GB1562099A

GB1562099A - Coning oils

Info

Publication number: GB1562099A
Application number: GB50504/76A
Authority: GB
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 1976-12-03
Filing date: 1976-12-03
Publication date: 1980-03-05
Also published as: AU3111877A; DE2753646C2; JPS5370273A; NL7713268A; TR19785A; BE861418A; FR2372887B1; AU508010B2; DE2753646A1; FR2372887A1

Description

(54) CONING OILS (71) We, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V., a company organised under the laws of The Netherlands, of 30 Carel van Bylandtlaan, The Hague, The Netherlands, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to novel textile lubricating oil compositions, to a process for treating or oiling textile fibres using such compositions and to the treated or oiled textile fibres so prepared.

Lubricating oils have been used in the processing of textile fibres for many years. Usually the lubricating oils are mineral oils but there is an increasing tendency to replace such oils by synthetic oils.

One textile process in which lubricating oils have been applied is the winding of yarns, e.g. continuous filament yarns onto cones. Such cones are then used in knitting processes. In such processes the yarn is wound at high speeds, e.g. from 300 to 1,000 metres/minute, onto the cone. Before being wound the yarn passes over a roller, usually described as a lick roller, which is partly immersed in a bath of the lubricating oil, by which means the yarn becomes lubricated or oiled. The lubricating oils used in this process are sometimes described as coning oils or knitting oils and the process is sometimes described as coning. Further information on coning oils may be obtained from the Book of Papers for the 13th Canadian Textile Seminar, 1972, pages 68 to 73.

Coning oils should preferably have the following characteristics. They should be good lubricants i.e. produce low yarn/yarn and yarn/yarn guide (metal, ceramic) friction; they should be water-soluble or emulsifiable in order that they may be scoured or washed from the final textile articles and they should be non-corrosive, non-toxic, biodegradable and physically and chemically stable.

A further desirable characteristic which is now receiving increasing attention is that they should be non-splashing or non-slinging. Splashing or slinging is a phenomenon observed during the high speed winding of yarns which results in oil droplets being "slung" off the yarns immediately after they loose contact with the lubricating rollers. Such oil droplets fall onto the winding machine and the floor which, apart from resulting in a loss of oil, endangers the operators and increases costs as a result of the necessary cleaning operation.

The Applicants have now discovered a lubricating oil composition which has the desirable characteristics required for coning oil. In particular the lubricating oil composition of the present invention are substantially non-splashing and are water-soluble.

According to this aspect of the present invention a lubricating oil comprises a major proportion of an ether of formula: R-Ot CmH2m wx H wherein R is a C1 to C10 alkyl group, m is an integer of from 2 to 4, and x is an integer of from 2 to 20 and a minor proportion of a polymer of an ethylenically unsaturated carboxylic acid.

According to another aspect of the present invention a process for treating or oiling textile fibre comprises contacting the textile fibres with a lubricating oil composition as defined in the previous paragraph. Although the lubricating oil compositions may be used in various textile processes, for example carding and spinning processes, they are particularly useful in coning processes. According to this preferred aspect of the present invention the textile fibres are contacted with the composition during the winding thereof onto cones. For example the textile fibres or yarns are wound onto cones by passing the fibres or yarns over a roller which is partly immersed in a lubricating oil composition. Alternatively the composition may be applied to the fibres or yarns during the winding thereof onto cones by nozzle-type applicators. Before the yarn is treated with the coning oil it is conventional practice to apply a texturising treatment to improve the bulk thereof. The yarn is suitably in the form of continuous filaments and the process is parficulafly suitable for treating texturized continuous filament yarns of synthetic material such as polyester or nylon. Usually the amount of lubricating oil composition picked up by the yarn is between 2 and 5 Ssw based on the weight of the yarn.

The lubricating oil components of the compositions of the present invention are suitably prepared by reacting one or more C1 to C10 alcohols, or a C2 to C4 alkoxylate thereof, with one or more C2 to C4 alkylene oxides i.e. ethylene oxide, propylene oxide or butylene oxide or mixtures thereof. Preferred components are those derived from C1 to C4 alcohols, i.e. compounds of the above formula wherein R is C1 to C4, in particular those derived from methanol, ethanol or mixtures thereof. Preferred components are those derived from ethylene oxide, i.e. compounds of the above formula wherein mis 2. Preferably the amount of C2 to C4 alkylene oxide is such that x has an average value of from 2.5 to 10, more preferably of from 3 to 8. Usually the alkoxylation product is a mixture of different chain length alkoxylates which may be separated into various fractions if desired.

An anti-splashing agent is also present in the compositions of the present invention. It should be pointed out that the function of the anti-splashing agent is not to thicken the lubricating oil but to impart to the oil the property of stringyness or pituituousness. This property prevents oil droplets being slung off the yarn during the oiling or coning process.

As stated hereinbefore the anti-splashing agent is a polymer of an ethylenically unsaturated carboxylic acid. Such polymers may be those derived from one or more ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid i.e. acids having the general formula: CnH2n-1COOH, and/or one or more ethylenically unsaturated dicarboxylic acids such as fumaric acid or maleic acid i.e. acids having the general formula: CnH2n-2(COOH)2 wherein, in both formulae, n is a whole number of from 2 to 10, preferably of from 2 to 6.

The aforesaid polymers may be homopolymers or copolymers i.e. polymers of an ethylenically unsaturated carboxylic acid and one or more different monomers. Examples of different monomers include unsaturated monomers such as ethers e.g. C1 to C4 vinyl ethers, esters e.g.

C1 to C4 esters of acrylic acid or methacrylic acid, amides e.g. acrylic acid amides, salts e.g. acrylic acid salts, and olefins e.g. ethylene. The only restriction on the type of monomers used is that the polymer should be sufficiently soluble in the lubricating oil component. The preferred comonomers are esters, in particular C1 to C4 vinyl ethers.

The polymers may be prepared directly i.e. by polymerizing an ethylenically unsaturated carboxylic acid, optionally in the presence of other monomers, or indirectly i.e. by polymerizing an ethylenically unsaturated carboxylic acid group precursor, e.g. an anhydride such as maleic anhydride, again optionally in the presence of other monomers, followed by conversion of the carboxylic acid group precursor, e.g. by hydrolysis, into carboxylic acid groups.

This conversion may take place before or after the polymer is added to the lubricating oil component.

Suitable polymers are those having an average molecular weight of from 4x 104to 2 x 107.

Suitable polymers are copolymers of maleic acid and a C1 to C4 vinyl ether and may be represented by the following formula

wherein B is a C1 to C4 alkyl group, preferably methyl, and p is an integer. Such polymers may be added to the lubricating oil comPonent in the form of its anhydride which is then hydrolysed, at least partially, e.g. by adding an alkali-metal hydroxide. Consequently most of the anhydride groups will be converted to acid groups and some of the acid groups may be in form of carboxylic acid salt groups. Polymers of these types are commercially available under the name GANTREZ (ex GAF). Specific examples include GANTREZ AN 169 and GANTREZ HY-H. ("GANTREZ" and "GAF" are registered Trade Marks) Other suitable polymers consist mainly of the recurring units of the formulae:

wherein R' is H or methyl, R2 is a carboxylic amide or ester group, and p and q are integers.

At least some of the acid groups may be present as carboxylic acid salt e.g. sodium groups.

Preferred polymers of this type are polyacrylic acid or polymethacrylic acid or copolymers of acrylic acid or methacrylic acid with a C1 to C4 ester of acrylic or methacrylic acid. Polymers of these types are commercially available under the names ROHAGIT (Ex Röhm & Haas) and VISCALEX (ex Allied Chemicals). Specific examples include ROHAGIT S, NV, MV, or HV and VISCALEX EM 15. ("ROHAGIT" and "VISCALEX" are regisered Trade Marks).

The aforesaid anti-splashing agents may be added to the lubricating oil in the form of powders, aqueous emulsions, solutions or gels. Suitably the amount of anti-splashing agent added is from 0.01 to 5%w, preferably from 0.05 to 2.5%w, based on the weight of the lubricating oil. Other additives may be present in the lubricating oil compositions. Additional additives include water, which may be necessary if clear solutions are desired, in amounts of from 1.0 to 25 %w, based on the weight of the lubricating oil composition; corrosion inhibitors, e.g. Na benzoate, Na salicylate, a salt of n-C12/C14-beta-propionic acid, a lauroylsarcosine, or a mono- or polyalkyl phosphate, phosphite or phosphonate in amounts of from 0.05 to 1.5%w, based on the weight of the lubricating oil composition; and/or anti-oxidants e.g. phenolic compounds such as di-tert-butyl cresol, diphenylolpropane and alkylated diphenylolpropanes in amounts of from 100 to 10,000 ppm. An alkaline compound, e.g.

NaOH or KOH, may also be added to increase the pH of the composition. In this case some of the acid groups of polymer may be in form of carboxylic acid salt groups.

The invention will now be illustrated by reference to the following Examples.

EXAMPLES I - 4 The lubricating oil used in these examples was a methanol ethoxylate containing an average of 3.5 moles of ethylene oxide for each mole of methanol.

The types of anti-splashing agents used were: (1) A polymethacrylic acid. It is characterized in that a 3%w solution in water, after addition of sodium hydroxide to produce a pH of 9-10, has a viscosity in the range of from 7700-11000 cP (Brookfield-Viscosimeter, Spindle III, 6 rpm at 20"C).

(2) A copolymer of acrylic acid and the methyl ester of acrylic acid (about 1:1 mole). It is characterized in that a 1 Now solution in water, after addition of sodium hydroxide to produce a pH of 7, has a viscosity of in the range of from 350-550 cSt ( suspended level viscosimeter).

(3) A poly(methylvmylether/ maleic anhydride). It is characterized in that it has a specific viscosity of 2.6-3.5 (measured as 1 g in 100 ml of methyl ethyl ketone at 250C).

(4) A poly(methylvinylether/maleic acid). It is characterized in that a 1%w solution in water, after addition of sodium hydroxide to produce a pH of 7, has a viscosity of 175 cSt at 20"C (suspended level viscosimeter).

Various lubricating oil compositions were prepared and details thereof are given in Table 1. The compositions were prepared by adding the anti-splashing agent and small amounts of water to the lubricating oil component and heating the mixture until a clear solution was obtained. In the case of Examples 3 and 4, 0.16 %w and 0.28 %w respectively of NaOH were added to the compositions. Consequently the ahydride groups of anti-splashing agent (3) are at least partly in the form of free acid groups.

The lubricating oil compositions were tested as coning oils by winding texturized continuous filament yarns of polyesters onto cones at a winding speed of 350 metres/minute.

The equipment used was conventional and included a steel lick roller, partly immersed in a bath of lubricating oil composition, over which the yarns passed before being wound onto cones. Sheets of absorbent paper were positioned around the equipment and the number of splashes of lubricating oil composition found on the absorbent paper after 10 minutes of winding were counted. In addition the %w of coning oil composition picked up by the filaments was also determined.

The coefficients of yarn/steel friction were also determined at a winding speed of 100 metres/minute according to ASTM D 3108 (using a steel friction pin of 8 mm diameter, an angle of wrap of 1800C and a measuring time of 10 minutes).

For comparative purpose the lubricating oil without the addition of an anti-splashing agent was also tested Examples (a) and (b). Also for comparison a commercial mineral oil lubricating composition was also tested (Example (c)).

The results are given in Table 1.

Table 1 Example Anti-splashing Agent pH of 5 %w Added water oil picked up number of splashed coefficient of Type Amount aqueous (%w) by yarn (wt %) oil droplets yarn/steel friction (%w) solution (100 m/min) a - - 5.1 - 3.2 196 0.25 b - - 5.1 10 2.58 341 0.26 1 1 0.5 5.3 2.5 3.5 0 0.25 2 2 0.2 5.0 10 3.5 0 0.24 3 3 1.0 4.3 10 3.5 0 0.24 4 4 0.5 5.1 10 3.5 0 0.25 c - - 5.32 - 3.87 297 0.25 1. Amount required to obtain clear solution except for example b where water has been added for comparative purposes.

2. 5 %w of emulsion of oil in water.

EXAMPLE 5 Knitted articles of polyester were dyed under pressure at a temperature of 1300C in an aqueous bath containing 2.4 Sow of a blue dye (Terasil Dark Blue RB) and 3.6 Sow of a pink dye (Terasil Brilliant Pink EG) on knitted articles. ("Terasil" is a registered Trade Mark).

The knitted articles were prepared from yarns treated with the compositions of Examples 2 and c. The %weight of oil on the knitted fibres before and after dyeing was determined. The results are shown in Table II.

Table II Example Composition Oil on article fYwJ before dyeing after dyeing 5 Example 2 39 0.08 d Example 4.0 0.18 EXAMPLES 6 to 9 Examples 2 to 4 were repeated using an ethanol ethoxylate containing an average of 3.5 moles ethylene oxide for each mole of ethanol and 15 Ssw of water. The compositions had a pH (5 %w aqueous solutions) of from 5 to 6. Substantially the same results were obtained.

EXAMPLES 10 to 13 Examples 2 to 4 were repeated using a methanol ethoxylate containing an average of 5 moles of ethylene oxide for each mole of methanol and 15 Ssw of water. The compositions had a pH (5 Xsw aqueous solutions) of from 5 to 6. Substantially the same results were obtained.

Claims

WHAT WE CLAIM IS:

1. A lubricating oil composition comprising a major proportion of an ether of formula: R - O + CmH2m - O wxH wherein R is a C1 to C10 alkyl group, m is an integer from 2 to 4, and x is an integer from 2 to 20; and a minor proportion of a polymer of an ethylenically unsaturated carboxylic acid.

2. A composition as claimed in claim 1, wherein R is a C1 to C4 alkyl group.

3. A composition as claimed in claim 2, wherein R is methyl, ethyl of a mixture thereof.

4. A composition as claimed in any one of claims 1 to 3, wherein m is 2.

5. A composition as claimed in any one of claims 1 to 4, wherein x is from 2.5 to 10.

6. A composition as claimed in any one of claims 1 to 5, wherein the polymer is at least partly derived from one or more ethylenically unsaturated monocarboxylic acid having the formula CnH2n-l COOH and/or one or more ethylenically unsaturated dicarboxylic acid having the formula: CnHZn-2(COOH)2 or an anhydride thereof, wherein in both formulae n is an integer from 2 to 10, and wherein, in the case that an anhydride alone is used, the polymer is hydrolysed to form carboxylic acid groups.

7. A composition as claimed in claim 6, wherein the polymer is polyacrylic acid or polymethacrylic acid.

8. A composition as claimed in any one of claims 1 to 6, wherein the polymer is derived from an ethylenically unsaturated carboxylic acid and a C1 to C4 ester of an unsaturated carboxylic acid and/or a C1 to C4 ether.

9. A composition as claimed in claim 8, wherein the polymer is a copolymer of acrylic acid or methacrylic acid with a C1 to C4 ester of acrylic or methacrylic acid.

10. A composition as claimed in claim 8, wherein the polymer is a copolymer of maleic acid and a C1 to C4 vinyl ether.

11. A composition as claimed in any one of claims 1 to 10, wherein the polymer has an average molecular wight from 4 x 104 to 2 x 107.

12. A composition as claimed in any one of claims 1 to 11, wherein the amount of the polymer is from 0.01 to 5 tow, based on the weight of the ether.

13. A composition as claimed in any one of claims 1 to 12, wherein the composition additionally comprises water in an amount from 1.0 to 25 now

14. A composition as claimed in any one of claims 1 to 13, wherein the composition additionally comprises a corrosion inhibitor and/or an anti-oxidant.

15. A composition as claimed in claim 1, substantially as hereinbefore described with particular reference to the Examples.

16. A process for treating or oiling textile fibres which comprises contacting the textile fibres with a lubricating oil composition as claimed in any one of claims 1 to 15.

17. A process as claimed in claim 16, wherein the fibres are contacted with the composition during the winding thereof onto cones.

18. A process as claimed in claim 16, substantially as hereinbefore described with particular reference to the examples.

19. Treated or oiled textile fibres whenever prepared by a process claimed in any one of claims 16 to 18.