NO139196B - PROCEDURE AND CIRCUIT TO RECOVER THE VIDEO OR DENAL CARRIED COLOR DIFFERENCE SIGNALS FROM A PAL COLOR FACE - Google Patents

Description

Procedure for processing polymeric materials.

The present invention concerns

treatment of polymeric materials containing at least one reactive -OH, >NH or SH group in each molecule, e.g. cellulose-containing material such as paper, wood or cellulose film, cellulose derivatives such as e.g. cellulose acetate, protein materials such as e.g. wool or leather, and polyvinyl alcohol. More particularly, the invention relates to the treatment of cellulose textile materials such as e.g. fibres, yarns and fabrics, including woven or knitted or non-woven fabrics, e.g. "bonded" fiber fabrics of cellulose or cellulose derivatives.

According to the invention, a polymeric material, which in each molecule contains at least one reactive -OH, >NH or SH group, is treated in the presence of an alkaline or potential alkaline catalyst, with a sulfonium salt which, in the presence of the catalyst, liberates the following sulfonium cation I, which has two free valences:

in which R 1 and R 2 are hydrogen or a lower alkyl ring. os is the same or different, and R., and R, is the group

CHR2-) or an alkyl, substituted alkyl, alicyclic, aralkyl, aromatic or heterocyclic residue, and may be the same or different.

The lower alkyl group preferably contains 1-3 carbon atoms. The substituent on the alkyl residue preferably does not contain -OH, >NH or -SH groups, but can e.g. be carboxyl, nitrile or halogen.

Since it is the cation that is the important part of the sulfonium salt for the purposes of the present invention, the anion can be any anion.

The polymeric material can be defined as GZH, where G represents the rest of a polymeric chain and Z represents O, N or S, and the invention also encompasses the reaction between the polymeric material and the sulfonium salt.

According to the invention, this therefore also includes the method of

production of a product which has the following general formula:

where G, R 1 , R 2 , R 8 , R 4 and Z have the meanings given above, or R s and/or R may represent CHR 1 -CHR 2 ZG.

Among substances that can react with the polymeric material and give products that fall within this definition are: 1) p-hatlo<g>em-ethyl salts such as e.g. (XCH2 CH2)2R., + Sy- or (XCH2<C>H2)3 S + y-, where R., has the above meaning, X represents halogen and y— represents an anion. An example of such a salt is tris-(p-chloroethyl)-sulfonium chloride; 2) esters of mono-, bis- or tris-(3-hydroxyethyl-sulfonium salts) such as e.g. where RH has the above meaning, or the disodium salt of tris-((3-sulfaethyl)sulfoinium inner salt having the formula:

In carrying out the present invention, material to be treated can, for example, be impregnated with a sulfonium salt as defined above in aqueous solution, which can be alkaline, or the material can be treated with alkali as a separate work step. For example, the material can be treated with an aqueous solution of the sulfomium salt and then treated at room temperature with an aqueous solution of a strong alkali, e.g. sodium hydroxide, after which the material is washed. It is therefore preferred to use sulfonium salts which are soluble in water or alkali. Alternatively, they can be used in the form of an emulsion.

When the materials are treated simultaneously with sulfonium salt and a potential alkali such as e.g. potassium hydrogen carbonate, it may be necessary to dry the materials by heating or to heat them to a high temperature, e.g. to over 100°C (ie "bake" them) to start the reaction. In all cases, the method according to the invention is very simple and quick to carry out, and under suitable conditions it only consists in impregnating the material in a cold state, without subsequent heating to a high temperature.

The invention includes the treatment of cellulose-containing and protein-containing textile materials with sulfonium salts and with resins or other agents that provide resistance to creasing or with formaldehyde or other agents that provide cross-linking compounds, whereby the textiles are given increased resistance to dry creasing and other properties. The increase in resistance to dry creasing is particularly noticeable in such textile materials which have been treated with small amounts of sulfonium salts.

This combined treatment is particularly useful in the case of textile fabrics which have been produced from cellulose-containing fibres, such as e.g. of cotton, linen or viscose artificial silk. In carrying out this combined treatment, the material can first be treated with the sulfonium salt and an alkali or a potential alkali, and then treated with an aqueous solution of an intermediate condensation product of a synthetic resin, e.g. urea-formaldehyde or melamine-formaldehyde, together with an acid catalyst, followed by drying and heating to harden the resin.

Alternatively, textile materials can be first treated with an intermediate condensation product of a synthetic resin and an acid

catalyst, and the materials then become

dried and heated to form the resin, and finally the textile materials are treated with a sulfonium salt and an alkali or potential alkali.

As yet another alternative, the textile materials can be treated with a mixture of the intermediate condensation product of a synthetic resin together with an acid catalyst and a sulfonium salt, after which the thus treated textile material is dried and suspended so that the resin is formed, after which it is treated with alkali.

If urea-formaldehyde resin is used in such combined treatments, sodium bicarbonate can be used as a catalyst both for the resin formation and to induce the reaction with a sulfonium salt.

Cellulosic or protein-containing materials, e.g. paper or non-woven fabrics, such as "bonded" nonwovens produced from cellulose or proteinaceous fibers, which have reacted according to the present invention with sulfonium salts as defined above, in which R;j and/or R, repre-i

center group (CHR,-CHR2-) has greater resistance to swelling than unreacted materials have. Woven cellulose or protein fabrics which have reacted according to the invention with sulfonium salts as defined above, in which R., and/or R4 re-i

presents the group (CHR,-CHRr) has increased resistance to shrinkage after washing, compared to untreated fabrics. Woven cellulose fabrics, e.g. made of cotton or viscose rayon, dries better to a smooth state than untreated fabrics, i.e. they require less ironing after washing. They also have the property that even when washed they retain curls and mechanically applied, e.g. pleated, gloss or embossed effects,

which have been produced before or during the treatment according to the invention, and they may have increased resistance to dry creasing, compared to unreacted fabrics. These vir tonings are accompanied by good wear resistance. Fixation of various stiffening substances, e.g. starch products on polymeric materials are improved compared to unreacted fabrics.

The reacted clothes do not retain chlorine in such a way that they are damaged or discolored when washed with chlorine-containing bleaches. Cellulosic materials, e.g. cotton or jute, and protein-containing materials such as e.g. leather, which has been treated according to the invention, has increased resistance to attack by powdery mildew, compared to untreated cellulosic or proteinaceous materials.

The inventors prefer to treat woven fabrics of cellulosic material, e.g. linen, cotton or viscose rayon.

Mixtures of polymeric materials with each other or with other materials can be treated according to the invention.

When materials that are thought to be damaged by alkali are treated, the type of alkaline catalyst and the treatment can be regulated so that the damage is as minimal as possible.

When carrying out the invention, alkaline catalysts of different strengths can be used, e.g. sodium hydroxide, carbonate or silicate. Alternatively, a potentially alkaline catalyst can be used, e.g. sodium or potassium bicarbonate. If the sulfonium salt is of the type that e.g. a fi-halogenethyl salt or an ester of mono-, bis- or tris-p-hydroxy-ethyl-sulfonium salt, it is necessary that alkali be present in sufficient quantity to neutralize any acid which may be liberated, and a small excess which is sufficient to catalyze the reaction with the polymeric material, e.g. to raise the pH value to 12.

The positive charge on the sulfur atom, which remains after the sulfonium salt has reacted with the polymeric material, gives the reacted material new properties. For example, cellulose fabrics have a greatly increased affinity to anionic dyes. As a result of the positive charge on the sulfonium salts defined above, such dyes become substantive in relation to materials that carry negative surface charges, and this is useful in the manufacture of e.g. paper.

When salts are used which, in the presence of alkali or potential alkali, release the cation I, R., and/or R, can be used to introduce other desirable properties into the compound. If e.g. R:! and/or R, is a long-chain alkyl group, the substance can act as a plasticizer or lubricant, or as a water-repellent agent, when it has reacted with the polymeric material. If R., and/or R, contain chromophoric groups, or constitute a residue of a dye, the compound constitutes a reactive dye, analogous to those sold by Imperial Chemical Industries under the trademarks "PROCION" and "REMAZOL", which is capable of reacting with suitable polymeric materials, e.g. cellulose or cellulose acetate, and give wash-fast dyes.

The sulfonium salts which release the cation I in the presence of alkaline or potentially alkaline catalyst, can e.g. are prepared by the addition reaction between hydrogen sulfide and ethylene oxide or substituted ethylene oxide, whereby hydroxyalkyl sulfides are formed, which are then reacted in an appropriate manner to form the sulfonium salts.

The invention is explained in more detail in connection with the following examples.

Example 1.

A poplin cotton cloth was impregnated with a solution 0.3 molar with respect to the disodium salt of tris-((3-sulfateethyl)sulfonyl)sulfonyl inner salt, and was pressed between the rolls of a rolling machine, which was set so that the cloth retained about 75% of its weight in the form of solution. The cloth was then placed on a needle frame, dried at 50°C and then dipped in a 10% solution of sodium hydroxide at 20°C for 10 minutes ., washed successively with dilute acetic acid, ammonium hydroxide and water, and then dried.

The treated fabric had greatly increased resistance to wet creasing and dried to a smooth state, compared to untreated fabric, and had satisfactory wear resistance and tensile strength.

The tensile strength did not decrease after the treated sample had been subjected to the chlorine resistance test described in the American Association of Textile Chemists & Colourists' Tentative Test Method 92/1958.

The sample treated as above with the sulfonium salt was also washed 20 times in 0.25% soap, 0.25% sodium carbonate at 70°C, each wash lasting 30 minutes. The washed sample also had good resistance to the chlorine test indicated above, and the physical properties were practically unchanged.

The test methods used in the above and in the following examples were as follows: S.D.I. (Smooth Drying Index) •— using an apparatus consisting of (1) a pleating apparatus, (2) a drying chamber, (3) a crease gauge. Sample pieces of the fabric are cut out in both the warp and weft directions. These are moistened, pressed through a small household roller and introduced into the curl maker, so that a sharp double fold or curl is formed. The test piece is then dried for y2 hours and during the drying the fold or crease introduced in the wet test piece decreases. The S.D.I. number is calculated based on how big this is

"recycling" is, and indicates the ability of the fabric to eliminate creases that form during normal household washing. The degree of recovery is measured by placing the dried test piece in the device's compartment (cabin net) and measuring the remaining fold or crease angle using the shadow that the fold casts when it is illuminated with directed light from a light source. The lower the number this test gives, the less, if any, ironing with an ironing machine the clothes need after washing. This measurement method is described in British patent no. 846 875.

Ring wear is determined using the Ringwear Machine described in Textile Recorder Year Book 1942-3, page H.36.

The tensile strength is determined using the Heal Tensile Testing Machine.

Example 2.

Resistance to microbiological attack.

The clothes in e.g. 1, treated as ex. 1, was also subjected to the decay test described in Journal of the Textile Institute, 51, T. 75 (1960). The tensile strength of the strips was measured after 9 and 30 days and the following data were found:

It can be seen that treatment with the sulfonium salt gives poplin cotton wool a significantly increased resistance to rotting.

Example 3.

Increased color affinity in treated

cotton cloth.

A piece of cotton cloth became as in ex. 1 treated with a solution of the disodium salt of tris-((3-sulfateethyl)-sulfonium inner salt, as described in example 1.

Pieces of this cloth, together with pieces of the untreated cloth, were dyed with different dyes, in the following ways: (a) The test pieces were boiled for 20 min. in a

solution that contained:

0.12 g sodium dichromate 5 ml 2 N sulfuric acid

100 ml of water,

was thoroughly rinsed and dipped in a solution containing: 0.08 g "Chrome Fast Violet B" (Colour Index, Mother Violet 5)

0.4 g sodium sulfate crystals,

0.5 ml 2 n acetic acid 100 ml water.

The exit temperature of this solution was 40°C. During approx. 30 min. the solution was heated to boiling and was kept at this temperature for a further 40 min. The test pieces were then washed well and dried.

The sulfonium-treated samples were found to be dyed to a deep shade, while the untreated samples of the cotton fabric were only very faintly dyed. It was also found that the samples treated with sulfonium could be dyed to a similar deep shade even if the pre-treatment with chromium was omitted.

(b) The test pieces were boiled for 45 min. in a

solution that contained:

0.03 g Durazol Blue 8G (150% strength)

(Colour Index, Direct Blue 86),

0.2 g sodium sulfate crystals,

0.06 g sodium carbonate crystals,

150 ml of water,

rinse well and dry. The sulfonium-treated sample had been deeply stained, while the untreated cotton fabric had only been slightly stained.

(c) A solution was prepared which

contained:

0.02 g "Lissamine Fast Red. B.G.” (Color

Index, Acid Red 37)

5.0 g sodium sulfate crystals 2.0 ml 2 N sulfuric acid 100 ml water,

and this solution was heated to 40°C.

The test pieces were dipped in this solution and during approx. 30 min. the solution was heated to boiling. Boiling was continued for a further 30 min. The test pieces were then washed well and dried.

The sulfonium-treated samples had been dyed to a deep shade, while the untreated cotton had only been very lightly dyed.

(d) A cold solution was prepared

that contained

0.05 g "Procion Yellow HAS" in 300 ml water.

The test pieces were placed in this solution for 16 hours and then boiled for 1 hour in a solution containing 0.25% soap and 0.25% sodium carbonate.

The sulfonium-treated test pieces acquired a deep orange color, while the untreated cotton was only slightly colored.

Example 4.

Treatment of cotton clothes.

A cotton fabric was treated with a solution 0.5 molar with respect to tris-((5-chloroethyl)sulfonium chloride) and then pressed between the rollers of a roller machine, which was adjusted so that the fabric retained about 75 percent of its weight as liquid. The cloth was then placed on a needle frame and dipped for 3 minutes in a 5% solution of sodium hydroxide at 20°C, and was then successively washed with dilute acetic acid, ammonium hydroxide and water, and then dried .

The -treated cloth had a greatly increased resistance to creasing when wet, and dried to a smooth state after washing, compared to untreated cloth, and had satisfactory wear resistance and tensile strength.

The treated fabric also had increased affinity to dyes.

Example 5.

Processing of paper.

Strips (15.2 x 2.5 cm) of a bleached and lightly pasted paper were dipped into a solution containing 0.5 mol/ltr. sodium salt of tris-([3-sulfateethyl)sulfonium salt and 1.6 mol/ltr. NaOH. They were allowed to drip off, were dried in a container at 70°C, then heated at 150°C for 2 min., washed for 5 min. in a 60° solution containing 0.25 per cent soap and 0.25 per cent sodium carbonate, rinsed and dried.

The wet strength of the strips was then measured in a Scott inclihed plane tensile tester, the jaws of which were set 127 mm apart. The treated strips had a breaking strength of 0.54 kg and the untreated 0.135 kg.

Example 6.

Treatment of cellulose acetate cloth.

An impregnation solution was prepared by mixing: 20 ml of a molar solution of the dinatrum salt of tris-((3-sulphate<y>l)sulfonimine salt, 50 ml of a 2 molar solution of potassium bicarbonate , and

30 ml of water.

A sample piece of a cellulose acetate fabric was passed through this solution, then through a roller set so that the fabric retained approx. 90 percent of its weight of liquid, dried for 90 min. at 90°C, and washed thoroughly with water.

The treated cloth did not dissolve in water, and had increased affinity to dyes, e.g. to "Durazol Blue 8B" (Colour Index "Direct Blue 86").

Example 7. I

Processing of cellulose film.

A test piece of a film of regenerated cellulose was dipped into it in ex. 6 described impregnation solution and the excess liquid was dried away using filter paper. The film was then dried for 90 min. at 90°C and washed thoroughly.

The treated film had increased affinity to anionic dyes, e.g. "Durazol Blue 8B, and had a somewhat greater breaking strength in the wet state than the untreated film.

Example 8.

Treatment of gelatin film.

A solution was prepared by mixing: 0.5 ml of a 0.96 molar solution of the disodium salt of tris-((3-sulfateethyl) sulfonium inner salt 16 ml of a 2.4 molar solution of ca -lium bicarbonate, and

79 ml of water.

A sample piece of a gelatin-coated cellulose acetate film was dipped in this solution for 5 min., the excess liquid was removed with the aid of a sponge, and the piece was then dried for 5 min. at 80° C in an oven. The specimen was then placed in boiling water together with a piece of the untreated gelatin coated film. Almost instantly, the gelatin coating on the latter blistered significantly and detached from the back layer, while the treated film could be boiled for at least 30 min. without blister formation or dissolution occurring. This shows that the gelatin had increased resistance to swelling.

Example 9.

Treatment of non-woven fabric.

A fiber mat was produced which contained 55 wt. rayon fibers and 45 wt. nylon fibers. The weight of the mat was approx. 0.04 g/cm-.

Two impregnation solutions A and B were prepared as follows:

["Galvatol 20-90" is the brand name of a copolymer of vinyl alcohol and vinyl acetate, where the alcohol is the main component. It is manufactured by Shawinigan, Resins Corporation, Massachusetts.]

Separate pieces of the mat were impregnated with solutions A and B, dried and heated for 3 min. at 140°C. The weight gain in both cases was approx. 12 per cent, referred to the treated cloth.

2.5 cm wide strips were cut from each mat, and their tensile strength

were measured after they had been dipped for 1 min. in cold water.

The results are listed below.

Example 10.

IN

Stiffening with starch and folding of viscose-rayon fabric.

Two impregnation solutions were prepared as follows:

[Solvitose HDF is the trade name of a preferred starch product.]

Sample pieces of a fabric of spun viscose rayon were passed through these solutions and passed between the rollers in a twisting machine or roller, which was adjusted so that 100 per cent of the liquid calculated on the weight of the fabric was retained in the fabric. Both test pieces were then dried and pressed so that sharp folding edges were formed.

The folded test pieces were then dipped for 2 min. in a cold 10 percent solution of potassium hydroxide, rinsed well and boiled for 30 min. in a solution containing 0.25 per cent soap and 0.25 per cent sodium carbonate.

The sample that had been treated with impregnation solution A retained its sharp folds, while the sample that had been treated with solution B showed only very light marks where the folds had been made.

The sample piece treated with solution A was very stiff after coking, while the other sample piece was only slightly stiffer than the original untreated rayon fabric.

Example 11.

Combined treatment with resin and sulfonium salt.

Three impregnation solutions were prepared as follows: A. 600 ml of a 45% solution of the disodium salt of tris-(p-sulfateethyl) sulfonium inner salt and

400 ml of water.

B. 400 ml of the resin product «L. 1714",

50 ml of a 20% aqueous solution of zinc nitrate, and 550 ml of water. C. 600 ml of a 45% solution of the disodium salt of tris-(p-sulfateethyl) sulfonium inner salt, 400 ml of the resin product "L. 1714", and 10 g of zinc nitrate crystals. ["L. 1714" is the trade name of a melamine/ethylene-urea-formaldehyde resin (50% solids content), sold by British Industrial Plastics Ltd.] Test pieces of cotton poplin fabric were treated as follows: Test piece 1 was dipped in solution A and passed through a wringer so that the laundry retained 50 per cent of its weight of liquid, dried and dipped for 3 min. in a 10% sodium hydroxide solution. The sample was then washed with water, diluted acetic acid and water again.

Sample 2 was treated in the same way as sample 1, and was then dipped in the impregnation solution B. It was then passed through a turning machine set as above, dried and heated for 3 min. at 150°C, and then washed in hot soap solution and water.

Test piece 3 was only treated in the impregnation solution B. The subsequent treatment was as for test piece 2.

Test piece 4 was treated in the same way as test piece 3, and was then dipped in the impregnation solution A. It was then dried, dipped for 3 min. in a 10% sodium hydroxide solution, and washed in water, dilute acetic acid and then water.

The test piece 5 was dipped in solution C, passed through a turning machine set as indicated above, dried and heated for 3 min. at 150°C.

All the test pieces were dried, conditioned and examined. The samples treated with resin contained approx. 10 weight percent resin.

[Dry creasing resistance (CR.) was

measured using the apparatus described on page 388 of "An Introduction to textile Finishing" by J. T. Marsh, published by Chapman and Hall in 1948.

S.D.I. means Smooth Drying Index, like this

as defined above.]

Example 12.

Processing of paper.

22 g of bis-((3-hydroxyethyl)ethylsulfonium bromide was boiled under reflux for 4 hours together with 4 g of phosphorus pent-otoside in sodium-dried benzene. After evaporation of the benzene, the resulting viscous mass was extracted with water ,

and the aqueous solution was neutralized to pH 6.0 using dilute sodium carbonate solution. This solution was then evaporated to dryness and extra-

hardened with methanol. The extract was analyzed and proved to consist of 60 percent of the desired phosphate ester and 40 percent of the original sulfonium bromide.

An impregnation solution was prepared by dissolving 2 g of this mixture in 50 ml of water. An alkali-resistant paper was dipped in this solution, lightly blotted with blotting paper, dried, and then dipped for 3 min.

in a 0.4% solution of sodium hydroxide. After prolonged washing, the treated paper was found to have increased affinity to acid dyes (eg Durazol Blue 8G) compared to paper that had only been treated in the alkali.

Example 13.

Processing of paper.

67 g (0.3 mol) of lauryl mercaptan were added

added to 0.3 mol sodium methoxide at room temperature. For the mixture, long-

to which 26.5 g (0.3 mol) of 2-chloroethanol were added and the whole was heated with reflux cooling for 15 min. The precipitated salt was filtered off and the filtrate was evaporated, leaving a residue consisting of crude lauryl-2-hydroxyethyl sulfide. This remainder was e-

quenched with benzene, whereby the pure sulphide was obtained, which melted at 26-27°C. The yield was 72 per cent.

The pure sulfide was dissolved in benzene

and refluxed for 1 day in an excess of methyl iodide. After removal of the solvent and excess halide, the sulfonium product was extracted with ether, washed with a solution of sodium thiosulfate, dried and evaporated to dryness. The pure methyl-2-hydroxyethyl-laurylsulfonium iodide melted at 9-11°C.

18.6 of this sulfonium iodide was treated with a small excess of chlorosulfonic acid and allowed to stand for 30 min. The mixture was then poured onto ice and extracted with chloroform. The chloroform was evaporated and replaced with anhydrous ethanol, to rest

when sodium ethoxylate was added slowly

south, until the pH was approx. 6.0. solvent

was easily evaporated, and as shown, an oily residue of methyl-2-sulfateethyl-lauryl-sulfonium inner salt was obtained.

A paper sample was treated with a solution of this compound, was dried and dipped in a 10% sodium hydroxide solution, washed with water, dilute acetic acid and again with water. The treated paper had a greatly increased affinity to anionic dyes.

Claims (11)

1. Procedure for processing polymeric material, characterized in that material, such as e.g. cellulosic textile material, paper, wood, wool or leather, which in each molecule contains at least one reactive -OH, >NH- or SH group, is treated in the presence of an alkaline or potential alkaline catalyst, with a sulfonium salt which, in the presence of the catalyst, releases the following sulfonium cation I, which has two free valences: in which R, and R2 are hydrogen or methyl, provided that both R, and R2 are not methyl, and R3 and R4 are the group (CR,-CHR2-), an optionally long-chain alkyl or an aralkyl residue, and may be same or different. 2. Method according to claim 1, characterized in that the sulfonium salt is an ester of a mono-, bis- or tris-(3-hydroxyethyl-Jsulfonium salt). 3. Method according to claim 2, characterized in that the sulfonium salt is where R3 has the meaning stated in claim 1. 4. Process according to claim 2, characterized in that the sulfonium salt is 5. Method according to claims 1-4, characterized in that the amount of catalyst is sufficient to raise the pH to 12. 6. Method according to any one of claims 1-5, characterized in that the catalyst is sodium hydroxide, sodium carbonate, sodium silicate, sodium bicarbonate or potassium bicarbonate. 7. Method according to claims 1-6, characterized in that the polymeric material is treated with an aqueous solution of the sulfonium salt and then with an aqueous solution of a strong alkali at room temperature, and then washed. 8. Method according to any one of claims 1-7, characterized in that the polymeric material is polyvinyl alcohol. 9. Method according to any one of claims 1-7, characterized in that the polymeric material is cellulose or protein-containing textile material, and that the treatment includes treatment with resin or other anti-creasing agent or formaldehyde or other cross-linking agent. 10. Method according to claim 9, characterized in that the polymeric material is treated with a mixture of an intermediate condensation product of a synthetic resin and an acidic catalyst, and the sulfonium salt, dried and heated to form the resin, and then treated with the alkaline or potentially alkaline catalyst. 11. Method according to claim 10, characterized in that R:1 and/or R4 contain a chromophore group or a residue of a dye.