using procedures known per se will. Quite generally, as in the case of the substitution reaction of cyanuric chloride, this is successively combined with compounds increasing reactivity implemented, whereby three substitution reactions can be carried out v / earth. In technical It is preferred to use water-soluble materials and the products in the form of water-insoluble ones Obtain compounds in the course of the substitution reaction. In some cases, water-insoluble materials remain, that have not reacted back and lead to a deterioration in the purity of the end product.

The substitution products obtained differ markedly in their physical properties depending on the nature of the substituents Properties. In general, a substitution product has three or two identical substituents has, i.e. has good symmetry, suitable crystallinity and a suitable melting point and will preferably used according to the invention. Yfenn all three substituents are different from each other, the product obtained generally shows poor crystallinity and a low melting point, and in certain cases is obtained in the form of a liquid. Y / they still own the Products whose substituents are cyclic (aromatic or alicyclic) have higher melting points and better crystallinity than products whose substituents are aliphatic.

The compounds of the general formula Ia in which the group X denotes an —NH group and the group D denotes a hydrogen atom show superior crystallinity. Compounds into which oxygen, sulfur or nitrogen atoms were introduced, show a poorer crystalline

309836/1 1 89

did and lower melting points than the compounds mentioned above, However, they have good solubility in organic solvents, so that these compounds are also called Can use means to increase the gas resistance.

The yield of the triazine derivatives is 70 to 95% _t wherein one receives the products with good symmetry in which three or two substituents are identical with yields of 80 to 95%. The products in which the three substituents are different from one another have relatively low melting points and are only obtainable with relatively low yields of 75 to 85%.

There is a general tendency that the yield with which the compound of the general formula Ia can be obtained decreases in the following series: ~ NH-, -NC, -S-, -O-. Farther the alicyclic and aromatic substituents lead to higher yields than the aliphatic substituents.

With regard to the structure of the triazine derivatives used according to the invention and the effect with regard to the increase the gas resistance it can be said that the triazine derivatives, in which the substituents are a combination of strongly hydrophobic groups, such as stearyl groups, and less hydrophobic groups Groups, such as methyl or ethyl groups, are preferred over the compounds in which the three substituents are present have the same molecular chain and structure. In other words, it is desirable that the molecules in are oriented in a different way.

In general, the presence of an -NH group is considered to be Groups X or Y in terms of the gas resistance increasing effect the most important of the compound of the general formula Ia. As a result, the effect of the enhancement decreases the gas resistance to the extent to which the number of

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NH groups decreases from 3 to 2 to 1. However, if the structure as a whole is considered, the nitrogen, oxygen and sulfur atoms are of great importance and play an additional role together with the NH group. Furthermore, these groups improve the solubility of the product and lead to an orientation of the molecules . As already mentioned, the triazine derivatives in which an aromatic group is directly bonded to the three NH groups have no effect on polyurethanes and are excluded according to the invention. Furthermore, triazine derivatives in which the NH ₂ "" G ^ru PP ^e is bound directly to the triazine ring, such as melamine or monosubstituted melamines, are easily soluble in water, slightly soluble in organic solvents and react undesirably with isocyanates. Furthermore, they show only a slight effect in increasing the gas resistance and show poor compatibility with polyurethanes and cellulose acetates.

The compounds of general formula I are described below classified according to various combinations of X and Y.

X and Y each mean nitrogen atoms:

(D

NH-R

Examples of the triazine derivatives of the formula I are in 'the summarized in the following table I:

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TABLE I.

Ver
binding
No. links A. G r u ρ pen E. R. Enamel
or
boiling point
( ⁰ C) 1 2,4-bis-benzylamino-6-stea-
ryl-amino-s-triazine Benzyl B. D. H Stearyl 87-90 2 2,4-BiS-BlIyIBmInO-O-CyCIo-
hexylamino-s-triazine Allyl Benzyl H H Cyclohexyl 204-206 CJ
O
act 3 2-butylamino-4-anilino-6-
hexylamino-s-triazine Butyl Allyl H H Hexyl glassier
Pestilence 1836 4th 2-propylamino-4-butylamino
6-octylamino-s-triazine Propyl Phenyl H H Octyl ι
200 - 205 / ^
0.5 mm Hg » / 1189 5 2-hexylamino-4-anilino-6-
(p-toluidino) -s-triazine Hexyl Butyl H H p-toluidino glassier
Solid 6th 2-hexylamino-4-anilino-6-
benzylamino-s-tri azine Hexyl Phenyl H H Benzyl 260 - 265 /
0.4 mm Hg 7th 2,4,6-tris-cyclohexylamino-
s-triazine Cyclo
hexyl Phenyl H H Cyclohexyl 195 - 196 8th 2,4,6-tris-benzylamino-s-
triazine Benzyl Cyclo
hexyl H H Benzyl KJ
155-158 CJ
O • 9 2,4,6-tris-phenylhydrazino
s-triazine Phenyl
amino Benzyl H H Phenylamino <D
240 - 241 ^ Phenyl
amino H

TABLE I continued:

link

links

groups

10 2,4,6-tris-allylamino-s
driazine Allyl Allyl H H Allyl CO
O
CO 11 2,4-bis-stearylamino-6-
ethylamino-s-triazine Stearyl Stearyl H H ethyl 1836 12th 2,4-bis-allylamino-6-
stearylamino-s-triazine Allyl Allyl H H Stearyl / 1189 13th 2,4-bis-stearylamino-6-
asyra-dimethylhydrazino-s-
triazine Stearyl Stearyl H H Dimethyl
amino 14th 2- (p-chloroanilino) -4,6-bis-
asym-dimethylhydrazino-s-
triazine p-chlorine
aniline Dimethyl
amino H H Dimethyl
amino 15th 2- (2 ^f , 5'-dichloroanilino) -
4,6-bis-asym-dimethylhydra-
zino-s-triazine 2.5 Di
chlorine-
anilino Tuesday
me thyl-
amino H H Dimethyl
amino 16 2- (o-Toluidino) -4,6-bis-
asym-dimethylhydrazino-s-
triazine 0-
Toluidi
no Dimethyl
amino H H Dimethyl
amino 17th 2-cyclohexylamino-4,6-bis-
asym-dimethylhydrazino-s-
triazine Cyclo
hexyl Tuesday
methyl-
amino H H Dimethyl
amino

Melting »

or

boiling point

( ⁰ C)

71-76

93
45

136 -

97 48

123-125

135-139

14f °

Ca> O CO

TABLE I continued:

Ver
binding
No. links A. G r u ρ ρ e η E. R. Enamel
or
boiling point
(° C) - I.
IO 2309 18th 2,4-bis-benzylamino-6-
morpholino-s-triazine Morpho
lino B. D. - Benzyl 185-187 waxy ι
Solid 105 19th 2,4-bis-stearylamino-6-
morpholino-s-triazine Morpho
lino Benzyl H - Stearyl 64 - 66 95-101 20th 2,4-bis-allylamino-6-
morpholino-s-triazine Morpho-
lino Stearyl H - Allyl 75-77 - 21 2,4-bis-laurylamino-6-di-
isopropylamino-s-triazine Iso-
propyl Allyl H Iso-
propyl Lauryl 22nd 2,4-bis-butylamino-6-di-
cyclohexylamino-s-triazine Cyclo
hexyl Lauryl H Cyclo
hexyl Butyl 23 2,4-bis-cyclohexylamino-6-
di butylamino-s-triazine Butyl Butyl H Butyl Cyclo
hexyl waxy
Solid 24 2,4-bis-stearylamino-6-di-
butylamino-s-triazine Butyl Cyclo
hexyl H Butyl Stearyl 127-130 25th 2-ethylamino-4-isopropyl-
amino-6-pip eridino-s-
triazine Pipera-
dino Stearyl H - Isopropyl oil 26th P —'RTi'kvi am i nruiuihewi »wH nrt_ Piperi
dino Butyl H - Hexyl 6-piperidino-s-triazine ltnyl H

TABLE II continued

link
No.

27

28

links

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2-butyl amino-4-hexylamino-6-dibenzyl aminos-triazine

2-dibenzylamino-4,6-bisa sym-dimethylhydrazino-striazine

2-diphenylamino-4,6-bis-

asym-dimethylhydrazino-s-

triazine

2,6-bis-morpholino-4-stearyl-amino-s-triazine

2, ö-bis-niorpholino-A-cy el ohexylamino-s- triazine

2 "6-bis-morpholino-4-benzylainino-s-triazine

2,6-bis-dibutylamino-4-butylamino-s-triazine

2,6-bis-diallylamino-4-benzylamino-s-triazine

G r u ρ ρ e η E. R. Enamel
or
boiling point
( ⁰ C) - A. B. · D. Benzyl Hexyl 250-256 /
0.6 mm Hg Benzyl Butyl H H Dimethyl
amino 135-139 Benzyl Di-
methyl-
amLno Benzyl H Dimethyl
amino 55-56 I.
ro
ro Phenyl Di-
methyl-
amino Phenyl - Stearyl 73-76 ι Morpho
lino Morpho
lino - - Cyclo
hexyl 172-175 Morpho
lino Morpho
lino - - Benzyl 164-166 Morpho
lino Morpho
lino - Butyl Butyl oil Κ>
CJ Butyl Butyl Butyl O Allyl Benzyl glassier
Solid 910 Allyl Allyl Allyl or

TABLE I continued :

Ver
binding
No. links A. G r u ρ ρ e η E. R. Enamel
or
Boiling point -
( ⁰ C) 35 2,6-bis-diethylamino-4-
laurylamino-s-triazine ethyl B. D. ethyl Lauryl waxy
Solid 36 '2,6-bis- (ß-dicyanoethyl-
amino) -4-cyclohexyl-
amino-s-triazine ß-cyano
ethyl ethyl ethyl ß-cyano
ethyl Cyclo
hexyl - 3098 37 2,6-bis-ethyleneimino-4-
stearylamino-s-triazine Ethylene ß-cyano
ethyl ß-cyano
ethyl - Stearyl 81-83 36 / 38 2-piperidino-4-propyl-
amino-6-morpholino-s-
triazine Piperi
dino Ethylene - - Propyl 149-152 1 189 39 2-dibutylamino-4-butyl-
amino-6-diethylamino-s-
triazine ethyl Morpho
lino - ethyl Butyl 130-135 /
0.1 mm Hg Butyl Butyl

40 2,6-bis-morpholino-4- (p-chlorobenzylamino) -s-triazine

Morpho-morpholino lino

p-chloro-165-166 benzyl

One of the groups X and Y means a nitrogen atom and the other means a sulfur atom

A - X

. N 6 2

NS. 3N

■ N - B D

(ID

NH-R

Examples of triazine derivatives of the general formula II are given in Table II below:

309836/1 189

TABLE II

Ver
binding
No. link G r A. u ρ ρ e η D. R. Melting
. Point
( ⁰ C) CJ
O 41 2,4-bis-benzylamino-6-
stearylthio-s-triazine Stearyl B. H Benzyl 92-93 105 42 2,4-bis-benzylamino-6-
laurylthio-s-triazine Lauryl Benzyl H Benzyl 93-95 43 2,4-bis-isopropylamino
6-butylthio-s-triazine Butyl Benzyl H Isopropyl 76-79 44 2,4-bis-ethylamino-6-
(p-methylphenylthio) -s-
triazine p-methyl
phenyl Isopropyl H ethyl 113-115 µ
I. 45 2, ^ bis-ethylamino-ö-
(p-chlorophenylthio) -s-
triazine p-chlorine
phenyl ethyl H ethyl 112-113 46 2,4-bis-allylamino-6-
benzylthio-s-triazine Benzyl ethyl H Allyl 120-125 47 2,4-bis-ο ctylamino-6-
stearylthio-s-triazine Stearyl Allyl H Octyl more vachous
Solid 48 2,4-bis (t-butylamino) ethyl Octyl H t-butyl 165-169 t-butyl

6-ethylthlo-s-triazine

TABLE II continued;

Ver
binding
No. link G r A. u ρ ρ e η D. R. Enamel
Point
( ⁰ C) 2309 49 2,4-bis-asym-dimethyl-
hydrazino-6-laurylthio-
s-triazine Lauryl B. H Dimethyl
amine 56-58 105 50 2,4-bis-asym-diinethyl-
hydrazino-5-stearylthio-
s-triazine Stearyl Dimethyl
amino H Dimethyl
amino 63-67 waxy
Solid 51 2-dibutylamino-4-cyclo-
hexylamino-6-stearyl-
thio-s-triazine Stearyl Dirnethyl
amino Butyl Cyclohexyl waxy
Solid 52 2-IIorpholino-4-lauryl-
amino-6-laurylthio-s-
triazine Lauryl Butyl - Lauryl 53 2-diallylamino-6-benzyl-
amino-6-methylthio-s-
triazine methyl Morpholino Allyl Benzyl Allyl

One of the groups X or Y means a nitrogen atom while the other, an oxygen atom means:

A-O

NB-R

(in)

Examples of triazine derivatives of the general formula III are summarized in Table III below:

309836/1189

TASEEIE III

Connection no.

54

55 56

57 58

59 60 61

link

G r u ρ ρ e n ..

2,4-bis-cyclohexyl-

amino-6-methoxy-s-

triazine

2,4-bis-stearylamino-6-methoxy-s-triazine

2,4-Bi s- (ß-cyano-ethylamino) -6-butoxy-striazine

methyl

Methyl butyl

2,4-bis-allylamino-6-butyl butoxy-s-triazine

2,4-bis-inethallylamino-butyl 6-butoxy-s-triazine

2,4-bis-ethylamino-6-. Phenyl phenoxy-s-triazine

2,4-bis-isopropylamino-o-methyl-6- (o-cresoxy) -s-triazine phenyl

2,4-bis-isopropylamino-2,4-di-6- (2,4-dichlorophenoxy) chlorophenyl s-triazine

Melting point

( ⁰ C)

H cyclohexyl 124-126

H. Stearyl 80-88 H. ß-cyano
ethyl 115-119
ι H Allyl ro
oil? H Methallyl 58-60 H Ethyl" 100-101 H isopropyl 115-116 H isopropyl 110-112 ^ J CD 105

TABLE III continued;

ο «ο co eo

Connection Hi · »

62

63 64 65

66 67 68 69

link

2,4-bis-butylamino-6-

pentachlorophenoxy-s-

triazine

2,4-bis-st e aryl amino-6-hexoxy-s-triazine

2,4-bis-laurylainino-6-butoxy-s-triazine

2,4-bis-asym-dimethylhydrazino-6- (o-cres -) - S-triazine

NS A. P. pen D. R. Butyl Melting Pentachlor
phenyl B. H ( ⁰ C) - -

2,4-bis-asym-dimethylhydrazino-6- (2,4-dichlorophynoxy) -s-triazine

2-dibutylamino-4-laurylamino-2-butoxy-striazine

2-diallylamino-4-cyclohexylamino-6-allyloxys-triazine

2-dimethylamino-6-stearylamino-6-methoxys-triazine

Hexyl Dimethyl
amino H Stearyl waxy
Solid Butyl Dimethyl
amino H Lauryl waxy
Solid o-methyl
phenyl Butyl H Dimethyl
amino 109-115 w
1 2,4-di
chlorine-
phenyl Allyl H Dimethyl
amino - Butyl methyl Butyl Lauryl öi ti
O Allyl Allyl Cyclohexyl —A
glassy °
Solid Oi methyl methyl Stearyl waxy
Solid

X and Y represent sulfur atoms

A-S

S-B

(IV)

NH-R

Examples of triazine derivatives of the general formula IV are summarized in the following table IV:

308836/1 189

link

No.

70 71 72 73 74 75

link

2,6-bis-methylthio-4-cyclohexylamino-a-triazine

2,6-bis-ethylthio-4-benzylamino-s-triazine

2,6-bis-methylthio-4-laurylamino-s-triazine

2,6-bis-methylthio-4-stearylamino-s-triazine

2, ö-bis-phenylthio ^ - stearylamino-s-triazine

2 _t 6-bis-laurylthio-4-

cyclohexylamino-s-

triazine

TABLE IV A. ρ ρ e η R. Enamel
Point Q r u methyl B. 'Cyclohexyl - ethyl Methyl " Benzyl 151-155 methyl ethyl Lauryl 72-73 Methyl. methyl Stearyl 80-85 Phenyl methyl Stearyl waxy
Pestilence Lauryl Phenyl Cyclohexyl 66 Lauryl

CS: UM

X and Y represent oxygen atoms

A-O

NH-R

0 - B

(V)

Examples of compounds of the formula V are given in Table V below:

309836/1189

TABLE V

Ver
binding
No. link 76 2,6-bis-allyloxy-4-
dodecylamino-s-triazine 77 2,6-bis-phenoxy-4-
laurylamino-s-triazine 78 2,6-bis-methoxy-4-
stearylamino-s-triazine 79 2,6-bis-butoxy-4-
benzylamino-s-triazine 80 2, o-bis-cyclohexoxy-JJ-
cyclohexylamino-s-
triazine 81 2,6-bis-allyloxy-4-
stearylamino-s-triazine. 82 2 .6-bis- (2 .4.6-tribromo-

groups

Phenyl

methyl

Cyclohexyl

Allyl

Phenyl

methyl

Butyl

Cyclohexyl

Allyl

Dodecyl

Lauryl

Stearyl

Benzyl

Cyclohexyl

Stearyl

phenoxy ^ - ^ l-octy laminos-triazine 2,4,6-tri-2,1,6-tri-octyl bromophenyl bromophenyl

Melting point ( ⁰ C)

49-51

75-78

140-146

glassy solid

glassy pest

waxy pest

190-192

One of the groups X or Y "means a sulfur atom while the other represents an oxygen atom:

A-O

NH-R

S-B

(VI)

Examples of compounds of the general formula VI are given in Table VI below:

309836/1189

Ver link TABLE VI A. - ρ ρ e η R. Melting ι binding
No. NS Butyl B. Dodecyl Point VJl 83 2-methylthio-4-dodecyl- methyl 40-45 I. ω amino-6-butoxy-s-triazine O methyl Stearyl CD 84 2-methylthio-4-3tearyl- methyl 140-145 OO amino-6-methoxy-s-triazine ethyl Cyclohexyl CJ
σ> 85 2-ethylthio-4-cyclohexyl- ethyl waxy p amino-6-ethoxy-s-triazine Pestilence - » Phenyl Octyl co 86 2-butylthio-4-octylaraino- Butyl glassier to 6-phenoxy-s-triazine Pestilence

The gas-resistant polymer composition according to the invention is obtained by incorporating the specified agent for increasing the gas resistance into a polymer, such as a polyurethane or a cellulose acetate, the agent being used in an amount of not more than 10% by weight, preferably in an amount of 0, 3 to 8 wt .-? O, based on the weight of the polymer used. If the amount is below 0.3 wt .- $, the effect of the agent added decreases, while the properties of the polymer, v / ie the toughness or elongation are deteriorated, if the agent is used in an amount of more than 10 wt. -% used. In one embodiment in which the agent for increasing the gas resistance is introduced into the polymer formed into an object (for example when the polymer present in fiber form is dyed with a dye liquor which contains the said agent for increasing the gas resistance), an excess amount leads the agent for increasing the gas resistance to a hardening of the surface of the fiber material so that it is preferred to use an amount which is not more than about 8 wt - represents.%.

With regard to the incorporation of the agent according to the invention To increase the gas resistance in the polyurethanes and cellulose acetates there are no restrictions and there are no restrictions Various procedures and devices can be used.

For example, the agent of the present invention for increasing the gas resistance can be incorporated into those used as the starting material Monomers are incorporated before the initiation polymerization to form the polyurethane elastomers or the means can be used at the beginning of the polymerization or during or after the polymerization reaction added to ground. Particularly preferred

309836/1 189

is to mix and disperse the agents in the polyurethane elastomer. In the case of cellulose acetates can the agent with the cellulose acetate flakes or with a Spinning mass are mixed, which can be obtained by dissolving the cellulose acetate polymer in an organic solvent, such as acetone, ethylene dichloride or dimethylformamide obtained

Furthermore, the agents according to the invention can be added before or during the shaping of the polymer. Farther it is also possible to treat an object molded from the polymer with a solution or an aqueous one Bringing the emulsion of the agent into contact to increase the gas resistance, e.g. by immersion or loading, spraying takes place. Furthermore, the agent according to the invention can be added to a dye liquor and at the same time be introduced into the polymer during the dyeing process. In short, the agent according to the invention can be used to increase the Gas resistance in the course of any stage in the preparation of the polymer or that formed from the polymer molded article are incorporated into the polymer. That to form a solution of the agent Solvents used to increase gas resistance can, for example, be a low molecular weight aliphatic alcohol such as Methanol, ethanol, n-propanol or isopropanol or a relatively low-boiling halogenated hydrocarbon, such as Be carbon tetrachloride, chloroform, tetrachlorethylene or trichlorethylene. These solvents can also do this serve to add the agent according to the invention in the polymer disperse. The emulsifying agent used to form the aqueous emulsion can be, for example, a nonionic surfactant An agent or an anionic surfactant, alone or in the form of a combination can be used. Examples of compounds of this type are sodium dodecylbenzenesulfonate, lauryl sulfate and alkylphenol / ethylene oxide adducts, which can be obtained by adding 10 to

309836/1189

30 moles of ethylene oxide to form an alkylphenol whose alkyl group Has 8 to 15 carbon atoms. These emulsifiers are preferably used in the form of a mixture in order to increase the stability of the emulsion.

The most preferred method of incorporating the invention Means to increase the gas resistance consists in adding this agent before the production of the polymer, so that the polymer itself has an increased gas resistance. In general, the effect is the The increase in gas resistance is more lasting if the agent according to the invention is incorporated into the polymer than when it is supplied in the course of dyeing an object formed from the polymer.

The polymer component of the gas-resistant polymer compositions according to the invention is a polyurethane or a cellulose acetate. Of course, the compositions according to the invention can contain other polymers that can be produced with these polymers are compatible.

Examples of polyurethanes are polyurethane elastomers that have a urethane bond, a urea bond and an acid amide bond have in a main chain. These polyurethane elastomers are generally obtained by Polyether glycols or polyester glycols containing hydroxyl groups and having a molecular weight of 500 to 6,000 with Treated organic isocyanate end groups containing diisocyanates in excess, whereby prepolymers are obtained, which can be used with bi-functional compounds, v / ie diamines, diols, hydrazine, water or hydroxylamine in polar solvents, such as dimethylformamide, dimethylacetamide or dimethyl sulfοxyd converts with chain extension, whereupon if desired, the product is reacted with an agent for blocking the end groups. It should be noted, however, that the

309836/1189

Polyurethanes that can be used according to the invention,

are not limited to those compounds that follow

can be obtained by the above method.

The cellulose acetates can be those materials obtained by acetylating rayon pulp, particularly diacetyl cellulose and triacetyl cellulose.

The gas-resistant polymer compositions according to the invention can furthermore contain known additives which are normally used together with these polymers. Examples of such additives are ultraviolet light absorbers, antioxidants, dyes, matting agents and fillers. The compositions of the invention can be in various forms. For example, they can be in the form of powders, granules, pellets, flakes, chips or shaped articles such as filaments, fibers, yarns, strands, knitted or woven fabrics, non-woven fabrics, films (including coated and laminated films) or sheets.

The following examples and comparative examples are intended to explain the invention further without, however, restricting it.

In these examples, the gas resistance test was carried out according to the following procedure:

Test method for determining the color fastness to nitrogen oxides (JIS L 0855)

Device and material:

(1) Apparatus: A glass vessel having a capacity is used of about 15 liters, so that you can easily see the object to be examined inside the vessel from the outside can watch. Agitator blades are also provided, see above

309836/1189

that the gases which are formed inside the vessel can be stirred well. The agitator blades are also grounded rotated at a speed of 70 to 80 rpm. There is a tripod inside the vessel. On the tripod a 500 ml evaporation dish is arranged, while a sample clamp is arranged below the tripod is.

(2) Phosphoric acid: test tube grade phosphoric acid (grade 1 according to JIS K 9003).

(3) Sodium nitrite solution: A solution of 10 g of sodium nitrite (reagent quality, grade 1 according to JIS K 8019), dissolved in 1 liter, distilled water.

(4) Urea: reagent grade urea (grade 1 according to JIS K 8731).

(5) Anionic surfactant: dioctyl sodium sulfosuccinate, purity at least 70 %, with no more than 0.1 % alcohol-insoluble material, pH

6 to 7.

(6) Fabric provided with standard dyeing: For this purpose, a woven acetate fabric which had been dyed with Celanthrene Billiant Blue FFS (Du Pont) to a prescribed color strength (the concentration of the dye should be about 0.5 % ) was used, the The size of the sample was 5 χ 1 cm in each case.

Preparation of the sample to be examined :

The size of the sample is usually 10 χ 4 cm. In the case of yarns these are arranged parallel in a thin layer, knitted into a fabric or parallel to a frame (e.g. a U-shaped wire).

30 9.8 3.6 / 1 189

Procedure:

The sample to be examined and the tissue, which had been dyed according to the standard, are arranged radially at a distance of 3 cm on a circular iron wire on the sample clamp below the tripod. The evaporation dish, which contains a mixture of 350 ml of distilled water and 6.7 ml of phosphoric acid (85 %) , is placed on the tripod. Then 25 ml of an aqueous solution of sodium nitrite is added and a lid is quickly placed on the device. The rotating blades are set in rotation at the prescribed speed in order to achieve a uniform gas mixture inside the vessel. The fabric dyed according to the standard is observed from the outside, whereupon the rotation of the agitator blades is stopped immediately at the moment when the color of the fabric corresponds to the color of a fabric which has a standard coloration of a bleached cloth. Then the lid and the evaporation tray are removed. The sample is taken into the fresh air together with the tripod. Then, one third of each sample is cut out and used as a unit test piece for evaluation. The bleached fabric dyed according to the standard is then replaced by a fabric freshly dyed according to the standard, and the device is then reassembled. The investigation is continued in the same way using a second and a third sample. The investigation is carried out under standard conditions, whereby in principle direct sunlight is avoided. The sample, which had been treated with nitrogen oxide gas, is immersed as quickly as possible in an aqueous solution containing 5 g of urea and 1 g of an anionic surfactant (dioctyl sodium sulfosuccinate) per liter of the solution (20 - 2 ° C) and in it 5 Leave for minutes, after which the sample is rinsed with distilled water, drained between sheets of filter paper and air-dried.

30-9836 / 1 189

If the specimen clamp is not attached to the specimen, a white tissue of the same size as the specimen is attached to it.

valuation

The evaluation of the bleaching of the color of the sample is carried out according to the standards given below using a Fading gray scale JIS L 0804 determines:

Valuation number Valuation standard ____ ^ __

When examining a unit, the color change is beyond number 3 in the Grayscale.

When examining a unit, the color change is beyond # 4 and up to number 3 in the gray scale.

When examining a unit, a change in color is observed, the Extent of color change up to number 4 on the gray scale.

When examining a unit, no color change is observed while when examining two units, the color change beyond No. 4 and up is number 3 in the gray scale.

When examining two or three

Units is the color change up to number 4 in the gray scale.

309836/1189

games 1 to 18 and comparative examples 1 bJ3 18

Made of polytetramethylene glycol with an average Mb - molecular weight of 2000 and diphenylmethane-4,4'-diisocyanate a prepolymer was prepared and then dissolved in dimethylformamide. With stirring it became an aqueous solution of hydrazine and diethylamine added in an amount to extend the chain and saturate the end groups. In addition, 2% by weight of titanium oxide was added to obtain a dimethylformamide solution of polyurethane.

The polyurethane solution thus obtained was divided into portions. Each of the compounds shown in Table VII was added to 100 parts (30 parts of polyurethane) of the resulting portions in an amount of 3% by weight. Each of the obtained mixtures was cast on a glass plate to form a film. After one-day standing, the film was / treated for 8 hours ater V washed and another 20 minutes at 100 ⁰ C. The obtained films were used in the gas resistance test.

309836/1189

at
game
No. used additive TABLE VII No. used additive Gas resistant
ability test
(Evaluation
digit) 1 Table I No. 1 Gas resistant
ability test
(Evaluation
digit) Comparison
example 1 5 2 "No. i 2 1-2 Comparison
example 2 5 CO
t — t 3 "No. 3 1-2 Comparison
example 3 Comparison ver
binding no, 1 5 « 1983 4th "No. 4 2 Comparison
example 4 Comparison ver
binding no. 2 5 <« 6/1 ' 5 "No. 8 1-2 Comparison
example 5 Comparison ver
binding no.3 4-5 OO
co 6th "No. 10 1-2 Comparison
example 6 Comparison ver
binding no. 4 5 < 7th "No.14 1-2 Comparison
example 7 Comparison ver
binding no. 5 5 IN »
CO 8th "No.16 1-2 Comparison
example 8 Comparison ver
binding no. 6 CO
² -3 p 9, "No.18 2 Comparison
example 9 Comparison ver
binding no. 7 5 < 2 Comparison ver
binding no. 8

TABLE VII continued:

at
game
No. used additive I number 20 Gas resistant
ability test
(Evaluation
digit) No. t
used additive Gas resistant
ability test
(Evaluation
digit) I. 10 Tabel No. 22 1-2
1 Comparison
example 10 Compare ver
binding no.9 2 4>
VJi
I. 3983 11 dd No. 28 2 Comparison
example 11 Comparative
binding # 10 2 6/1 12th If No. 30 1-2 Comparison
example 12 Comparison Ver
binding no.11 3 189 13th It No. 31 1-2 Comparison
example 13 Comparison ver
binding no.12 5 14th ti No. 32 1-2 Comparison
example 14 Comparison ver
binding no.13 3-4 230 15th Il No. 35 1-2 Comparison
example 15 Comparison ver
binding no.14 - 3-4 910 16 Il No. 36 2 Comparison
example 16 Comparison ver
binding no.15 2-3 cn 17th It No. 37 2 Comparison
example 17 I forget
binding no.16 2-3 18th Il 1-2 Comparison
example 18 Comparison ver
binding no.17 2-3

AMMBRKUNG ;

Comparative compounds of the comparative examples

No. 1 - 2,4,6-tris-dimethylamino-s-triazine

No. 2 - 2,4,6-tris-dibutylamino-s-triazine

No. 3 - 2,4,6-tris-phenylamino-s-triazine

No. 4 - 2,4,6-tris-morpholino-s-triazine

No. 5 - 2,4,6-tris-diallylamino-s-triazine

No. 6 - 2,4,6-tris-ethyleneimino-s-triazine

No. 7 - 2,4,6-tris-ethylamino-s-triazine

No. 8 - 2,4-bis-phenylamino-6-dibutylaraino-s-triazine

No. 9 - 2,4,6-tris-methylamino-s-triazine

No. 10 - 2,4-bis-hydrazino-6-dimethylamino-s-triazine

No. 11 - Adipic Acid Dihydrazide

No. 12 - 1,1-dimethylstearyl semicarbazide

No. 13 - poly-diethylaminoethyl methacrylate)

No. 14 - phenylurea

No. 15 - stearyl alcohol

No. 16 - stearic acid

No. 17 - Stearic Acid Arid.

309836/1189

Jed *; the film obtained above was further immersed in an aqueous solution containing 0.5 g of lauryl sulfate per liter of the solution and ^{treated for 60 minutes at TOO 0} C, then washed with water and dried again for 20 minutes at 120 ° C, whereupon the material at the gas resistance test was used. In Examples 1 to 18, no reduction in the gas resistance effect was observed, while in Comparative Examples 8, 10 and 11, the gas resistance effect showed a score of 5 or more, indicating poor durability. In Comparative Examples 16 to 18, the surface of the film showed strong hydrophobicity and repelled the water. The gas resistance properties of these films were very uneven, with a notable reduction in effectiveness in some cases.

Examples 19-25 and Comparative Examples 19-26

The polyurethane solution prepared according to Example 1 was divided into proportions. Each of the following Table VIII specified compounds were in an amount of 2 wt .-%, based on the polyurethane, each with 100 parts of the proportions (30 parts of polyurethane each) mixed. The mixture was then processed into films in the same manner as described in Example 1 and with regard to the gas resistance effect examined. The results obtained are shown in Table VIII below.

309836/1189

used Additive Gas resistant
ability test
(Evaluation
digit) TABLE VIII used additive Gas resistant
ability test
(Evaluation
digit) 2309 ' at
game
No. Table II No. 41 1-2 Control no. Comparison ver
binding no.18 5 < O
cn 19th »T No. 43 2 19th Comparison
binding no.19 3-4 20th It No. 46 1-2 20th Comparison ver
binding no.20 5 < 21 It No. 48 2 21 Comparison ver
binding no.21 5 22nd Jt No. 49 1-2 22nd Comparison ver
binding no.22 3-4 23 ft
JJ No. 50
No. 53 1-2
2 23 Comparison ver
binding no.23
Comparison ver
binding no.24 5
4th 24
25th 24
25th Comparison ver
binding no.25 3-4 26th

NOTE :

Comparative connections of the comparative examples

No. 18 - 2,4-bis-phenylamino-6-phenylthio-s-triazine

No. 19 - 2,4,6-Tris-acetylamino-s-triazine

No. 20 - Dilaurylthiopropionate

No. 21 - Tridecylthiophosphite

No. 22 - triethanolamine

No. 23 - Phenylmorpholine

No. 24 - 1,4-dibenzylmorpholine

No. 25 - N-Phenylpiperazine

Each of the films indicated in Table VIII was further immersed in an aqueous solution containing 0.5 g of lauryl sulfate per liter of solution contained and treated for 60 minutes at 100 ⁰ C, washed and then the film with water and was dried. The treated films were examined for the Ga3 resistance effect. In Examples 19 to 25, no reduction in the gas resistance effect could be found, while in Comparative Examples 19 and 22 the gas resistance effect was given the rating number 5, which corresponded to the rating number of a film to which the agent for increasing the gas resistance was not added . This indicates a bad one

309836/1189

Durability of the effect. In Comparative Examples 24 and 25, the gas resistance effect showed a rating number of 4-5, which in the same way as in the case of Comparative Examples 19 and 22 indicates poor durability indicates.

Examples 26 to 34 and Comparative Examples 27 to 32

The polyurethane solution prepared according to Example 1 was divided into shares, after which each of the compounds indicated in the following Table IX with 100 parts by weight of the units (each 30 parts polyurethane) in an amount of 2.0 wt -.% Based on the _t Were mixed by weight of the polyurethane. The mixture was shaped into films in the same way as described in Example 1, whereupon the films were examined with regard to their gas resistance and effect. The results obtained are summarized in Table IX below.

309836/1189

at
game
No. used Additive TABEL IX ■ 27 , additive used Qas resistant
test
(Valued
digit) 5 I.
VX K)
CJ
O
CO 26th Table III No. 54 Gas-resistant control no.
ability test
(Evaluation
digit) 28 • 5 I. O
cn 27 It No. 55 1-2. 29 Comparison ver
binding no.27 4-5 28 ff # 56 2 30th Comparison ver
binding no.28 5 < 098 29 ti No. 58 1-2 31 Comparative
binding # 29 5 36/1 30th TI No. 60 1-2 32 Comparison ver
binding no.30 5 < 189 31 ti No. 64 2 Comparison ver
binding no.31 32 dd No. 65 1-2 Comparison ver
binding no.32 33 dd No. 67 . 1-2 34 dd No. 69 2 2

NOTE :

Comparative Compounds of Comparative Example No. 27 - 2,4-bis-phenylamino-6-phenoxy-s-triazine

No. 28 - 2 _f 4-bis- (p ~ chloroanilino) -6- (p-chlorophenoxy) -striazine

No. 29 - 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene

No. 30 - 2- (2 ^t -hydroxy-3 ^l , 5 ^l -diisoamylphenyl) -benztriazole (Tinuvin-328 from CIBA GEIGY AG.)

Nr. 31 - tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4 ^l hydroxyphenyl) propionate] methane
(Irgenox 1010 from CIBA GEIGY AG.)

No. 32 - 6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis-octadecylthio-s-triazine

(Irganox 565 from CIBA GEIGY AG.)

Examples 35 to 46 and Comparative Examples 33 to 36

The polyurethane solution prepared according to Example 1 was divided into proportions and each of the compounds listed in the following Table X was in an amount of 3.0 wt .-; o, based on the polyurethane, with 100 parts (30 parts each Polyurethane) of the proportions mixed. The mixture was processed into foils, whereupon the foils with regard to the Gas resistance effects were investigated. The results obtained are summarized in Table X below.

309836/1189

at
game
No. used additive IV No. 70 TABLE X No. used additive Gas resistant
ability test
(Evaluation
digit) 35 Tabel No. 71 Gas resistant
ability test
(Evaluation
digit) Example 43 Table VI No. 83 2-3 approx 36 ti No. 72 1-2 44 "No. 84 2-3 CD
co 37 ti No. 74 2 45 "# 85 ² a CJ 38 ft V No. 76 1-2 46 "No. 86 2-3 T 39 Tabel No. 78 2-3 Comparison
example 33 Comparison ver
binding no.33 5 co
CD 40 It No. 79 2 Comparison
example 34 I forget
binding no.34 41 It No. 81 2 Comparison
example 35 Comparison ver
binding no.35 5 < 42 It 1-2 Comparison
example 36 Comparison ver
binding no.36 5 ro
co 2

NOTE:

Comparative Compounds of Comparative Examples No. 33 · * ■ Zjö-bis-phenylthio- ^ - phenylamino-s-triazine No. 34-2 _f 6-bis-butylthio-4-phenylamino-s-triazine No. 35-2,6-bis -phenoxy-4-phenylamino-s-triazine No. 36 - 2-phenylthio-4-phenylamino-6-phenoxy-s-triazine

Examples 47 to 64 and Comparative Examples 37 Ms 47

The polyurethane solution prepared according to Example 1 was divided into proportions, whereupon each of the compounds indicated in Table XI in an amount of 0.5, 3.0 or v /. 6.0 wt % with 100 parts (30 parts polyurethane) each
Proportion was mixed. The mixture was then made into films, whereupon these were examined for the gas resistance effect. The results obtained are summarized in Table XI below. In Table 11, the letter A indicates that the additive was used in an amount of 0.5% by weight, while the letters B for 3.0% by weight and C for 6.0% by weight. -% stand.

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TABLE XI

at
game
No. used
. Additive No. 2 Gas resistance
test
(Valuation number) B. C. No. t 62 40 used
Additive No. 83 No. 11 Gas resistance
test
(Valuation number) B. C. I.
VJI
VT
I. No. 4 A. 1-2 1-2 63 41 No. 85 No. 15 A. 1-2 1-2 47 Table I. No. 14 2-3 1-2 1-2 example 64 42 Comparison
connection no. 1
¹¹ No. 2
¹¹ No. 9 No. 19 3 2 1-2 co 48 ti No. 20
No. 28
No. 31 2-3 1-2 1-2 Comparison
example 37
"38
39 43 Table V No. 79 ti No. 21 3-4 2 1-2 OO
IO 49 It No. 42 3 1-2
1-2
1-2 1-2
1-2
1-2 It 44 ti It No. 25 3 IVJ VJl VJl 5
5
2 ro 6/1189 50
51
52 ti
ti
It No. 46 2-3
3
3 1-2 1-2 ti 45 It Il No. 27 5
5
3 3 3 O
<o 53 Table II No. 49 2-3 1-2 1-2 ti ti 4-5 2-3 2-3 SOL 54 It No. 54 3 1-2 1-2 ti It 3 3-4 3-4 55 ti No. 64 3 1-2 1-2 It It 5 5 5 56 Table ΠΙ No. 69 2-3 1-2 1-2 ti 5 3-4 3-4 57 ti 3 2 1-2 5 5 < 5 < 58 Il 2-3 5 <

Continued TABLE XI:

Bel- used game additive No.

Gas resistance test (Valuation number)

No.

59 Table IV No. 70 2-3

60 "# 73 3

61 Table V number 76 3

i-2

2
2

Comparative Example 46

used Additive

Comparative compound no. 32

47 "no addition

No. 35

Gas resistance test (evaluation number)

ABC

5 < 5 <

5 < 5 < 5

5 <

5 <5

I. CO CD * CD I. O Oil

Each of the films obtained above was immersed in an aqueous solution containing 1 g lauryl sulfate per liter of the solution contained therein and treated for 60 minutes at 10O ⁰ C ^ after which the films were washed with water and dried. Then each sample was subjected to the gas resistance test. In Examples 47 to 64, no reduction in the gas resistance effect was observed, while in Examples 39 to 42 and 44, the gas resistance effect rating number was 4-5.

Examples 65 to 72 and Comparative Examples 48 to 53

A prepolymer prepared from polytetramethylene glycol with a molecular weight of 2000 and diphenylmethane diisocyanate was prepared in a manner known per se and then dissolved in dimethylformamide. A mixture of hydrazine hydrate and di-n-butylamine was added with stirring to extend the chain and saturate the end groups. To the resulting solution was added 3.0 wt -.% Of (in each case based on polyurethane) in the following Table XII indicated compounds and 2.0 wt .-% titanium oxide. The mixture was then dry spun into a polyurethane elastomer yarn (40 denier). In the same way, a polyurethane solution which did not contain these additives was dry-spun by forming a polyurethane elastomer yarn. The gas resistance test was carried out using these elastic yarns. The results obtained are summarized in Table XII below.

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at
game
No. used additive TABLE XII Comparative,
example no. used additive Qas resistant
ability test
(Evaluation
digit) I.
VT
α
ϊ 2309 ' 65 No. 2 of Table I. Gas-resistant
ability test
(Evaluation
digit) 48 Comparison ver
binding no. 7 2-3 «« MB
CD
Oil 66 Number 28 of Table I. 2 49 Comparative
binding no.11 4-5 co
O 67
68 31 of Table I.
Number 49 of Table II 2 50
51 Comparison ver
binding no.15
Comparison Ver
binding no.17 5
4-5 9836/1 1 69 Number 54 of Table III 2
2 52 Comparative
binding # 25 5 CD
CO 70 Number 70 of Table IV 2 53 Comparison ver
binding no.30 4-5 71 No 76 of Table V 2-3 1 no addition 5 72 No. 83 of Table VI 2-3 3

Each of these elastic yarns was dipped in an aqueous solution containing sodium dodecylbenzenesulfonate in an amount of 1 g / l of the solution contained 1 hour at 7O ° C-treated, then 1 hour at 100 ⁰ C cooked, then washed well with water and dried. The treated yarns were examined with regard to the gas resistance effect. As a result, it was found that the elastic yarns treated according to the present invention showed no reduction in gas resistance effect, while the gas resistance effect in Comparative Example 48 showed a score of 5 after the treatment, indicating no durability.

The compounds used in Comparative Examples 50 and 51 showed relatively good gas resistance effects when examining films while the effect did not show in the materials spun into yarn. This indicates that the compounds where gives an effect of bleeding on the surface of the molded articles, are not capable of the To improve gas resistance properties of the polyurethane polymer significantly.

Examples 73 to 87 and Comparative Examples 54 to 59

_# 3 weight parts by the compounds shown in the following Table XIII was dissolved in 50 parts by weight of a 1: 1 mixture of methyl alcohol, isopropyl alcohol and benzene, and with 1 part by weight of a nonylphenol / ethylene oxide adduct (9 moles: 1 , calculated as ethylene oxide) mixed. The mixture was emulsified and dispersed in 50 parts by weight of water with vigorous stirring to give an aqueous dispersion containing 3 parts by weight of the active ingredients.

3 09836/1189

Then a strong fabric made by weaving nylon and 20 wt .- # polyurethane made into a fluorescent dye was dyed, immersed in said dispersion for 10 seconds and then squeezed off so that the Content of the active ingredient (compound of Table XIII) 2.0% by weight based on the weight of the fiber, was followed by heat treatment at 170 ° C for 5 minutes. These test samples incl. some untreated samples were examined with regard to the gas resistance effect. The results obtained are summarized in Table XIII below.

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TABLE XIII 1 of Table I. 3 Gas resistance
test • greater than 5 Examples and
Comparison
examples used additive 12 ^l! 9 1-2 1-2 73 No. 16 » 15th 1-2 1-2 74 No. 28 " 20th 1-2 2-3 75- No. 32 " 26th 1-2 2-3 76 No. 41 of Table II 34 1-2 4-5 77 No. 47 ^lf 1-2 4th 78 No. 50 » 1-2 79 No. 55 of Table III 1-2 80 No. 65 " 1-2 81 No. 72 of Table IV 1-2 82 No. 75 " 2 83 No. 76 of Table V 1-2 84 No. 81 » 1-2 85 No, 84 of Table VI 1-2 86 No. 1-2 87 No. Comparison connection no. Comparison
examples 54 55 56 57 58 " No. 59 ¹¹ No. 60 " No. ⁿ No. " No. untreated sample

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These treated tissues were 30 minutes under USAGE dung an aqueous solution containing 1 g lauryl sulfate contained per liter, washed at 40 ⁰ C by means of a domestic washing machine and / ater rinsed for 10 minutes by V at 22 C. The fabrics were dried and examined for the gas resistance effect. In Examples 73 to a score of 2 was found in the gas resistance effect to 2-3, while the evaluation point of equal Ver Examples 55 to 58 5, indicating no resistance was.

Examples 88 to 101 and Comparative Examples 60 to 68

An acetone solution which contained 10 % by weight of cellulose diacetate was divided into proportions, whereupon each of the compounds given in Table XIV below in an amount of 1.0% by weight , based on the weight of the diacetate with 100% by weight. Parts (10 parts by weight of cellulose diacetate) per portion was mixed. Each of the obtained mixtures was cast on a glass plate using a doctor blade to form a film of a certain thickness. The film was left to stand for 2 hours at room temperature, whereupon a transparent film was obtained after evaporation of the acetone. The obtained film v / urde £ dyed with Kayalon Fast Blue FN (dispersion dye of NIPPON KAYAKU KOGYO Kabushiki Kaisha) at a concentration of 3 wt .-? For 50 minutes at 80 ⁰ C. The ratio of coloring product to liquor was 1: 100. For comparison purposes, a film to which the compounds listed in Table XIV had not been added was examined with regard to the effect of gas resistance.

Since the films obtained in Comparative Examples 61 and 63 became cloudy because of insolubility in acetone, became

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they are not examined with regard to the gas resistance effect The results obtained in the investigation are summarized in Table XIV below:

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TABLE XIV

Examples and
Comparison
examples used additive 2 the Tabel I. No. Gas resistance
test
(Assessment number) 1 1-2 88 No. 14th Il No. 3 1-2 89 No. 20th Il No. 9 1-2 90 No. 28 Il No. 15th 2 91 No. 32 Il No. 19th 1-2 92 No. 46 the Tabel II No. 23 1-2 / ⁹³ No. 53 II No. 24 2-3 94 No. 58 the Tabel III No. 25th 2 95 No. 60 ti 26th 2 96 No. 65 It 2 97 No. 70 the Tabel IV 2 98 No. 71 Il 2-3 99 No. 79 It 2 100 No. 85 the Tabel VI 2 101 No. Comparison
examples Comparison connection no. 4-5 60 - 61 4-5 62 - 63 3-4 64 5 65 4-5 66 4-5 67 5 68 5 control Il It It It Il It It Il no addition

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Examples 102-109 and Comparative Examples 69-71

Each of the compounds listed in Table XV below was added in an amount of 1.0% by weight to a 15 % strength solution of diacetyl cellulose, and the mixture was dry-spun to form acetate filaments (100 denier). Separately, the above solution to which the additive had not been added was spun in the same manner. Each of the filaments obtained was treated for 20 minutes at 70 ⁰ C in an aqueous solution containing 1 g of a nonionic surfactant (ethylene oxide (15 mol) / Nonylphenoladdukt) contained per liter and then for 60 minutes at 80 ⁰ C with DIACELLITON Fast Blue-B (disperse dye from MITSUBISHI CHEMICAL CO.LTD.) (3% by weight dyed. The liquor ratio was 1:50. The dyed filaments were washed with water / water and dried, and then subjected to the gas resistance test. The results obtained are summarized in the following Table XV.

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TABLE XV Gas resistance
test
(Valuation number) Examples
and Ver
same examples used additive 1-2 102 No. 2 of Table I. 1-2 103 No.14 " 2 104 No.28 " 1-2 105 No.31 " 1-2 106 Number 46 of Table II 2-3 107 No.53 " 2 108 No. 60 of Table III 2 109 Number 70 of Table IV Comparison case
games .1 4-5 69 Comparison connection no .7 4-5 70 ¹¹ No. .24 4-5 71 5 control no addition

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Examples 110 to 121 and Comparative Examples 72 to 78

.3 parts by weight of the compounds listed in Table XVI below were dissolved in 50 parts of a 1: 1 mixture of methyl alcohol and benzene, v / o up to 1 part by weight of a nonylphenol / ethylene oxide (9 mol) adduct · The mixture was emulsified and, with vigorous stirring, dispersed in 50 parts by weight of water, an aqueous dispersion being obtained which contained 3% by weight of the active ingredient .

Then, "was a taffeta fabric made of cellulose diacetate, which with Kayalon Fast Blue FN (dispersion dye of NIPPON KAYAKU KABUSHIKI KAISHA) with a concentration of 3 wt -% at 80 ⁰ C for 60 minutes. (Liquor ratio 1: 100) was dyed, while 70 seconds immersed in said aqueous dispersion, and such abge squeezes that the tissue had received the attached in Table XVI compound added as an active ingredient in an amount of 2 wt. -56, whereupon the material was heat treated for 3 minutes at 170 ⁰ C. the treated. Fabrics were examined together with an untreated fabric for the gas resistance effect and the results obtained are summarized in Table XVI below.

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TABLE XVI 3 of the table I. No. Gas resistance
test
(Valuation number) 3 1-2 Examples and
Comparison
examples 10 " No. 7th 1-2 110 used additive 16 " No. 15th 1-2 111 No. 28 »
32 " No. 20th 2
1-2 112 No. 43 of the table II No. 23 1-2 113
114 No. 48 " No. 24 2 115 No.
No. 56 of the table III 26th 2 116 No. 65. 2 117 No. 70 of the table IV 2 118 No. 79 " 2 119 No. 85 of the table VI 2 120 No. 121 No. Comparison connection no. 2-3 Comparison
examples No. 1-2 72 5 73 2-3 74 2-3 75 2-3 76 2-3 77 5 78 Il control Il Il « Il Il no addition

309836/1189

Each of the treated fabrics was performed at 4O ° C for 30 minutes using an aqueous solution containing 1 g lauryl sulfate contained per liter, washed by a household washing machine, for 10 minutes at 25 ⁰ C was rinsed with water and finally dried. The samples were then examined for gas resistance effect. It was found that Examples 110 to 12-1 gave the gas resistance effect rating of 2-3, while Comparative Examples 72 and 79 were markedly reduced in gas resistance effect. The results obtained are given in Table XVII below.

TABLE XVII

No gas resistance test

(Valuation number)

Examples 110 to 121 less than 2-3

Comparative examples

72 4-5

73 4-5

74 5

75 5

76 5

77 4-5

78 4-5

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Claims (10)

PATENT CLAIMS: 1. Agent for increasing the gas resistance of polyurethanes and cellulose acetates, containing a triazine derivative of the following general formula I. A-X (E) Y-B (D) (D NH-R X and Y, which can be the same or different, Represent nitrogen atoms, sulfur atoms or oxygen atoms, where η is 1 when X represents a nitrogen atom or is zero when X is a sulfur atom or an oxygen atom and m is 1 when Y is a nitrogen atom represents and represents zero when Y represents a sulfur atom or an oxygen atom, A, B and R are alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 3 to 18 carbon atoms, cycloalkyl groups substituted with 3 to β carbon atoms, benzyl groups Benzyl groups, cyanoalkyl groups with 3 to 5 carbon 309836/1189 lenstoffatomen , dialkylamino groups with 2 to 8 carbon atoms, phenylamino groups, phenyl groups or substituted phenyl groups , with the proviso that the groups A, B and R do not represent phenyl groups or substituted phenyl groups at the same time and R does not represent a phenyl group or substituted phenyl group when X and Y Sulfur atoms or oxygen atoms mean and D and E are hydrogen atoms or groups represented for A, B and R of the given kind, where the groups A and E or the groups B D may form a hetero cyclic ring having 2 to 5 carbon atoms and, together with X and Y, and wherein R represents no phenyl group or substituted phenyl group , if the two groups E and D are different from hydrogen , wherein the groups A and R do not represent phenyl groups or substituted phenyl groups ^ if only the group Ξ denotes a hydrogen atom and in which the groups B and R do not represent phenyl groups or substituted phenyl groups if only the group D is a hydrogen atom and in which the sum of the carbon atoms contained in groups A, B, D, E and R is at least 10. 2. Agent according to claim 1, characterized in that the triazine derivative is a compound of the following general formula Ia NH-R 3098 3 87 1 18 9 is where X is a nitrogen atom, a sulfur atom or an oxygen atom is, where η is 1 when X is a nitrogen atom or is zero when X is a sulfur atom or a Represents oxygen atom, A, B and R are alkyl groups with 1 to 18 carbon atoms, alkenyl groups with 3 to 18 carbon atoms, cycloalkyl groups with 3 to 6 carbon atoms, benzyl groups, substituted benzyl groups, cyanoalkyl groups with 3 to 5 Carbon atoms, dialkylamino groups with 2 to 8 carbon atoms, Phenylamino groups, phenyl groups or substituted Phenyl groups mean, with the proviso that the groups A, B and R are not phenyl groups at the same time or represent substituted phenyl groups and D and E represent hydrogen atoms or groups as indicated for groups A, B and R, v / obei the groups A and E and the groups B and D together with X and the nitrogen atom have a heterocyclic ring May form 2 to 5 carbon atoms, with the proviso that the group R is not phenyl or substituted A phenyl group is when X is a sulfur atom or an oxygen atom and D is a group other than hydrogen and the groups B and R do not simultaneously represent phenyl groups or substituted phenyl groups if X is a sulfur atom or an oxygen atom and D is a hydrogen atom mean, v / whether R does not represent a phenyl group or a substituted phenyl group when X is a nitrogen atom and the two groups E and D of hydrogen denote groups different from one another, with A and R not at the same time Represent phenyl groups or substituted phenyl groups when only the group E is a hydrogen atom and the groups B and R do not represent phenyl groups or substituted phenyl groups when only the group D is Hydrogen atom and v / orin denotes the sum of the carbon atoms contained in groups A, B, D, E and R at least 10 is. 309836/1189 3. Composition according to claim 1, characterized in that the triazine derivative is a compound of the following general formula Ib is A-X (Ib) NH-R X is a nitrogen atom, a sulfur atom or an oxygen atom represents wherein η is 1 when X is a nitrogen atom and is zero when X is a sulfur atom or represents an oxygen atom, A is an AlKyl group with 1 to 18 carbon atoms, a Alkenyl group with 3 to 18 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a benzyl group, a substituted benzyl group, a cyanoalkyl group having 3 to 5 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, a phenyl group or represents a substituted phenyl group, R denotes a group of the formula -N (R) p, v / orin the two groups R _t, which can be identical or different, denote alkyl groups with 1 to 4 carbon atoms, E represents a hydrogen atom or a group of the kind as defined for the group A, and where "'the Groups A and Ξ together with X can form a heterocyclic ring with 2 to 5 carbon atoms and v / orin the Sum of the carbon atoms contained in groups A, E and R is at least 10. 309836/1189 4. Gas-resistant polymer compositions, characterized in that it comprises a polyurethane or a cellulose and not more than 10 wt -.% Of a triazine derivative according to claim 1, based on the polymer contain. 5. Polymer composition according to claim 4, characterized in that it is a tirazine derivative as the active ingredient according to claim 2 included. 6. Polymer composition according to claim 4, characterized characterized in that they contain a triazine derivative according to claim 3. 7. Compositions according to claim 4, characterized in that the compositions, in the form of filaments, Fibers, strands, yarns, knitted or woven fabrics, non-woven fabrics, foils, sheets, powders, granules, Pellets, flakes or chips are present. 8. Compositions according to claim 4, characterized in that that the triazine derivative before or during the polymerization of the polyurethane or before, during or after it Processing in the polyurethane was incorporated. 9. Compositions according to claim 4, characterized in that that the triazine derivative in the course of any stage before or after the processing of the cellulose acetate incorporated into the cellulose acetate. 10. Compositions according to claim 4, characterized in that that the amount of the triazine derivative 0.1 to 10 wt .-? o, based on the weight of the polymer. 308836/1189 ^ .