JP2003528988A - Use of polyalkoxylated terpene derivatives in the treatment of textile fibers - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention provides a method of using a wetting / penetrating agent which has the same effect as compounds normally used in textile fiber processing steps, but which does not have the drawbacks associated with the appearance of air bubbles. The present invention relates to a method for using a polyalkoxylated terpene derivative of the formula Z _i -X- [CH (R ³ ) -CH (R ⁴ ) -O] _n -A in treating textile fibers. [Wherein, Z is a bicyclo [a, b, c] heptenyl group or a bicyclo [a, b, c] heptyl group (a, a) which may be substituted with at least one C ₁ -C ₆ alkyl group. b and c are such that a + b + c = 5, a = 2, 3 or 4, b = 1 or 2, c = 0 or 1). X is —CH ₂ —C (R ¹ ) (R ² ) —O— or —O—CH (R ′ ¹ ) —CH (R ′ ² ) — (where _Ri represents a hydrogen or a hydrocarbon group) ). R ³ and R ⁴ represent hydrogen, an alkyl group or an alkenyl group. n means a value in the range of 1 to 200. A is hydrogen, alkyl, (alkyl) aryl group, _{halogen, -CH 2 -CH (OH) R} 5 -SO 3 M, -OPO 3 (M) 2, - (CH 2) a -COOM, - (CH ₂₎ represents a mixture of _b -SO ₃ M or the compound. The use of the above compounds is particularly advantageous for dyeing operations.

Description

Detailed Description of the Invention

The present invention relates to a method for treating textiles, a polyalkoxylated terpene compound, and more particularly to a dyeing operation.

The text and references below refer only to woven fibers (this term designates fibers), knitting yarns (yarns), knitted fabrics, woven and non-woven fabrics.

Furthermore, the invention is applicable to the treatment of natural textile fibers (natural or regenerated cellulose, (cotton), wool) and synthetic fibers (polyester, polyamide (nylon), polyacrylonitrile (acrylic)).

[0004] The treatment of textile fibers consists of various processes including tanning, desizing, washing, bleaching, causticizing, dyeing and finishing. During these steps, wetting agents and / or penetrants need to be used as agents effectively used during these steps. Ethoxylated noniphenol is commonly used. Although these agents are very effective, there is a problem that a large amount of bubbles are formed. While it is possible to use defoamers such as emulsifying silicone defoamers with it, under the severe shearing conditions that may be encountered during dyeing operations, the defoamers often become unstable and silicone gels , Causing the appearance of persistent stains on the fabric that adhere to the fibers.

The present invention therefore relates to a method of using a wetting agent / penetrating agent which has the same effect as the compounds normally used in textile fiber treatment processes, but which does not have the disadvantages associated with the appearance of bubbles.

That is, the present invention comprises at least one of a) fried, b) desizing, c) washing, d) bleaching, e) caustic treatment, f) dyeing, and g) finishing. The compound according to formula (I), which is constituted, is used in at least one of the above steps, to provide a method for treating textile fibers. At least one Z _i -X- ^{[CH (R 3) -CH (R} 4) -O ] _n -A [wherein, · Z _i is, C ₁ -C ₂ alkyl groups, among preferred methyl, A bicyclo [a, b, c] heptenyl group or bicyclo [a
, b, c] heptyl group (a, b and c are a + b + c = 5, a = 2, 3 or 4,
b = 1 or 2, c = 0 or 1) and is selected from those represented by the formulas below (Z ₁ to Z ₇ ) and the corresponding heptyls having no double bond. Including the skeleton

[Chemical 2] · X ^{_{is, -CH 2 -C (R 1)}} (R 2) -O- or ^{-O-CH (R '1)} -CH (R' 2) - represents, (in this case R ¹ and R ² They may be the same or different and represent hydrogen or a linear, branched or cyclic, saturated or unsaturated C ₁ -C ₆ hydrocarbon group, R ′ ¹ and R ′ ² may be the same or different, and hydrogen or Represents a linear, branched or cyclic, saturated or unsaturated C ₁ -C ₂₂ hydrocarbon group). R ³ and R ⁴ may be the same or different, and are a hydrogen atom or a linear or branched C ₁ -C ₂₂ (cyclo) alkyl group or (cyclo) alkenyl group, · n represents an average value in the range of 1 to 200; in · a, a hydrogen atom, an alkyl group of C ₁ -C _6, aryl or alkylaryl group, a halogen atom, or -CH ₂ -CH (OH) R ⁵ group (wherein, R ⁵ is a linear, branched It is properly cyclic C ₁ -C ₂₂ alkyl group or aryl group, or -SO ₃ M, -
_{OPO 3 (M) 2, -} (CH 2) a -COOM, - represents a _{(CH 2) b -SO 3 M} . In this case, a and b are 1 to 6, M represents H, Na, K, Li, N (R ₄ ) ⁺ , and the group R
Are the same or different and represent a hydrogen atom or a linear, branched or cyclic C ₁ -C ₂₂ alkyl group which may be hydroxylated), or a mixture of these compounds.

The compound used (designated as a terpene compound) will be described. As mentioned above, the terpene compound derivative used in the method according to the present invention has the formula given above.

In this formula, the Z _i group is attached to the chain residue via any one of carbon atoms 1-6. In a more detailed embodiment, the Z _i group is attached to the chain residue via carbon atoms 1, 5 and 6.

In an advantageous variant of the invention, the compound is C ₁ -C ₆ having at least two Z _i groups.
Such as substituted on at least one of its carbon atoms by an alkyl group, preferably two methyl groups. More specifically, the substituent is 7 carbon atoms.
Located on top.

The first family of compounds corresponds to those in which X represents —CH ₂ —C (R ¹ ) (R ² ) —O—. In this case, the Z _i group corresponds in particular to the groups Z _{3 to} Z ₇ . Furthermore, the ring is
Contains an ethylenically unsaturated bond. Furthermore, they have two substituents on carbon atom 7,
It preferably has methyl. Suitable compounds are defined by Z ₄ and Z ₅ which have two methyl groups on the carbon atom.

A second family of compounds corresponds to those in which X represents —O—CH (R ′ ¹ ) —CH (R ′ ² ) —O—. More specifically, the ring has no ethylenically unsaturated bond and is represented by a Z ₃ group. In this family, at least R ^'1 or R' ² It should be noted that not hydrogen.

Accordingly, in a preferred embodiment, the compound is such that R ′ ¹ or R ′ ² is a methyl group. In the detailed characteristics of the compounds of this family
Has two methyl substituents and one C ₁ -C ₆ alkyl substituent, preferably methyl, is located at carbon atom 2 or carbon atom 5.

With respect to the-[CH (R ³ ) -CH (R ⁴ ) -O-]-unit, R ³ and R ⁴ have already been defined as being the same or different and may be hydrogen or linear. Alternatively, it represents a branched C ₁ -C ₂₂ , preferably C ₁ -C ₆ (cyclo) alkyl group or (cyclo) alkenyl group. More specifically, the R ³ group and the R ⁴ group may be the same or different and represent a hydrogen atom, a methyl group or an ethyl group.

[0014] If - ^{[CH (R 3) -CH (R} 4) -O ] - if different units, their distribution is statistically a is or a block shape. With this latter possibility, two or more different blocks are possible. By way of example, suitable compounds have the following sequences. −
[CH ₂ -CH ₂ O] _q - ^{[CH (R 3) -CH (R} 4) -O ] _r or - [CH (R ³⁾ -C
H (R ⁴⁾ -O] _r - [CH ₂ -CH ₂ O] _q - (wherein, R ³ and R ⁴ is other than hydrogen, n = q + r)

One type of block compound suitable for practicing the invention is as shown in the following sequence:-[CH (R ³ ) -CH (R ⁴ ) -O] _p- [CH ₂ -CH ₂ O] _q - ^{[CH (R 3) -CH (R} 4) -O ] _r - (wherein, R ³ and R ⁴ is other than hydrogen, n = p + q + r) .

In a detailed embodiment, the units correspond to oxyethylenated and / or oxypropyleneated units. n is an average value in the range up to 1 to 200, it - [CH (R ³⁾ -CH (
R ⁴⁾ -O -] - corresponds to the total number of units. Preferably, the total number of oxyethylenated units is in the range 1 to 200, more preferably in the range 1 to 50, and more particularly in the range 1 to 20.

With respect to the total number of oxypropylenated units, their average total number is in the range 0-20, more particularly in the range 1-10, preferably in the range 1-4.

It is very advantageous to use a terpene compound corresponding to a mixture of compounds of the formula (I), at least one of which has the blocks mentioned above.

These compounds and the process for preparing them are described in International Patent Application WO-A-
96/01245 and WO-A-98 / 28249. See them for the definition and preparation of these compounds.

The method of the present invention consists in using the compounds described above in one or more of the steps carried out when treating textile fibers.

The above compounds have been demonstrated to have important textile fiber wetting properties that facilitate the penetration of the reactants into the textile fibers.

Furthermore, the compounds used in the present invention are also resistant to the often harsh conditions encountered during fiber treatment. Many steps are performed in highly alkaline media.

In addition, the compounds of the invention have the advantage that their structure is compatible with the manipulations required when using them. Thus, it is possible to use nonionic or ionic active compounds which, when in general use, are compatible with the various compounds present in the solution intended for fiber treatment.

Textile fibers which can be treated are like lubricants, softeners (lubricants for dyeing in the case of synthetic fibers), polyvinyl alcohol, carboxymethylcellulose), fiber flocculants (starch), film formers (hydrocolloids). Containing residual additive from the previous step. Desizing (step b)) is used to carry out this operation.

The desizing step is enzymatic (to reduce the molecular weight of starch, if any) and / or
Or by chemical oxidation and / or by alkaline treatment. More specifically, the oxidation reaction is carried out with an oxidizing agent selected from, for example, hydrogen peroxide, peroxosulfates, or perborates.

It is also carried out in alkaline medium, like alkaline treatments. Alkali metal hydroxides (such as sodium hydroxide) and alkali metal carbonates and bicarbonates can be used. Usually the concentration of alkaline agent is around 2-5 g / l in order to obtain a pH in the range of 10-12. The desizing operation usually includes additives such as chelating agents.

[0027]   This step is performed in a 70% to 80% aqueous solution.

[0028]   Further, it is performed at a high temperature. That is, the temperature is 50 ° C. or higher.

Furthermore, desizing is carried out in the presence of the described terpene compounds, the use of which is the subject of the present invention.

The amount of this compound in the desizing liquor is more particularly in the range 1-5 g / l. Generally, the textile fibers are impregnated in the solution (either continuous (steambox) or rotary (spinning roller)).

[0031]   This step is performed by passing it once or more.

Depending on the natural textile fibers, it may be necessary or simply advantageous to carry out a preliminary step known as fried (step a)). This process gives textile fibers with a smooth surface. This consists of baking the fibers protruding from the surface.

It should be noted that performing this fried process does not facilitate the desizing process. Woven fibers treated in this way are actually too dry, and as a result,
A solution with a strong wetting power is absolutely necessary if the effect of the desizing process is to be sustained.

After the desizing step is performed, the washing step (step c)) can be performed. This process is more commonly used when the textile fibers include cotton. This procedure is used to remove compounds normally present in cotton fibers such as cellulose (hemicellulose, immature cellulose), natural oils or waxes that cause heterogeneity in the final dyed or undyed fiber. To do.

This washing operation is performed in a highly alkaline medium. The concentration of the alkaline agent in the liquid is usually 20 to 40 g / l. Effectively, sodium hydroxide is used.

This medium also contains a terpene compound. An effective amount of this compound is 1-5 g /
The range is l. More specifically, this step is performed at a temperature of approximately 60-80 ° C.

This step is usually performed in a steam box. At the end of this operation, the textile fibers can be dyed directly if the color is dark.

However, this method of treating textile fibers usually continues until the bleaching step (step d)). This operation is performed using an oxidizing agent, more specifically hydrogen peroxide. It is effective to use stabilizers such as silicates, hypochlorous acid or polyphosphoric acid.

[0039]   The bleaching step is performed at a high temperature of approximately 70 ° C to 80 ° C.

At the end of the bleaching step, a caustic treatment or a mild caustic treatment (step d)) can optionally be carried out. This step consists of immersing the textile fibers in an alkaline solution. The textile fibers are optionally exposed to mechanical tension during this process. This operation improves the effectiveness of the dyeing process of the fiber and the tear strength of the fiber.

[0041]   Some possibilities can be expected with this operation.

In the first possibility, the dipping is carried out with an alkaline agent concentration of approximately 200 to 300 g / l.
With a solution that is In a variation of this process, this process is approximately 15 ° C to 25 ° C.
Perform at a temperature of ° C.

In a further variation of this process, the textile fibers are placed under tension at about 55 ° C.
It is possible to carry out this operation by immersing in a solution containing an alkaline agent at a concentration of about 200 g / l when it is known to be in the range of ~ 77 ° C.

On the other hand, it is also possible to carry out this step with the solution in which the concentration of the alkaline agent is 100 to 160 g / l when the textile fibers are not under tension and at a temperature in the range of about 20 ° C. to 40 ° C. Is. In such a case, it is named “mild caustic treatment” rather than “caustic treatment”.

The alkaline solution may also contain a terpene compound, more specifically 1 to 5
It is a concentration within the range of g / l.

The textile fibers are dyed in a series of steps e). These steps are well known in the art. Disperse dyes, i.e. pigments which are insoluble in water, can be used, or reactive dyes, i.e. water-soluble pigments which settle on the reaction sites present in the fiber.

By way of example, the fibers are a mixture of synthetic and natural fibers (eg polyester / cotton).
, The dyeing consists of the following steps. Dyeing synthetic fibers (step e1)), fixing these pigments (step e2)), washing non-fixed pigments (step e3)), dyeing natural fibers (step e4)), washing non-fixed pigments (step e5). )).

If the fibers consist of only one type of fiber, only the steps specific to this type of fiber are performed.

Suitable dyeing operations are carried out at a pH of at least 7, preferably at least 8. Such a pH is obtained by using an alkaline compound such as an alkali metal hydroxide.

[0050]   The solution or dispersion used is a liquid.

Also, in addition to the pigments or dyes, the solutions or dispersions preferably contain various anionic or nonionic surfactants. For example, alkoxylated (ethoxylated and / or propoxylated) fatty alcohol sulfate ethers, alkoxylated phosphate esters, mono and dialkyl sulfosuccinates, polyalkoxylated fatty alcohols, lignosulfonates, formaldehyde and aromatic sulfonic acids. A condensate with (for example, naphthalene sulfonic acid) or the like can be used.

It is also possible to use the following dye liquid additives. Polysulfonate,
Colloids such as polycarboxylates (polyacrylates, acrylic acid / maleic acid copolymers), polyvinylsulfonates, alginates, polysaccharides or cellulose derivatives.

These surfactants and colloids stabilize the dispersion but can prevent impurities from precipitating or aggregating in the liquid.

The solutions and dispersions also include terpene compounds. They are preferably nonionic.

The use of the terpene compounds mentioned above is very advantageous for the dyeing process. They have little or no foaming and can even be foam breakers even under dyeing conditions where they are sheared very violently.

Therefore, the use of the terpene compounds described above no longer requires large amounts of antifoaming agent. It is likewise possible to dispense with the use of defoamers.

[0057]   The amount of these terpene compounds is advantageously in the range 1 to 5 g / l.

The actual dyeing operation is customarily carried out in particular batchwise (jet or jigger). They can be carried out continuously or preferably batchwise.

Dyeing is usually carried out at elevated temperatures, ie in the range 50 ° C. to 90 ° C. Higher temperatures are possible if the operation is carried out under pressure.

In the continuous method, the textile fibers are first impregnated with the dyeing liquor and then passed through rollers to remove excess dyeing liquor. The fibers are passed many times before the color is fixed.
Heavy shear conditions are often present during the infiltration process, causing the appearance of bubbles.

In the batch method performed in a jigger, the fibers are spread from one cartridge to the other by dipping in the middle of the liquid. In this case, stir gently. The reason is that the amount of bubbles formed is small. However, air bubbles accumulate in the textile fibers,
Moreover, it causes the appearance of spots.

In the jet type batch method, many bubbles appear. The fibers actually float in the water stream. When using a centrifugal pump, the shear is very strong and the agitation is very strong. Conventional defoamers become unstable and accumulate on the fiber, resulting in speckle appearance.

[0063]   When impregnation is complete, the dye is fixed by heat on the textile fibers.

Once the textile fibers have been dyed, a finishing step can be carried out in order to impart to the fibers the individual properties according to the final use form.

Thus, textile fibers may be softeners (anionic, cationic, silicone), agents that impart a somewhat stiffer fiber, non-staining agents (fluorocarbons), or change the appearance of the fiber. It can be treated with agents such as polyurethane to which flock can be applied to give the appearance of velvet.

The examples are now described without limitation. Examples The test results described below demonstrate the effect of terpene compounds in the process of desizing (branching) the microfibers of polyester fabrics, compared to common surfactants.

Test Conditions Desizing (Blanching) Solution Composition: Sodium hydroxide (flake) 2 g / l Chelating agent (Neocrystal 70 sold by Nicca) 1 g / l Desizing agent (terpene compound or general Surfactant) 1 g / l woven fabric was stretched on a substrate and then droplets of oil (HN100 paraffin mineral oil), esterified oil (methyl ester of rapeseed oil) or wax (ethylene bis-stearamide) were deposited. . All of these were processed at 180 ° C for 1 minute. The fabric was then dipped in the desizing solution at 110 ° C. for 20 minutes. The weight ratio of the article to be treated and the desizing solution was 1 to 20. The fabric was then rinsed with plenty of water for 30 seconds and then drained for 30 seconds. As a result, the fabric is then treated with a disperse dye (1% by weight paranyl violet 3RL-BASF).
Stained with. The article was immersed in the solution containing the dye at room temperature and then the temperature was raised to 80 ° C. with stirring. The areas where the deposited oil was not removed were dyed differently. The following desizing agents were tested.

[0068]Comparative test 1 : Igepal NP8.5, noniphenol containing 8.5 moles of ethylene. Testing according to the invention : A compound corresponding to ring 4), carbon 3 has two methyl groups,
X is -CH₂-CH₂Represented by -O, and 5 mol of propylene oxide and 9 mol
Containing ethylene oxide.Comparative test 2 : Corresponds to a composition containing no desizing agent.Desizing test (removal of oil stains)   The results were evaluated from 1 (impossible) to 7 (excellent).Extraction test by desizing   A portion of the treated fabric is used to remove the residue (oil, desizing agent) remaining on the fabric.
Used to measure percentage.   The residue was extracted with ethyl ether. The residue is "100 x dry extract weight /
"Weight of piece of fabric". For this measurement, the desizing solution was 3 g / l desizing agent
Was included.Measurement of bubble height   The desizing solution used was that used in Test 1. Turbo bubbles
Agitator (40 mm turbine, 2000 rpm) for 5 minutes, stirring 900 g of solution
It was obtained by doing. The temperature was 50 ° C. The height of the bubbles should be 5 minutes after standing still.
The sample was recorded.   The results are shown in the table below:

[0069]

[Table 1] The agent according to the invention was as effective as the agent of comparative test 1 with respect to the desizing agent and, surprisingly, the residuals remaining on the treated fabric. In contrast, the desizing agent of the present invention was more effective than the reagent of Comparative Test 1 in terms of maximum bubble value.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, C H, CN, CR, CU, CZ, DE, DK, DM, DZ , EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, K G, KP, KR, KZ, LC, LK, LR, LS, LT , LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, S E, SG, SI, SK, SL, TJ, TM, TR, TT , TZ, UA, UG, US, UZ, VN, YU, ZA, ZW F-term (reference) 4H057 AA02 CA30 CB27 CC02 DA01                       DA34                 4L033 AB01 AB05 AC15 BA14 CA48

Claims (9)

[Claims] 1. A method comprising at least one of a) fried, b) desizing, c) washing, d) bleaching, e) caustic treatment, f) dyeing, g) finishing. textile fiber treatment method which comprises using at least one compound of formula used in the step of the step (I): Z _i -X- ^{[CH (R 3) -CH (R} 4) - O] _n -A [wherein, • Z _i is a bicyclo [a, b, c] heptenyl group optionally substituted by at least one (preferably methyl) C ₁ -C ₆ alkyl group or Bicyclo
[a, b, c] heptyl group (a, b and c are a + b + c = 5, a = 2, 3 or 4
, B = 1 or 2, c = 0 or 1), and selected from those represented by the formulas below (Z ₁ to Z ₇ ) and corresponding heptyls without double bonds. Including a skeleton represented by: · X ^{_{is, -CH 2 -C (R 1)}} (R 2) -O- or ^{-O-CH (R '1)} -CH (R' 2) - (
In this case, R ¹ and R ² may be the same or different and represent hydrogen or a linear, branched or cyclic, saturated or unsaturated C ₁ -C ₆ hydrocarbon group, and R ′ ¹ and R ′ ² are , May be the same or different and represent hydrogen or a linear, branched or cyclic, saturated or unsaturated C ₁ -C ₂₂ hydrocarbon group), and R ³ and R ⁴ may be the same or different. Often, a hydrogen atom or a linear or branched C ₁ -C ₂₂ (cyclo) alkyl group or a (cyclo) alkenyl group is represented, n is an average value within a range of 1 to 200, and A is hydrogen. Atom, C ₁ -C ₆ alkyl group, aryl or alkylaryl group, halogen atom, —CH ₂ —CH (OH) R ⁵ group (wherein R ⁵ is linear or branched or cyclic C ₁ -C ₂₂ alkyl or aryl group, or _{-SO 3 M, -OPO 3 (M} ) _{2, - (CH 2) a} -COOM, - (CH 2) b represents a -SO ₃ M, in this case, a and b are 1 to 6, M is, H, Na, K, Li , N ( R ⁴ ) ⁺ , where the group R
Are the same or different and each represents a hydrogen atom or a linear, branched or cyclic C ₁ -C ₂₂ alkyl group which may be hydroxylated) or a mixture of these compounds. ]. 2. A formula (I) in which the Z _i group is bound to the chain residue preferably via any one of the carbon atoms 1 to 6 (more preferably carbon atoms 1, 5 and 6). Method according to claim 1, characterized in that the compound according to (1) is used. 3. In a compound of formula (I), the Z _i group has at least one of its carbon atoms, preferably at 7 carbon atoms, two C ₁ -C ₆ alkyl groups. 3. The method according to claim 1, wherein the method is replaced by 4. X represents —CH ₂ —C (R ¹ ) (R ² ) —O—, and the Z _i group is Z _3
4. A method according to claim 1, characterized in that a compound of formula (I) corresponding to the group Z ₇ to Z ₇ (preferably Z ₄ and Z ₅ ) is used. 5. A formula (I) in which X represents —O—CH (R ′ ¹ ) —CH (R ′ ² ) —O— and Z _i is a Z ₃ group containing no ethylenically unsaturated bond. 5. A method according to any one of claims 1 to 4, characterized in that the compound according to) is used. 6. A compound of formula (I) wherein Z is bicyclo carbon 2 or 5
C ₁ -C ₆ alkyl group above, preferably the method according to any one of claims 1 to 5, characterized in that it is substituted by a methyl group. A mixture of 7. compounds of formula (I), corresponding to at least one of the following sequences of which - ^{[CH (R 3) -CH (R} 4) -O - ] - to have a group 7. A method according to any one of claims 1 to 6, characterized in that:
- ^{[CH (R 3) -CH (R} 4) -O ] _p - [CH ₂ -CH ₂ O] _q - [CH (R ³⁾ -CH (
R ⁴⁾ -O] _r - (wherein, R ³ and R ⁴ is other than hydrogen, n = q + r). 8. The method according to claim 1, wherein the compound of formula (I) is used during the dyeing step e). 9. The method according to claim 1, wherein the compound of formula (I) is used at a concentration in the range of 1 to 5 g / l.