NO764172L - - Google Patents

Description

The present invention relates to new hydrophilic, linear polyurethanes with a high molecular weight and their use as anti-settling, anti-soiling and anti-static agents, when

they are mixed into detergents and used when washing textile items and more particularly those containing polyester fibres.

It is described in the French patent document 1,499,508 that polyesters contain acidic groups or polymeric hydrophilic groups which can give rise to a solvation with the water, where the use as an anti-redeposition agent is particularly effective. In the aforementioned patent document, polyesters are described in particular, which are formed from the polycondensation of phthalic acid with a lower glycol and a polyoxyalkylene glycol. A polyester molecule is then formed containing hydrophobic groupings which are made up of chains of phthalic acid-lower glycol and hydrophilic groupings that are formed from polyoxyalkylene glycol - the groups. The bond between these groupings is secured by forming an ester function by proceeding from an acid function and an alcohol function, as the reaction takes place at a temperature above 200°C.

The products thus obtained have a relative viscosity between

1.1 and 1.5.

By relative viscosity, one understands the relationship between the flow time for a given volume of a solution of 1 percent by weight of the polymer in orthochlorophenol through a calibrated capillary tube, and the flow time for the same volume of orthochlorophenol through the same apparatus, the measurements being made at 25°C .

It has now succeeded in synthesizing products with hydrophobic and hydrophilic groupings where the bond is secured by means of a urethane function which gives the polyurethanes thus obtained a collection of advantageous properties when they are used in detergent mixtures.

The invention relates to a hydrophilic and linear polyurethane which is written from the reaction between - 10 to 70 percent by weight of a base polyester where the acid number is lower than or equal to 3 mg KOH/g and where the hydroxide number is lower than 120 mg KOH/g, and - 90 to 30% by weight of a prepolymer with terminal isocyanate groupings, obtained by reduction of at least one hydrophilic, non-ionic macrodiol, with at least one diisocyanate,

with the molar ratio NCO/OH being between 0.8 and 1.

- with a molecular weight such that the relative viscosity of a solution with 1% by weight of the polymer in orthochlorophenol is at least 2, at 25°C.

The basic polyester with terminal hydroxyl groups and where the acid number is lower than or equal to 3 can be produced in a manner known per se, by any reaction with polyesterification starting from a diacid, one of its diesters or its anhydride and at least one lower diol which does not give the polyester a marked non-ionic hydrophilic character.

As diacids one can use aliphatic saturated or unsaturated diacids, the aromatic diacids, such as succinic acid, adipic acid, cork acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, the anhydrides of these acids and their diesters such as methyl, ethyl -, propyl, butyl diesters, etc.

Aliphatic glycols can be used as diols such as ethylene glycol, diethylene glycol, and higher homologues with a molecular weight lower than or equal to 300, propanediol-1,2, dipropylene glycol and higher homologues, butanediol-1,4, hexanediol-1,6, neopentyl glycol, cycloalkane glycols like for example. cyclohexanediol and dicyclohexanediolpropane.

For practical reasons, in certain cases, in order to treat the products in concentrated solution, it may be of interest to give the base polyester a slightly ionic character. For this, a small amount of sulfonated diacid is mixed in during the production of the polyester, in a known manner, e.g. introduces 5-sulfoisophthalic acid or its methyl diester in the form of one of its alkali metal salts.

In general, the ratio of the molar amount of sulfonated

diacid and the total molar amount of diacids included in the polyester composition is lower than or equal to 15%.

Preferred base polyesters included in the composition of the polyurethanes according to the invention are those which are mainly produced by starting from terephthalic acid or one of its diesters. They have preferred a number average molecular weight between 1000 and 4000, corresponding to a hydroxyl number IQH of between 25 and 120 mg KOH/g.

The prepolymer with terminal isocyanate groups is prepared by

to react at least one hydrophilic nonionic macrodiol and at least one diisocyanate.

As a non-ionic hydrophilic macrodiol, a polyethylene glycol can be used where the number average molecular weight is generally between 300 and 6000 and preferably between 600 and 4000.

All organic, aromatic, aliphatic or cycloaliphatic diisocyanates are suitable for use in the invention. Nevertheless, some of them are used preferentially due to their availability, and it concerns in particular the diisocyanates of toluene, hexamethylene diisocyanate, isophorone diisocyanate, the di(isocyanatophenyl)alkanes such as di(isocyanatophenyl)methane, and the di(isocyanatocyclohexyl)alkanes, such as di(isocyanatocyclohexyl) methane

The relative molar amount of the diisocyanate used in relation to the total amount of macrodiol and base polyester is determined by the molecular weight of the final polyurethane that one wishes to obtain.

In general, the percentage by weight of diisocyanate in the final product is between 2 and 15%.

When you generally want to obtain an end product with a high molecular weight, the molar ratio between the NCO groupings to the total amount of hydroxyl groupings that comes into use is very close to 1, and then lower than 1. In general, the ratio is between 0.8 and 1.

For the production of these polyurethanes, which is the purpose of the present invention, is produced by atmospheric pressure on the . on the one hand in a first reactor the base polyester by means of a known method, and is kept in a molten state, and on the other hand, in another reactor, the aforementioned prepolymer is prepared by starting from a hydrophilic macrodiol and a diisocyanate, the temperature is just sufficient to maintain the prepolymer in the melt.

In this second reactor, a temperature of between 25 and 70°C is usually sufficient. One preferably works under a nitrogen atmosphere.

The prepolymer is then added to the polyester and the temperature is kept between 150 and 200°C, the pressure being atmospheric pressure, until the reaction is complete, i.e. until the viscosity becomes stable.

If you dispose of a sufficient facility, you can implement it

the various operations in a continuous manner. By means of dosing pumps, the mixture of the base polyester and the prepolymer with terminal isocyanate groups is carried out. The reaction can then be terminated on a conveyor belt which consists of a material on which

the end product does not stick, e.g. polytetrafluoroethylene, sold under the name "TEFLON".

When working in reactors, it is advisable, for reasons of stirring and removal of the product, not to exceed a certain viscosity. With such an apparatus, polymers can be produced with a relative viscosity, measured in a solution of a weight percent polymer, in orthochlorophenol, at 25°C, of up to 4.

The following examples illustrate the invention.

EXAMPLE 1

A - Production of basic polyester

In a reactor, a polyester is produced by starting from:

The condensation is carried out as a classic polyesterification with catalyst tetraisopropyl orthotitanate.

The final conditions for condensation are 220°C for the temperature and 20 mm Hg for the pressure.

700 parts of polyester with the following properties are then obtained: Acid number (Ia) . 0.5 mg KOH/g Hydroxyl number (IU_„H) 29.9 mg KOH/g Number average molecular weight (Mn) 3746.

B - Preparation of prepolymers with terminal isoc<y>anat groupings

300 parts of polyethylene glycol with a molecular weight of 600 are introduced into a reactor under a nitrogen atmosphere. It is heated to 50°C

and introduce at once 115.5 parts of hexamethylene diisocyanate.

The reaction is allowed to continue for 1 ■ hour at a temperature of 70°C.

C - Production of the polyurethane

The temperature in the reactor R is reduced to 190°C and in the course

of approximately 30 min. the contents of the reactor are introduced into the reactor R^ and the prepolymer is allowed to react with the base polyester, for approximately 45 min., at the same temperature..,

t

1115.5 parts of a polyurethane with a certain relative viscosity, measured as previously described, of 2.05 are obtained.

EXAMPLE 2

A - Production of basic polyester

In a reactor R^, a polyester is produced using the method described in example 1 by starting from:

The final conditions for the condensation are 240°C and a pressure of 20 mm Hg.

330 parts of polyester with the following properties are obtained:

B - Production of prepolymer with end isocyanate groups

In a reactor R ? 670 parts of polyethylene glycol with a molecular weight of 4000 are introduced under a nitrogen atmosphere and heated to 70 C. 58 parts of toluene diisocyanate (commercial mixture of isomers 2,4 and 2,6 in a quantity ratio of 80 or 20%) are then added at once.

The reaction is allowed to continue for approximately 30 minutes. at a temperature of 70°C.

C - Production of the polyurethane

One proceeds as in example 1 and pours the prepolymer, prepared

in Example 2-B, into the polyester in Example 2-A. L>

1058 parts of a polyurethane with relative viscosity are obtained

measured as previously described at 2.1.

EXAMPLE 3

In 250 parts of polyester produced as in example 2-A, as described in example 1, a prepolymer with end-isocyanate groupings produced by reacting 750 parts of polyethylene glycol with a molecular weight of 1500 and 109 parts of toluene diisocyanate (commercial, mixture as described earlier) is poured in.

1109 parts of polyurethane are obtained with a certain relative viscosity, measured as previously indicated, of 2.31.

EXAMPLE 4

A - Production of basic polyester

A polyester is produced using the method described in example 1 by starting from the following components:

The polyesterification is terminated at 240°C under a pressure of

20 mm Hg.

This results in 250 parts of a polyester with the following properties:

B - Production of prepolymer with terminal isocyanate groups The prepolymer is produced by starting from:

750 parts polyethylene glycol with a molecular weight of 1500

111 parts toluene diisocyanate (commercial mixture described earlier).

The working conditions are the same as described in example 1-B.

C - Production of the polyurethane

The prepolymer described in 4-B is poured into the polyester

from example 4-A and then obtain small portions of a polyurethane with a relative viscosity, measured as previously described, of 3.13.

EXAMPLE 5

A - Production of basic polyester

A polyester is produced, using the method described in example 1, starting from the following components:

The polyesterification is terminated at 240°C and under atmospheric pressure.

250 parts of polyester with the following properties are then obtained:

B- Production of prepolymer with terminal isocyanate groups The prepolymer is produced by starting from:

3920 parts polyethylene glycol with molecular weight 1500

575 parts toluene diisocyanate (commercial mixture previously described).

The working conditions are the same as described in example 1-B.

C - Manufacture of polyurethane

The prepolymer described under 5-B is poured into the polyester from example 5-A and 4745 parts of a polyurethane with a relative viscosity, measured as described earlier, of 2.05 is then obtained.

The following table summarizes the results and allows comparison of the properties of the obtained polyurethanes.

BAS ICE POLYESTER

DMT: Dimethyl terephthalate

AA: Adipic acid

DMSIP: Sodium 5-dimethylisophthalate sulfonate

EG: Ethylene glycol

R %: Ratio between the molar amount of sulphonated diacid to the total molar amount of diacids included in the polyester composition.

POLYURETHANES

PEG: Polyethylene glycol

HMDI: Hexamethylene diisocyanate

TDI: Toluene diisocyanate

i) r: Relative viscosity

It has been determined that the above-described products are excellent anti-fouling/anti-fouling and anti-static agents, and are therefore modified in the presence of a detergent composition for washing synthetic fibres.

By an anti-soiling agent is meant a product which facilitates the removal of stains on the fabrics on which the agent has been applied.

It is known that substances containing a greater proportion of polyester fibers tend to be very hydrophobic. This property allows fat stains deposited on the tissue to adhere, making their removal difficult. Another well-known disadvantage of polyester fibers is that during washing the detergents present in the washing bath can redeposit on the fabric. In addition, the polyester fibers are charged with static electricity both when wearing them and during the drying operation. One of the means to remedy these disadvantages is to deposit a coating on the fibers which gives them a certain hydrophilic character.

It has been established that the described products are suitable as finishing materials to give the desired hydrophilic character to polyester fibers on which they are deposited.

The deposition of the products according to the invention can be carried out in any suitable way, i.e. in particular by applying a finish to the raw fabric by foularding or powdering after dyeing or to the textile item after washing by the user. In any case, it is preferred to carry out the deposition of the products during the washing operations for the fabrics, i.e. that the polyurethanes according to the invention are introduced into the detergents.

The mixing of the products according to the invention can be carried out regardless of the type of detergents, whether these are anionic, non-ionic, cationic, ampholytic or zwitter-ionic. The mixtures generally contain, in addition to surface-active substances and builders, a certain number of classical components in variable quantities. Examples of these ingredients are agents that favor foaming or allow control of the foaming such as the polysiloxanes, mineral salts such as sodium sulfate, bleaching agents alone or in admixture with precursors for bleaching agents and anti-redeposition agents such as carboxymethylcellulose as well as small amounts of perfume, dyes, fluorescent agents and enzymes.

The mixing of the components can be carried out on a "which

any way, e.g. by addition in the form of a solution or emulsion besides_by atomization or granulation of powdered mixtures or in the form of granules of the said mixtures.

The polyurethanes according to the invention have an elastomer

• character which is more evident when the chain of the macrodiol which

included in their constitution is long, and it is advantageous to introduce a finely dispersed mineral to obtain the polyurethanes in the form of a powder that can be more easily mixed into the detergents.

Suitable fillers that disperse easily are made up of a lot

fine particles, and has a high absorption capacity and suitable fillers include kaolin, silicoaluminates of sodium and silica.

o The preferred fillers are synthetic silica or silicoaluminates of sodium, products obtained by precipitation using known methods. The fillers are neutral or slightly basic. The fillers, which are made up of elementary particles with diameters varying between 50 and 1000 Å, have a specific surface area, measured using the BET method, of between 50 and 600 m/g. Furthermore, the aforementioned fillers have a porosity of 50 to 200 cc/100 g, measured by mercury solution porosimetry, and the pore diameter range varies between 400 Å and 2.5

Their oil absorption, measured using dioctyl phthalate, is over

70 cc/100 g, which may amount to 250 cc/100 g in the case of sodium silicoaluminates and 460 cc/100 g in the case of silica.

In general, you can use 10 to 90 parts by weight of filler for 90 to 10 parts by weight of polyurethane. Preferably, 40 to 70 parts by weight of filler is impregnated with 60 to 30 parts by weight of the polymer/to obtain a powder which is sufficiently dispersible in water, without ever introducing excessive amounts of insoluble components into the wash bath.

To fill the polyurethane with an inorganic element, one can melt the polymer in advance, add the desired amount of filler,

and then finely grind the product thus obtained. In the case of polymers with a hydrophilic ability sufficient to obtain an aqueous dispersion containing 15 to 20 percent by weight of the said polymers, one can prepare in advance a solution or emulsion of the said polymers in the amount of the desired filler therein and then dry and finely grind it obtained product.

This is especially the case with products containing anionic groups where the task is to facilitate dispersion of the aqueous concentrate.

In general, the polyurethanes according to the invention are used i

an amount of 0.1 to 5% by weight in the detergents.

0.5 to 3% by weight polyurethanes are preferably used in the aforementioned mixtures.

It has been established that the polyurethanes according to the invention mixed in a washing powder and stored under conditions that approach the real ones show an efficiency when washing synthetic fibers that is much greater than the products previously known to the person skilled in the art.

The following examples further illustrate the invention by showing the remarkable properties of the mentioned products when they are used as anti-repositioning and anti-fouling agents.

The inorganic filler used in the examples is a product manufactured by Société SIFRANCE, with the designation "TIX-O-SIL 38". The

concerns a synthetic silica, obtained by precipitation.

They . the following examples illustrate the use in the form of powder of the polyurethane according to the invention. The quantities are expressed as quantities by weight.

Example 6

A - Used in the form of a pre-melted polyurethane powder.

1000 parts of "TIX-O-SIL 38" are heated to 200°C in a ball mould, and under a nitrogen atmosphere. One adds e.g. 1000 parts polyurethane produced in ex. 3 or 4, melted in advance. A finely divided powder is then obtained.

B - Application in the form of a powder of polyurethane previously dispersed in water.

One would rather e.g. 1000 parts polyurethane produced in ex. 1 or 2 out in 4000 parts of water maintained at a temperature of 60°C, and under vigorous stirring. The entire mixture is poured into a mixing device and 1000 parts "TIX-O-SIL 38" is added. The obtained paste is dried in a ventilated oven at 60°C before it is ground.

In the following example, the stability during storage of the polyurethanes according to the invention is shown.

Example 7

The products according to the invention are mixed in an amount of

3 percent by weight in the following detergent mixture:

To the products according to the invention, silica filler "TIX-O-SIL 38" is added, as described earlier. The obtained powder is mixed into the above-mentioned detergent in a mixing device made by HENRY. The resulting mixture is then stored in a cabinet kept at a temperature of 40°C for 4 weeks.

The stability of the polyurethanes according to the invention is then tested in the following way: Two strips (20 x 115 cm) of polyester-cotton cloth (67/33) with reflection C are washed in an automatic washing machine "Miele 421 S"

(colour program - 60°C) in the presence of 5 g/l of the detergent containing the relevant polymer. The textile strips are then dried at room temperature and cut into patches (12 x 12 cm) on which waste oil, Spangler dirt (see J. Am. Oil Chem. 1965-42, 723-727), tomato concentrate and lipstick with 6 patches per strip are deposited. type of stains. The patches are then aged for a period of one hour in a cabinet at 60°C. The reflection R is measured on an Elrépho device with a filter FMY/C for the waste oil and the Spangler dirt and a filter FMX/C for the tomato concentrate and the lipstick.

The stained patches are then basted onto 10 clean cotton strips and then washed and dried. Their reflection is then measured. The effectiveness of the tested product as an anti-fouling agent is judged as the percentage removal of the stains calculated using the formula:

For each product that was tested, the average percentage removal of the various stains is calculated. The results of the experiments are indicated in the following table.

PU^: Denotes the polyurethane described in example "i".

X % : Denotes the amount by weight of "TIX-O-SIL 38" mixed into the polyurethane, in relation to 100 parts by weight of the mixture (filler + polyurethane).

I : Denotes average percentage removal of the different

spots for storing the polymer.

F., : Denotes the same percentage removal after storage of

the polymer for 4 weeks at 40°C.

The following table shows the advantage of high molecular weight for the polyurethanes according to the invention, during their storage. In the table, ^ r denotes the relative viscosity of the investigated products, which are the polyurethane described in ex. 3 (PU) and

the polyester described in ex. 2 of the French patent document

/1,401,581 (P-E).

The following example shows the antifouling properties of the polyurethanes according to the invention, used in an anionic detergent.

Example 8

Two strips (20 x 115 cm) of polyester-cotton cloth (67/33) with reflection C are washed in an automatic washing machine "Miele 421 S"

(colour program - 60°C) in the presence of 5 g/l of the detergent described in ex. 7. The investigated product is then introduced in an amount of 3% by weight in relation to the aforementioned mixture. The products are mixed in either in the form of an aqueous solution with 5% by weight or in the form of a powder. The textile strips are then dried at room temperature and cut into strips (12 x 12 cm) on which waste oil, Spangler dirt, tomato concentrate and lipstick are deposited with 6 strips per strip. type of stains. The patches are then aged for one hour in an oven at 60°C. Their reflection R is measured on an Elirépho device with a filter FMY/C for the waste oil and the Spangler dirt and a filter FMX/c for the tomato concentrate and lipstick.

The stained patches are then basted onto 10 clean cotton strips and then washed as before and dried. One measures their reflection R^. The effectiveness of the investigated product as an anti-soiling agent is assessed using the percentage removal of the stains calculated using the formula:

For each examined product, average percentage removal of the various stains is calculated. The test results are listed in the following table:

The confidence interval associated with this test is 2%;

In this table, a polyester-polyurethane that is not part of the scope of the present invention Ise, denoted by PU, was investigated.

This polymer produced using the general method described in example 1 has the following properties:

Composition

Basic polyester: 22.67% by weight

Polyethylene glycol

M- = 1500 : 68.02 - " -

n

Toluene diisocyanate

(commercial

mix) : 9.31"

Relative viscosity (measured as previously described); 2.63

The starting polyester was produced by starting from 10 mol of adipic acid with 30 mol of ethylene glycol and had the following properties:

IA:0.5MgKOH/g IOH:16.5MgKOH/g Mn: 6590

In the following example, the anti-soiling properties of the products according to the invention used in a non-ionic detergent are demonstrated.

EXAMPLE 9

The tests are carried out under identical conditions as described in example 8, but with the following non-ionic detergent mixture:

- Alcohol content from 0 to 12 carbon atoms and more

The results of the experiments are set out in the following table:

In the following example, the properties of the products according to the invention as an anti-reposition agent are shown.

EXAMPLE 10

Fluffy pieces of cloth (12 x 12 cm) made of polyester-cotton cloth (67/33) are washed in a Lini-Test (ORIGINAL HANAU) machine for 20 min. at 60°C in hard water (33°TH) containing 0.75 g/l of the following classic detergent mixture:

A Spangler dirt is introduced into each washing container in a quantity of 5 parts per thousand in relation to the weight of the washing solution. The product according to the invention is examined on the basis of 3% by weight in relation to the detergent mixture in which it is mixed.

The renewed deposition or redeposition of the Spangler dirt on the textile is judged by the value R for the reflection of the washed textile in the presence of the product according to the invention. The reflection is measured on a Gardner device (GARDNER INSTRUMENT). As a comparison, unwashed textiles have a reflectance of 85.6.

The results obtained with a certain number of products described in

the foregoing is indicated in the following table:

The confidence interval for these conditions of the experiment is

1. The following example shows the anti-static properties of the products according to the invention.

EXAMPLE 11

Two strips (20 x 115 cm) of polyester cloth ("Dacron" type 54).

TEST FABRICS INC) is washed in an automatic washing machine "Miele 421 S" (colour program - 60°C ) in the presence of 5 g/l of the detergent mixture described in example 7. The investigated product is introduced in an amount of 3 percent by weight in relation to the detergent in which it is involved. The textile strips are then dried at ambient temperature and cut into slices with a diameter of 10 cm. The slice-e of the textile is then conditioned for 24 hours in an oven where the temperature and humidity are controlled (22°C. 46% relative humidity). Each of the test pieces is charged by electrostatic impact and the time for half-discharge and three-quarter discharge is measured using an electrostatimeter (CreusotrLoire).

Claims (9)

1. Linear hydrophilic polyurethane with relative viscosity greater than or equal to 2, characterized by the fact that it is formed by reaction between: - 10 to 70% by weight of a base polyester, obtained mainly from terephthalic acid or one of its diesters, with a hydroxyl number up to 120 mg KOH/g and an acid number up to 3 mg KOH/g with 90 to 30% by weight of a prepolymer with terminal isocyanate groups, obtained by reaction of at least one hydrophilic nonionic macrodiol with at least one diisocyanate, with the molar ratio NCO/OH being between 0.8 and 1. 2. Polyurethane as specified in claim 1, characterized in that the number average molecular weight parent polyester is between 1000 and 4000. 3. Polyurethane as stated in claim 1 or 2, characterized in that the macrodiol that is included in the composition of the prepolymer is a polyethylene glycol with a number average molecular weight of between 300 and 6,000. 4. Polyurethane as specified in claim 3, characterized in that the number average molecular weight of the polyethylene glycol is between 600 and 4,000. 5. Polyurethane as stated in claims 1-4, characterized in that the dicyanate included in the composition of the prepolymer is selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, di(isocyanato-phenylmethane) and isophorone diisocyanate. 6. Polyurethane as stated in claim 5, characterized in that the amount of diisocyanate used is between 2 and 15 percent by weight in relation to the polyurethane. 7. Polyurethane as stated in claims 1 - -6, characterized in that the base polyester is obtained mainly by starting from terephthalic acid (or its diesters), and at least one lighter saturated diol selected from the group consisting of ethylene glycol, diethylene glycol and higher homologues with molecular weight up to 300, butaridiol-1,4 and propanediol-1,2. 8. Polyurethane as specified in claim 7, characterized in that the base polyester is obtained by starting from a mixture of terephthalic acid or one of its diesters and adipic acid or one of its diesters. 9. Polyurethane as stated in claim 7 or 8, characterized in that during the production of the base polyester, sulfoisophthalic acid or its methyl diester is introduced, in the form of one of its alkali metal salts, the molar ratio between sulfonated diacid and the total molar amount of diacids included in the polyester composition- is lower than or equal to 15%.