DE2758313A1 - PROCESS FOR IMPROVING THE STILLABILITY OF MOLDED SOLID SYNTHETIC POLYMER SHAPED BODIES BY ACID DYES - Google Patents

Description

MÜLLER-BORE DEUFIiL SCHÖN HEKTTiJL

PATE Nl ¹ ANWILTE

DR. WOLFGANG MÜLLER-ΒΟΗέ (PATENT ADVERTISER FROM 1927-1975) DR. PAUL DEUFEL. D1PL.-CHEM. DR ALFRED SCHÖN, DIPL.-CHEM. WERNER HERTEL. DIPL.-PHYS.

S / R 14-180

Rohm and Haas Company,
Independence Mall West,
Philadelphia, Pa. 19105 / USA

Process for improving the dyeability of molded solid synthetic polymer moldings

acidic dyes

β UÜSCHEN 8a · SISBERTSTK. i · POSTFA '

OPAT TEL. (039) 17 40 03 · TELEX 5-21283

Description

The invention relates, in particular, to improving the properties of polymeric moldings, including their dyeability the dyeability with acidic dyes (acid dyes); it relates specifically to a preparation (composition) for the treatment of polymeric moldings in order to make them easier to dye with acidic and other dyes make, a process for improving the dyeability and other properties of polymeric moldings, as well as the resulting polymeric moldings.

Synthetic polymeric moldings vary considerably in the degree to which they accept dyes and in terms of how they are used on the washing fastness of the dyes. For example, polyester moldings, such as polyester yarns, dyed with disperse dyes (disperse dyes), there acidic dyes (acid dyes) or cationic dyes tend to wash out of the yarn, or at all not to be included. These unsatisfactory effects are often even more pronounced when the polymer Molded body in a highly oriented shape, e.g. B. in the form of stretched threads, fibers or films is present.

It is known that the dyeability of synthetic polymeric moldings with acidic dyes (acid dyes) Can be improved by the incorporation of cationic centers into the polymeric material, these efforts were however, not always successful because the treatment adversely affects (degrades) the yarn or because the treatment is uneconomical or the purposes for which the

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molded bodies obtained in this way can be supplied, are limited.

For example, in US Pat. No. 3,932,126, dyeing aid preparations, containing organic amines and carboxylic acids for coloring a polyester material with acidic Dyes (acid dyes) described. In the US patent 3,082,053 is the use of covalent compounds formed by reaction with a hydroxylating agent such as Ammonia or an organic amine, can be converted into an ionic state to improve the colorability of molded polyesters with acidic dyes. In US Pat. No. 3,128,265, resinous Preparations (masses) described which consist of a mixture of an epoxy resin and a quaternized amino group containing Are made of polyester. These preparations are soluble in common organic solvents and they are according to the information in this patent specification usable as coatings for hydrophobic polymer moldings, their ability to absorb dyes and their resistance to accumulation to improve of electrostatic charges and to make the moldings hydrophilic. In the case of the US patent 3,910,860, attempts are made to improve the dyeability of polymeric moldings by adding of amines including those referred to below as "sterically hindered" Amino compounds "designated amines to form a polymer mass in the molten state.

The aim of the present invention is now to determine the dyeability and other properties of polymeric moldings, in particular molded polyester molded articles such as films, fibers and yarns. The aim of the invention is also

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a preparation (composition) for the treatment of shaped indicate polymeric moldings with the help of which it is possible to improve their dyeability without the moldings to impair (degrade), so that the colors with which the molded article is stained are washable. goal of The invention is also the dyeability of polymeric moldings, such. B. those made of polyesters, at high Improve temperature in order to take advantage of dye carriers and high temperature treatments. Further objects of the invention are to improve the dyeability and other properties of polymeric moldings, whereby a variety of coloring and finishing effects can be achieved.

These and other objects, features, and advantages are in accordance with the present invention achieved by treating molded polymeric moldings with a new and improved preparation (composition), which contains or consists of a mixture or a reaction product of an amino compound and an difunctional organic alkylation compound for the Amino compound, the amino compound containing at least one sterically hindered primary or secondary amino group and wherein all other amino groups, if any, have a tertiary structure.

The amino compound creates coloring centers for the attraction and retention of dye molecules the polymeric shaped body treated with the preparation (mass) is created without, however, the polymeric shaped body being thereby created excessively impaired (degraded). It is assumed that the absence or minimization of the impairment

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-JV-

Trächtigung (degradation) is due to the sterically hindered character of the amino compound. The sterically hindered Structure also makes the amino compounds more soluble in solvents such as those commonly used to swell of polymeric substrates are used to allow better penetration of the coloring materials (dyes) into the molded body to promote. The primary purpose of the alkylating agents for the amino compounds is to keep the amino compound on the surface to hold or bind to the polymeric shaped body, so that the subsequently carried out coloring of the shaped body is stable and essentially washable.

The present invention not only improves the dyeability of polymeric moldings, but allows it also variations in terms of color effects and designs, such as. B. 2-color effects on the simultaneous or successive Applying a disperse dye and acidic staining are based. In addition, the invention Preparations for treating the polymeric substrates are inexpensive to manufacture and they can be any Time to be applied to the molding, whereby the irreversible binding to the end use is avoided, which is a consequence of the introduction of staining centers in a melt of the polymeric molding. The treatment also allows dyeing at higher temperatures, which, preferably in Connection with the use of dye carriers, required is to avoid unwanted dye patterns, such as e.g. B. free line (Bars), to be kept to a minimum. In addition, the present invention avoids the coloring of polymeric moldings is only limited to a uniform color, as is the case when amino compounds are incorporated into a melt polymeric bodies or in those for the production of the polymeric

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Molded comonomers used is the case. The ability to color polymeric moldings irregularly or randomly being able to do so is a major advantage, as it enables unusual and highly aesthetic effects to be achieved, such as a shimmering appearance that simulates the appearance of dyed natural fibers. Finally it was found that it is possible in certain cases to make polymeric moldings hydrophilic by the treatment according to the invention make and / or give them antistatic properties.

The preparation (composition) according to the invention is either a mixture in at least stoichiometric amounts of an amino compound and a difunctional organic alkylating compound for the amino compound or it is the product of the reaction between the amino compound and the alkylating compound. For the success of the invention it is essential that the amino compound contains at least one sterically hindered primary or secondary / mino group and that any other amino groups, if any, are tertiary amino groups. These conditions make the amino compound suitable for the use according to the invention, so that the amino compound coloring centers in the polymer molded article generated without impairing (degrading) the molded body.

Preferred classes for the amino compounds which can be used according to the invention, However, to which the invention is in no way limited, can be represented by the following structural formula become: · 1 * 2 / W

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in which the radicals R are selected independently of one another Hydrogen, substituted alkyl or aryl and unsubstituted Alkyl or aryl and in which one of the radicals R can be linked to another radical R to form a ring, provided that when an amino group is a primary amino group, at least one of the carbon atoms in the α- and β-positions is fully substituted to the nitrogen atom of the primary amino group, and provided that if a carbon atom in the α-position to a nitrogen atom is not completely substituted, the carbon atom in the ß-position is fully substituted to the nitrogen atom, and wherein m is an integer from 0 to about 4 and η is an integer from mean about 1 to about 10.

The alkyl groups include both open and cyclic structures containing from about 1 to about 12 carbon atoms or more included, such as B. methyl, ethyl, propyl, butyl, octyl, dodecyl, Cyclohexyl and the like. The aryl groups include mononuclear and polynuclear aryl groups, such as. B. phenyl and naphthyl. Substituents on alkyl or aryl include cyano, hydroxyl, aralkyl groups such as banzyl and phenethyl, dialkylamino and any other groups which can alkylate the primary or secondary amino groups and improve the dyeability do not bother.

Representative hindered amino compounds include the following:
tertiary alkyl (C, -Cq) amines
Menthane diamine

2,5-dimethyl-2,5-hexanediamine α, α-dimethylbenzylamine 1-amino-1-cyclopentanemethanol

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Tri-hydroxymethylaminomethane 1-adamantanamine

2-Amino-2-methyl-1,3-propanediol 2- / mino-2-methyl-1-propanol 1-amino-1-methyl-cyclohexane 1-amino-1-mathylcyclopentane 1,3-diaminoadamantane

Neopentylamine

Isophorondiarain

1,2-diamino-2-methyl-propane 1,3-diamino-2,2-dimethylpropane 4-amino-2,2,6,6-tetramethylpiperidine 3,3,5,5-tetramethyl-cyclohexylamine 2,5,5,7,7,10-hexamethyl-6-aza-2,10-diaminoundecane 1,3,5-trimethyl-1,3,5-triaminocyclohexane 1,3,5,7-tetraaminoadamantane 1,3,5-triarainoadamantane.

Among the above amino compounds are tertiary ones from the standpoint of commercial availability
Alkyl amines such as t-butylamine, neopentylamine, and menthediamine
(also known as 1,8-diamino-p-menthane), the preferred compounds.

The alkyl compounds can be any bifunctional organic compound, including resins, which react with the amino compounds by adding carbon to a nitrogen center in the amino compounds. A preferred one
Class of alkylating compounds are polyepoxy compounds and resins, such as. B. the low molecular weight diepoxides:

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1,2,5,6-Diepoxycyclooctane 1,2,7,8-Diepoxyoctane

3,4-epoxycyclohexy! Methyl-3,4-epoxycyclohexane carboxylate l-epoxyethyl-S ^ -epoxycyclohexane.

The preferred epoxy compounds are the resinous polymeric materials which are produced by reacting epichlorohydrins with pheno compounds or with aliphatic glycols or polyethers such as polyethylene glycol or polypropylene glycol. Examples are the reaction products of epichlorohydrin with bisphenol A, e.g. B. the reaction products of the following structure:

■ A

H ₀ C — CH — CiL

- O

O CH,

CH CH,

CH - CH:

where η is an integer from O to about 18 and X is hydrogen, Mean chlorine or bromine.

Representative examples of polyether polyepoxy compounds are the reaction products of epichlorohydrin with polyether, such as products uvlt: the structure

CH ₂ -CH-CH ₂ -O

CH ₂ -CH-O

R ι

- CH ₂ -CH-O-CH ₂ -CH-CH

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where η is an integer from 0 to about 70 and R is alkyl (C - C) or aryl (phenyl, naphthyl).

Other polyepoxides can be represented by the structure:

V7orin η is an integer from 0 to about 5.

The above and other polyepoxides are known per se and they are for example in US Patents 2,512,996, 2,548,447, 2,582,985, 2,643,239, and 2,694,694.

Another class of alkylation compounds are the polyhalides, which have no tertiary carbon atoms in the α-position to the halogen atoms, of which the following are representative:

X - (CH ₂ ) _n - X

X - CK,

CH ₂ - X

In the above formulas X is chlorine, bromine or iodine and η is one is an integer from about 2 to about 10.

Other useful polyhalides are oligomers of vinylbenzyl halides with the following recurring unit

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where X is chlorine or bromine and η is an integer from about 2 to about 10.

The polyfunctional Michael acceptors represent a further class of alkylation groups. These include known classes of compounds which can be characterized as α, ß-polyethylenically unsaturated compounds with a carbonyl group adjacent to the ethylenic unsaturation. These compounds may vary depending on the location of the
Ethylenic unsaturation have one or more carbonyl groups. In the well-known Michael reaction, the ethylenic unsaturation of the Michael acceptor is caused by the
primary amino group of the amino compound gebunder.e hydrogen atom protonated, usually as follows:

S PVNCH ₂ YY \ η ₂ -ηζ _{

wherein R is an alkylene or arylene group. '

Michael acceptors useful in the present invention include
Acrylates such as ethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, butanediol diacrylate, pentaerythritol tetraacrylate and the corresponding methacrylates; Fumarates, maleates, crctonates and itaconates; and ketone compounds such as divinyl ketone and 4,4-dimethyl-2,5-cyclohexanedienone.

As stated above, the preparations according to the invention represent (Compositions) either mixtures or reaction products of the amino compounds and the alkylation compounds. The

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Mixtures are made in any suitable manner, for example by mixing at least stoichiometric Quantities of the compounds in a common solvent. It can be a stoichiometric excess, for example of about IO%, one of the connections can be used in however, there is generally no benefit if it is desired that the resulting resin be substantially linear to keep. The linear structure produces sufficient softness, a property that is required if the polymeric molding is intended for textile applications. If, of course, toughness is required, so can a larger proportion of the polyepoxy compound is used.

The alkylation reaction can be promoted in the mixture by appropriate heating or the mixture can be used directly to treat the polymeric molded article. Alternatively can the reaction product after carrying out the alkylation reaction separated from the solvent medium and, if desired, redissolved for the production of the treatment preparation. The reaction products are simple adducts or complex products, depending on the amino compounds chosen and alkylating compounds.

The preparations (compositions) can by any suitable method, for example using a Spraying process, dipping process, capillary application process, Roller application process or any other process to which polymeric moldings are applied. In addition- from it is also possible to use a To apply solution of the amino compound and then a solution of the alkylating agent or vice versa. When the amino compound and the alkylation compound separately or in mi

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Schung are applied to the polymer moldings, is by exposing the shaped body treated in this way to elevated temperatures, as is the case, for example, with a subsequent one Texturing processes can occur when the molded article is a polyester fiber that causes the Components react with each other. However, the components also react at room temperature or at a lower temperature within a longer period of time.

The degree of dye uptake by a polymer molding, treated with the preparation according to the invention can be controlled (controlled) by the type and proportions of the amino compound and the alkylation compound will. In general, for a given amino compound, the dye uptake decreases as the equivalent weight increases of the alkylation compound increases, since only the amino group of the amino compound acts as a dye center (dye center).

That as a medium for the mixture or the reaction product the amino compound and the alkylation compound preferably but not necessarily used solvent can also depending on its effectiveness as Swelling agents are selected for the polymeric substrate. Such solvents generally include aromatic ones Hydrocarbons, ethers, chlorinated aliphatic compounds, Esters, ketones and other compounds which promote the alkylation reaction or the properties that promote the colorability Do not interfere with the preparation. Such solvents are often also dye carriers.

Pie Ausv / ah 1 of a solvent that is not only a swelling

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solvent, but also a dye carrier or a dye auxiliary has the obvious advantage that it is the dye uptake of the treated by the formulation polymer molded body promotes. It is well known that the ability of a solvent to use a special polymeric material depends on it To bring about swelling, of the solubility parameter of the solvent in relation to that with the solvent in contact coming off polymeric material. The selection of swelling solvents viewed from the point of view of the solubility parameter is in "Interaction of Non-aqueous Solvents With Textile Fibers" in "Textile Research Journal", 42, 720 (1972), and in "The Solubility of Non-electrolytes" by Hildebrand and Scott, 3rd ed., Reinhold Publishing Co. (New York, 1949), described in more detail. In these studies it is indicated that the ability of a solvent to dissolve a polymeric material such as e.g. B. to swell a polyester, from the composition and crystallinity of the polymeric material depends. in the In the case of a polyester fiber, the degree of crystallinity depends on the spinning speed and the size of the used to produce the Fiber used spinneret.

Preferred swelling solvents for polyesters are aromatic Hydrocarbons, halogenated hydrocarbons, esters and ethar. Solvents that have little or no swelling The polyester effect are aliphatic hydrocarbons, alcohols and water. Usually should be water should be avoided as it tends to outweigh the beneficial properties of the sterically hindered amino compounds. Special swelling solvents for polyester moldings are the following: aromatic compounds such as benzene, Toluene, xylene (o-, m- and p-)> ethylbenzene, chlorobenzene,

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Dichlorobenzene (ο-, m- and ρ-)} bromobenzene, methyl benzoate, Ethyl benzoate and pyridine; Ethers, such as tetrahydrofuran, dioxane, dimethoxyethane; chlorinated solvents such as methylene chloride, Chloroform, trichlorethylene, 1,1,1-trichloroethane and perchlorethylene; as well as other solvents such as ethyl acetate, acetonitrile, nitromethane, dimethyl sulfoxide, dimethylformamide, Acetone and methyl ethyl ketone. Some of the solvents differ in terms of their activity against Polyester depending on the degree of orientation of the polyester from each other. For example, dimethyl sulfoxide is known to be used and dimethylformamide only used to swell a more oriented polyester.

The above-mentioned and other solvents can be used for other polymeric moldings. So tolerated for example nylon more active solvents, such as dimethylformamide, diethylformanide, Dimethylc.ee tain id, dirne thylsulfoxid and formic acid.

The polymeric moldings to which the inventive Preparation (composition) can be applied, include synthetic polymeric materials of any shape, such as fibers, films, and tapes, their dye receptivity by creating cationic centers in the polymer to attract and retain the acidic dye molecules can be improved. Except for the use. of certain more active soaking solvents the Treatment essentially equally good on non-stretched, partially stretched or fully stretched or oriented polymeric moldings. Although the polyester is of primary importance for its persistence

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against acid staining, improvements can also be made according to the invention can be achieved with respect to the dyeability of other polymers. Such other polymers include polyacrylonitrile, Polyvinyl chloride, polyvinylidene chloride, polymethacrylate, polymethyl methacrylate, polystyrene, polyethylene, Polypropylene, polyamides such as nylon 6 and nylon 6,6, and organic cellulose esters such as cellulose triacetate, cellulose propionate and cellulose butyrate or cellulose acetate butyrate. The polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate and other polymers in which part of the terephthalic acid is replaced by an aliphatic dibasic carboxylic acid such as adipic acid and / or sebacic acid. Particularly preferred are the copolyesters which contain at least 85 mol% ethylene terephthalate units contain.

The preparations (compositions) according to the invention can are applied in the form of coatings to the entire surfaces of the polymeric moldings or the preparations (Compositions) can be applied in the form of patterns or randomly to obtain a specific coloring to achieve in the resultant colored molded body. In addition, the treatment can cause color on color or different shades of the same color can be achieved. For example, a polymeric molded body stained with a background color using standard disperse staining techniques, simultaneously or then a treatment with an acidic dye (acid dye) is carried out.

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One color is achieved which is visible on the background color or a combination coloring is achieved. It is therefore now possible to use polyester moldings such as B. those made of fibers, yarns and fabrics, a colored pattern on a white background, such as. B. blue stripes on white background, apply tone-on-tone effects with good contrast, e.g. B. yellow patterns on a yellow background, and good tone-on-tone coloring to achieve on a dark background. The present invention opens up entirely new areas of dyeing techniques and color effects on polymeric moldings, dia with acidic dyes (acid dyes) or with a acidic dye (acid dye) in combination with a Disperse dye without impairment (Abbrai) the shaped body are difficult to stain.

The invention is illustrated in more detail by the following examples, but without being limited to it. The parts and percentages given therein relate if nothing else is stated on the weight.

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example 1

Each 1 equivalent of 2,5-dimethyl-2,5-hexanediamine and Neopentyl glycol diacrylate were in toluene at room temperature dissolved to form a 20% strength by weight solution. The solution was applied to undyed, partially oriented polyester yarn of 170 denier applied by dabbing the solution onto the ends of a cone of the yarn. After the solution was dried, the yarn was textured to 100 denier by drawing, and a sleeve was knitted therefrom. The whole The surface of the sleeve was then boiled for 45 minutes with a commercially available acid dye (0.1% aqueous solution from Merpacyl Blue SK). The parts of the yarn that have been pretreated with the diamine / diacrylate solution were stained slightly, as was the case with the untreated Sharing was not the case. The color was washable and the treatment did not render the yarn essential worsened (impaired).

Example 2

A first solution (solution A) was prepared by dissolving 1 part of menthediamine in 4 parts of toluene. Then became a second solution (solution B) prepared by dissolving 1 part of epoxy resin ("DER 73V, an epichlorohydr in / polyether adduct from Dow Chemical Co.) in 4 parts of toluene. Equal parts by volume of solutions A and B were mixed with one another forming mixtures with concentrations of diamine + adduct of 10, 15, 20, 25 and 30% by weight. The mixes were applied to a polyester yarn and the yarn treated in this way was dyed according to the method of Example 1,

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The results obtained were essentially the same as in Example 1. It was found that concentrations below 15% result in poor dye uptake and that no noticeable increase in dye uptake occurred at concentrations above 20%.

Example 3

The procedure of Example 2 was repeated in all essential points, but with the exception of the concentration the menthandiamine / epoxy resin mixture, which was 20% by weight, and the blend was applied to partially oriented polyester yarn of 355 denier using xylene as the solvent in the mixture as well as a partially oriented one 255 denier polyester yarn using toluene applied as a solvent in the mixture. Before applying The mixes were left on the yarn for 15 minutes, 30 minutes, Age for 1h, 2h, 4h, 24h and 9 days. Also the influence of the dyeing of yarns textured by Sredcen, which with the mixtures had been treated within 24 hours after application and after 1 week of storage at room temperature * door was examined. It was little or no Change in the dyeability, the running ability of the yarn and the fastness to washing of the dye was determined. The wash fastness was determined by boiling a sample from one Sleeve knitted from the pretreated dyed yarn in a 5% sodium phosphate solution for one Period of 30 minutes and also according to an ASTM procedure.

Example 4 Influences of accelerated aging

Knitted sleeves were made from a textured polyester yarn

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prepared as essentially described in Example 1, this time, however, the pretreatment with (A) a 20% solution of Menthandiarain alone, (B) a 20% solution which stoichiometric proportions of menthane diamine (MDA) and an epichlorohydrin / bisphenol Α resin ("EPON 828" from Union Carbide Corp.), and (C) a 20% solution of aminoethylpiperazine (AEP) was performed. With the aminoethylpiperazine it is a well-known reagent for the introduction of staining centers in polyester. The arms were wound up and wound on cones and duplicates of the cones were placed in ovens of 42, 63 and 126 C. Then the Tensile strength and elongation at break of the yarn on the cones determined after various oven heating times. The received Results are summarized in Table I below, in which the control represents an untreated yarn sample. The abbreviation "St.D" stands for "standard administration". The data show that yarn samples made with Preparations (B) that were pretreated and colored were essentially not impaired (degraded) like that Samples treated with an amine (AEP) that was not sterically hindered (C) ^. With samples treated with a solution (A) containing only MDA stained well and exhibited resistance to deterioration (Degradation) which was between that of the samples treated with the preparations (B) and (C). With (A) treated samples, however, had a poor wash fastness, indicating that the alkylation is required, e.g. B. by the epoxy resin to the amino compound to the Tie polyester.

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Table I. Tensile strength (g) elongation (%)

high low average !. Hours. high goring average1. Hours.

(A) HD A.

Control 635 520 568 45.91 38 27 31.5 4.51

5 days at 43 ⁰ C 620 460 570 62.85 38 25 33.8 '5.07

18 days at _63O ^ ₅ ^ ₆ ^ ₉ ^ ^. ^ _Q ^ ₄₄

43 ^V

; i
43 ° C

£ ^{25 days be} ^ ₃ o _c 622 535 586.7 4 ₅ .7 37 28 33.3 '4.73

Control 635 520 568 45.91 38 27 31.4 4.51

5 days at 63 ⁰ C ^ ₅ ^ ₅ ^ ₀ ^ ₇₂ ^ ^ . ^ _Q ^ ₅₃

18 days at ^ ^ ₀ ^ _QQ ^ ₃ , ^^ ^ _2Q ^^ ^^ _Q

27 days at ₆₃ o _{c 6l5} ^ ₇₅ ^ ₇ ^ ₇₀ ^ ^ ^ ₃₁ ^ ^ ₅₁

520 568 • 45.91 545 58O VJl 29.72 500 573 64.7 475 547. 5 70.3 575 599 6th 04/21 555 567. 13.23 533 551. 22.92

(B) Epon 82 8 / MDA

Control 625 575 599 21.04 32 30 31.3 O.96

5 days at 42 ⁰ C 585 555 567.5 13.23 34 31 32.5 1.29

ο Ui

18 days at 42 C 590 533 551.6 22.92 34 27 30.4 2.6l

OJ CJ

Table I continued for 27 days at 42 ^° C

⁵ ^ ⁷

522.3

21.36

27.7

_{3 # 51}

Koi roll 625 575 • 599 .5 21. 04 32 30th 31 .3 0 .96 5 days at 63 ° C 565 540 552 11. 9 33 '29 30th .3 1 .89 S 18 days at 63 ⁰ C
oa 610 545 '576 .8th 26th 2 33 27 30th .6 2 .51 2 27 days at 63 ⁰ C 553 500 531, 23 0 29 26th 27 .5 1 ^^
O ( S (C) AEP OT Λ / ■ / ■ SPY • 5 - · Control eleven 497 143 .2 38 17.5 29 > 2 '9, .05 5 days at 42 ° ^C 570 23Ο 435 3 176 .0 36 13th 25th , 6 10, .76 18 days at 42 ^° C 595 210 463. 2 162 .9 36.5 11 27 3 10. , 6 27 days at 42 ^° C 602 170 454 5 213 .7 37 6th 26th 3 14th 3 control 605 210 497 .8th 1 ^ 3, .2 38 17.5 29 2 9. ho
05-y 5 days at 63 ^° C 590 200 517. 140 5 36. 9.5 30th 6th 9. 42 00 CO CO

CVl

Q.%

in

ο co

VO CVJ

CO

ro

co co

CVJ

in

CO r- \

VD CO

in O

• ·

^ f CO

O in

in - = f

co

vo

O
VO 595 CJ
O
η
VO CJ
O
OK at at Days Days σο
ri r »
OJ

101027/0931

- 3 -

Examples 5 to 18

In the following Table II there are others according to the invention Preparations and polymeric materials treated therewith, essentially as described in Example 1, together with practically the same favorable results.

The present invention is useful for improving the dyeability and other properties of mixtures of shaped, synthetic polymer fibers, yarns or other materials as indicated above, as well as mixtures of any synthetic polymeric materials with natural materials or natural fibers, such as mixtures of polyester or nylon fibers with wool or cotton. The molded materials (molded articles) may have any shape including that of fibrous materials such as fibers, yarns and fabrics (woven and non-woven fabrics), and others Shapes, like films and tapes.

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Table II

preparation according to the invention

τ. . "Amino compound alkylating compound

.tic * J. Sp 1λ 3Γ

11

12th

13 14

15th

tert-butylamine

DER-736

6th tert-octylamine 7th Ad araant y1amin 09
^^ 3 1,2-diamino-2- (O rne thy I-propane OO 9 4-amino-2,2,6,6- \ te tr aiai: thy! piperidine O CO
<- * 10 2-amino-2-methyl-1-

propanol menthane diamine

^ Araldite RD-2

³ DEN ⁴ OF ⁵ ERL-4221

⁶ ERL-4206 total concentration (wt.%)

14.3 "

17.6

18.8

15th
19.1

20th
I7.7

I8.9

20th

16.8

I3.8

solvent

Polymer material

Toluene 263 denier.

POY ^;

255 denier POY

et »approx

Table II continuation

? rfindun, g; s proper preparation

play amino connection

No.

16 2,5-dimethyl-2,5-hexanediamine

Alkylating compound total concentration solvent (% by weight) medium

DER-736

17.2

Il

Il

Trimethylolpropane triacrylate 21.4

Neopentyl glycol diacrylate 17.8

Epichlorohydrin / polyester resin from Dow Chemical Co. Diglycidyl ether / butanediol resin from Ciba-Geigy Corp. Epichlorohydrin / methylenebisphenol resin from Dow Chemical Co.

_ »Epichlorohydrin / bisphenol Α resin from Dow Chemical Co. 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carbocylate 1-epoxymethyl-S ^ -epoxycyclohexane partially oriented polyester yarn

Dimethyl
sulfoxide

Dimethylformamide

toluene

Polymer
material

denier
textured yarn

Il

denier
POY

ro -j cn oo

Alternatively, those preferably used according to the invention can be used Amino compounds are represented by the following formula

H R I 1 °

R ₁ N (R) (N -R ₇ ) m

wherein R-, R-. and R _{7 are} each H or alkyl, ζ. Β. one with 1 to 6 carbon atoms, R a saturated or ethylenically unsaturated hydrocarbon group, 2. B. one with at least 10 carbon atoms, which has a valence of m + 1 and optionally aryl? Contains hydroxy, keto or aza (- NH -) - substituents, and m denotes the number 0 or an integer from 1 to 4, with the proviso that in each case two of the radicals R,, R, R-. and R ₇ can be linked to one another to form a cyclic group, and that in the radicals R ,, R, R ^ and R _{7 there is} at least one fully substituted carbon atom in the α- or ß-position to any amino group which is a non- has a tertiary structure, or that the carbon atom in a-position to such a non-tertiary amino group is bonded to two different carbon atoms which form part of a ring.

Most preferred are monotertiary alkyl amines; H. those in which m is the number 0 and R is a tertiary alkyl group, cycloalkylamines and alkylcycloalkylamines and diamines, d. H. those in which m is the number 0 or 1 and R is cycloalkyl, cycloalkylene, alkylcycloalkyl or alkylene cycloalkylene, and di-tertiary alkyl arenes, d. H. those in which m the Number 1 and R are di-tert-alkyl.

809827/0931

Claims (13)

Claims 1. Process for improving the dyeability of shaped, solid (solid) synthetic polymer moldings by acidic dyes by treating the solid polymer with a Acid dye receptor, marked thereby net that the reaction product is used as a dye receptor of or a mixture containing (a) an organic amino compound with at least one sterically hindered primary or secondary amino group, with the proviso that all other amino groups contained in the molecule and which are not in a sterically hindered position have a tertiary structure and (b) a difunctional alkylating agent. 2. The method according to claim 1, characterized in that there is used as the dye receptor, the reaction product of or a reaction mixture which contains components (a) and (b) in essentially stoichiometric amounts. 3. The method according to claim 1 or 2, characterized in that the polymer with a solution of the dye receptor treated in an organic solvent. 4. The method according to claim 3, characterized in that the solvent / for the dye receptor also a swelling agent represents for the polymer. 5. The method according to any one of claims 1 to 4, characterized in that that the dye-receptor used is the reaction product of or a mixture which is used as the amino component (a) contains a compound of the general formula ORIGINAL. INSPECTED " ⁵ T J m wherein R ₁ to R _{7 are} each H, alkyl (including cycloalkyl), substituted alkyl (including substituted cycloalkyl), aryl, or substituted aryl, with the proviso that (i) one of _{R 1 to R 7} with another of the groups R 1 to R ₇ can be linked to form a cyclic group and (ii) that when an amino group has a primary or secondary structure, at least one of the carbon atoms in a cc or beta position thereto is fully substituted, and in which m is the number 0 or an integer from 1 to 4 and η is an integer from 1 to 10. 6. The method according to any one of claims 1 to 4, characterized in that the dye receptor used is the reaction product of or a mixture which contains one or more of the following compounds as amino component (a): a tertiary (C, -C _Q ) -Alkylamine
a menthane diamine
2,5-dimethyl-2,5-hexanediamine
α, a-Dine thylbenzy lamiri
1- / imino-1-eye 1 openty! Methanol
Trishydroxymethylaminomethane
1-aminoadamantane
2-amino-2-methyl-1,3-propanediol
2-amino-2-methyl-1-propanol
1-amino-1-methyl-cyclohexane 809827/0931 1-amino-1-methyl-cyclopentane 1,3-D iaminoadamantane Neopentylamine Is οphorondi amine 1,2-diamino-2-methylpropane 1,3-diamino-2,2-dimethylpropane 4-amino-2,2,6,6, tetramethylpiperidine 3,3,5, S-tetramethylcyclohexylamine 2,5,5,7,7,10-hexamethyl-6-aza-2,10-diaminoundecane 1,3,5-trimethyl-1,3,5-triaminocyclohexane 1,3,5,7-tetraminoadamantane or 1,3,5-triaminoadamantane. 7. The method according to any one of the preceding claims, characterized in that one is used as the difunctional alkylating agent a polyepoxy compound, a polyhalide that is adjacent has no tertiary carbon atom to a halogen atom, or an α, ß-polyethylenically unsaturated compound with a carbonyl group which is adjacent to at least one of the ethylenic double bonds is used. 8. The method according to claim 7, characterized in that there is one or more as difunctional alkylating agent of the following connections are used: 1,2,5,6-Diepoxycyclooctane 1,2,7,8-Diepoxyoctane 3,4 ~ epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate l-epoxyethyl-3,4-epoxycyclohexane a polyepoxy adduct of epichlorohydrin with a polyhydroxy phenol or a polyether glycol, a dihalide of the formula X (CH ₂ > _n X or XCH ₂ C ₆ H ₄ CH ₂ X, wherein X is Cl, Br or J and η is an integer from 2 to 809827/0931 10 mean
a vinylbenzyl halide oligomer containing 2 to 10 units of the formula -CH - CH - wherein X is Br or Cl C ^ H ₇ CH ₉ X means,
an ester of a cx, ß-ethylenically unsaturated polycarboxylic acid with a polyhydroxy alcohol or polyhydroxy polyether, divinyl ketone and
4,4-dimethyl-2,5-cyclohexadienone. 9. The method according to claim 7, characterized in that there is an adduct of as the difunctional alkylating agent Epichlorohydrin used with bisphenol A, methylenebisphenol or a polyalkylene ether glycol. 10. Process for coloring synthetic polymer molded articles with an acidic dye (acid dye), in which the polymer is pretreated with an acid dye receptor under-throws to the dye uptake capacity to improve the polymer, and then dyes the treated polymer with an acidic dye (acid dye), characterized in that the acid dye absorption capacity the polymer improved by treating the polymer by a method according to any one of the preceding Expectations. 11. The method according to claim 10, characterized in that after the pretreatment, the polymer is sequentially or simultaneously with an acid dye and a disperse dye different colors or tints. 809827/0931 12. Acid dye receptor preparation, characterized in that that it contains the reaction product of or a mixture which contains (a) an organic amino compound with at least one sterically hindered primary or secondary amino group, with the proviso that all other amino groups present in the molecule which are not in a sterically hindered position have a tertiary structure, and (b) a difunctional alkylation agent. 13. Preparation according to claim 12, characterized in that the dye receptor has a composition such as it is required according to one of claims 2 and 5 to 9, 809827/0931