DE3245997T1 - MIXTURE OF CHEMICAL COMPOUNDS FOR THE TREATMENT OF CELLULOSE FIBERS CONTAINING OR PRODUCTS COMPOSING THEREOF TO IMPROVE THEIR FIRE RESISTANCE AND METHOD FOR CARRYING OUT THE TREATMENT - Google Patents

Abstract

The blend of chemical compounds is specially meant for the treatment of products containing or consisting of cellulose fibres or similar, such as textiles, carpets, boards, etc. in order to improve their fire resistance. The main components of the blend (phase 1) are preferably 15 - 50 w.p. urea phosphate, 0.01 - 0.05 w.p. preferably non-ionic moisturizing agent and 7 - 23 w.p. amonia, diluted in water. The blend also contains (phase 2) about 4 - 10 w.p. (solid matter) melamine resin or similar, 1 - 4% polythene solution and 0.1 w.p. di-ammonium phosphate. For the treatment the product is dipped in the solution, whereafter surplus solution is squeezed out and the product is dried and condensed at the temperature of about 170-220<o>C. It is of advantage to carry out the treatment in two successive phases, where in the first phase the product is dipped in a solution containing 15 - 50% urea phosphate, 0.01 - 0.05% moisturizing agent and 7 - 23 % of 25 % ammonia water, whereafter the product is dried and roasted and, in the second phase, dipped in a solution containing 4 - 10 % melamine resin or similar, 1 - 4 % polythene solution and about 0.1 % di-ammonia phosphate, and the product is dried and roasted after each dip. The temperature used in drying and roasting in the first phase is about 170 - 220<o>C and in the second phase 120 - 160<o>C.

Description

Mixture of chemical compounds for the treatment of cellulose fibers containing or products made therefrom to improve their fire resistance and processes to carry out the treatment

The subject of the invention is a mixture of chemical compounds as described in the introduction to the patent claim 1 is described.

Heretofore, for example in US Pat. No. 3,629,052, the use of urea phosphate as the main ingredient has been found such a composition is known. The disadvantage of this composition, however, is that the treatment does not make the product resistant to washing, at least not to the extent required. This is a serious disadvantage as work clothes, overalls, etc. have to be washed frequently while Garments made from textiles treated with this known agent by the known method are no longer sufficiently fire-resistant after washing. However, fire resistant fabrics are available these days required where safety regulations for work clothes have become stricter, which are worn under certain working conditions. The procedure however, the fabric referred to in the above U.S. patent is primarily for use in treatment determined by upholstery fabrics made of fiber material, how they are used in the auto industry etc. In this case, the lack of washability is not one

particular problem as such products are seldom washed.

The object of the invention is to develop a chemical composition and a method that the Make treated products containing cellulose fibers or the like in the long term fire-resistant, so that frequent washing does not impair their fire resistance, at least to a significant extent.

Another important task is to establish a method and a means for using the at the production of urea phosphate produced waste liquor, urea phosphate as such from the liquor not can be separated. This will add to the economics of manufacture to a considerable extent.

The task is further to develop a chemical composition necessary for the fire resistance treatment a wide variety of fiber products such as e.g. B. paper, cardboard, fiberboard, particle board, etc., can be used.

The invention is characterized in that the mixture chemical substances contains at least the following active ingredients: 15-50% by weight urea phosphate, 0.01-0.05% by weight of a known, preferably non-ionic wetting agent and 7-23% by weight 25% ammonia water. The rest of the mixture is mostly water.

Makes a mixture corresponding to the main characteristic, used according to the method according to the invention Cellulose fiber products are fire resistant, which means

that frequent washing does not significantly affect this property.

According to an additional feature of the invention, the invented mixture of chemical compounds contains 4 - 10% Melamine resin (solid) or the like, 1 - 4% polyethylene emulsion and 0.1% diammonium phosphate accordingly about 3% of the amount of resin. This mixture can contain all or one or two of these substances.

Some benefits are obtained by adding these funds achieved, such as B. Shrink resistance, improved wash resistance and better tensile strength and flexibility of the fiber product.

The inventive method provides for merely immersing a cellulosic fiber product according to the invention in the mixture, after which the product in one or more stages at about 120 - is (condensed) 220 ⁰ C temperature dried and roasted.

According to an advantageous embodiment, the cellulose fiber product is treated in two phases. First, the product is immersed in a salt solution which contains the above-mentioned wetting agent, urea phosphate and ammonia, after which the product is dried and condensed ^{at about 170 220 ° C.} In the second stage, the product is immersed in another solution containing the above-mentioned melamine resin or the like, as well as polyethylene emulsone and diammonium phosphate. The product is then preferably at about 120 to 160 ⁰ C dried and condensed.

The invention will become some in the following description

mixtures according to the invention with reference to tables explained. These blends were used for the treatment of cellulosic fiber products, after which their Fire resistance and some physical properties were investigated. The test results are in given the form of a table, where the effect produced is graphically visible.

The composition of the in the following table (Table 1) Different made up mixtures shown varies in different proportions to get the most beneficial Find out the amount of each ingredient.

The ingredients used were

1. "Tinovetin-JU" v £ /, one manufactured by Ciba-Geigy AG non-ionic wetting agent. Similar fabrics are also manufactured and sold by other companies. The Wetting agent contributes to the even distribution of the solution in the product, e.g. B. cloth, at. The means will used at about 0.01 to 0.05 wt.%.

2. Urea phosphate is a water soluble salt of urea and phosphoric acid, also a commercial product. It is used in the mixture according to the invention to to make the product refractory. Urea phosphate can can also advantageously be used in the form of a waste liquor, which is a by-product of its industrial production is and where the urea phosphate content is about 43% amounts to. The amount used is about 15 to 50% by weight.

3. Ammonia is used in the form of a 25% solution. It is used to neutralize the acidity caused by urea phosphate, thereby preventing the product, e.g. B. cloth becomes brittle.

It also brings in nitrogen, which contributes to the formation of polyphosphates. The amount used is about 7 to 23% by weight.

4. "Lyofix CHN" is the trademark of a melamine resin product, which is sold in different slightly different derivatives. The function of this The substance in the mixture according to the invention is the durability of the fire resistance properties to improve compared to washing as well as the tensile strength, shrinkage resistance and flexural strength of the To improve the product. Melamine is the source of cyanamide, which contributes to the formation of amidopolyphosphates. The amount used is about 4 to 10 weight percent solids.

5. Polyethylene emulsion acts as a plasticizer. The amount used is 1 to 4% by weight.

6. Diammonium phosphate acts as a catalyst that helps polymerize the melamine resin. The used Amount is about 0.01 wt%.

7. The substances are dissolved in water, which is what the rest of the mixture consists of.

Table 1. Compositions used in the experiments, where the content of each component is given in g per kg of the mixture is.

re
scep
No. "Tino-
vetin
JU "1) Finishing agent g / kg NH ₃
(25%) "Lyofix
CHN "1) PE
emul-
s ion
2) (NH ₄ ) ₂
HPO ₄ water 108 Ia 0.10 Urine-
material-
phos-
phate
2) 40.0 27.8 1.0 781.1 b 0.10 150.0 - 40.0 27.8 1.0 631, 1 108lIa 0.10 300.0 - 80.0 27.8 2.0 740.1 b 0, 10 150.0 - 80.0 27.8 2.0 590.1 109 Ia 0.10 300.0 76.4 40.0 27.8 1.0 704.7 b 0.10 150.0 152.8 40.0 27.8 1.0 478.3 10911a 0.10 300.0 76.4 80.0 27.8 2.0 663.7 b
110 ³⁾
Yes 0.10
0.10 150.0 152.8
153.2 80.0 2.0 437.3
546.7 b 0.10 300.0
300.0 204.3 - - - 395.6 C. 0.10 400.0 255.3 - - - 244.6 11011a
b
C. 0.10 ⁴⁾
0.10 ⁴⁾
0.10 ⁴⁾ 500.0 153.2
204.3 ⁵⁾
255.3 ⁵ > 8O, O ⁶⁾
8O, O ⁶⁾
8O, O ⁶⁾ - 2, O ⁶⁾
2, O ⁶ >
2, O ⁶ > 917.9 ⁶⁾
917.9 ⁶⁾
917.9 ⁶⁾ 300, O ^5J
400, O ^5J
500, O ^5}

Explanation of the reference numbers in the table:

1) Manufacturer: Ciba-Geigy AG

2) Supplier: Aaltosen Tehtaat Oy Sarvis

3) single phase

4) 0.1% in each phase

5) First of two phases

6) Second of two phases

Three fabric materials were treated with the compositions given in Table 1: Printed 100% cotton, 150 g / m 2; 100% wool overall fabric, 320 g / m ² ; and "Wo / Vi / Pa" 60/20/20 upholstery fabric,

400 g / m. Tissue samples (5.5 χ 16 cm) with normal air conditioning were immersed in the finish solution (5 s), excess solution was squeezed (humidity 70-100%), then the material was dried for 6 minutes at 170 - roasted 220 ⁰ C. In the two-phase treatment, the sample was dried after immersion in salt solution and ^{roasted at 180 °} C., and after the subsequent immersion in resin solution, it was ^{dried at 120 °} C. and ^{roasted at 160 °} C. (3 min).

Since it is known that certain changes in urea phosphate within the range of 170 - 220 ⁰ C temperature takes place, it seems that the drying and roasting should preferably take place within this range.

The samples were rinsed in water (40 ⁰ C) four times, then dried, air-conditioned and weighed. The “L0I” values (oxygen index) were measured using “FTA Flammability Unit Equipment” in accordance with the “ASTM 2863-70” standard in order to check the fire resistance achieved.

The results of the preliminary finish tests are shown in Table 2 on the following page.

Explanations of the reference numbers in table 2:

-) Precipitation in the solution

1) Immersion in saline solution in the first phase

2) Immersion in resin solution in the second phase

3) Weight gain caused by salt

4) Weight gain after soaking in resin and drying

5) Weight gain after immersing in resin, drying, and condensing

6) Pressure increase after washing

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Table 2

A. I I a, b I a Immersion% Weight gain% 11th 105 owing to W 12.5 Coverall fabric I a 48 ²⁾ 5.3 4 8 51 ²⁾ 16.6 -0.4 Au , 7 ⁶⁾ "DOI" value:% 3printed cotton fabric Ila, b b Cotton fabrics were - fragile due to acid hydrolysis 26.3 Immersion ' b 39 9.3 4; i ⁶⁾ 38 29.5 -21.7 ⁶⁾ , 4 Recipe No. I a Ha solution 15.9 72 Ha 7.1 4.1 16.0 +2.1 108 b b 85 30.8 76 b 9.1 12.0 32.9 -4.5 19.7 108 Ha I a 89 25.5 72 I a 6.1 2.5 18.3 5.0 > 25.0 109 b b 88 37.6 83 b 7.6 4.8 36.8 3.1 21.0 I a C.
Ha 91 ³⁾ 26.0 71 Ha 16> 11.8 ⁵⁾ 23.0 ⁴⁾ 15.4 ⁵⁾ 12.9 6.8 29.8 109 b b 93 42.9 68 b 25.9 20.0 20.1 11.6 51.3 12.0 > 27.5 C.
Ha C. 94 48 ²⁾ , - 1) ₆ g I a - - 33.4 -1.1 8th 31.5 110 b 33 71 b 62.2 -0.5 11th 31.5 C. C.
Ha ■
h weight gain% Immersion% weight gain% 3) ₃₂ " ₉ 20.1 ⁴⁾ 10.0 ⁵⁾ - 30.8 110 B. Dyed C. polyester fabric b ς » ¹¹ ' ² 97 46 * 3 27.5 15.0 6.2 ⁶ > Recipe No. Recipe No. C. ^D '22.9 97 6.8 109 108 12.0 88 IF "IDI" value:% 32.4 93 19.7 109 108 17.3 94 23.0 29.2 104 21.8 110 109 ³⁾ 28.0 82 25.0 30.7 101 25.0 110 109 96 25.2 ("WO / VI / PA") 113 25.6 110 ¹⁾ 96 25.8 99 110 "IDI" value:% 21.0 , 2 ⁶ > 24.0 , 4 22.0 24.0 21.0 21.7 21.0 21.1 22.3 4th 23.1 4th 21.5 22.0

The results show that there are only finishes in neutralized (ammonia) solutions for cotton fabrics suitable. In acidic solution (108) will give the best result obtained for a wool blend fabric, but the effect is not sufficient according to the "LOI" value.

According to the "LOI" values of cotton fabrics, the Recipes 1101Ia, 11011b and 110Ib in this stage as can be considered equally effective. In addition, recipe 10911b was good for a high "LOI" value. On consideration of the alternative methods (1-phase, 2-phase), recipes 11011a, 110Ib, 10911b are another Worth investigating. The "LOI" values 31.5-29.8 of printed cotton fabric treated with these recipes show good fire resistance, but the corresponding values of overall fabric, 25.8 - 25.0, were not fully satisfactory (around 26-27). This condition can likely be improved by the amount of immersion and the proportion of protective agents in the fabric is increased or the absorption properties of the Tissue improved.

In order to test the durability and durability of the fire resistance to laundering achieved by the mixtures and methods of the invention, three most effective of the above recipes were selected: 10911b, 110Ib and 11011a. They were made on 100% cotton (148 g / m ² calico,
applied as follows:

2
wool (148 g / m calico, printed), 10 χ 0.3 m each,

- Immersion in 90% finishing solution

- drying at 180 ⁰ C, 3 min (109II, 1101)

- Roasting at 180 ⁰ C, 3 min (109II, 1101)

- drying at 180 ° C, 3 + 3 minutes, and secondary drying at 120 ⁰ C and roasting at 150 ⁰ C, 3 min (110II)

2A5997

- washing of the finish 60 ⁰ C for color wash, normal washing powder "SIS A" 5.6 g / l, five wash cycles

- Drying in room air.

The finished fabrics were air-conditioned (24 hours, 20 ⁰ C, 65% relative humidity), and their flame resistance and technical textile properties were measured. The remainder of the fabrics were washed, including intermediate air conditioning, and the properties noted above were measured after one, three, ten and twenty washes. The average hardness of the water used was 4 ° dH.

The properties and laundry durability of the finished Fabrics are given in Table 3 on the next page. The following determination methods were applied:

"LOI" value: "ASTM standard 2863-70" (FTA Flammability Unit% O ₂ )

Tensile strength and elongation at break: "SFS 2983" Dimensional change: "SFS 2998" Crease resistance: "SFS 3377"

Flexural strength: "TAPPI" method ("Handle-O-Meter" (g), opening width 20 mm)

Square dimensions: "SFS 3192

Explanations of the abbreviations above the columns:

Drop in tensile strength

Elongation at break

Dimensional change

k = in the weft direction

1 = in chain direction

Flexural strength ο = correct η = reversed.

Table 3

Wash durability and other properties of the finished fabrics

recipe , 8 g / l 0 Weight "LOI" - Tensile strength k 1 Elongation at break k 1 Dimensional change % 1 _ Crease Flexural strength. η 1 growth worth waste % change -1.5 firm sturdiness , 1 g / i % % % 43.5 37.9 13.6 9.8 speed 17.0 109 II b 3 49.0 45.4 14.4 9.3 k -2.9 0 28.5 UF 300.0 g / l g / i 10 -4.5 NH ₃ (25%) 152 20th 22.2 24.2 59.4 44.4 12.7 11.3 _ -5.8 _ 16.5 23.5 Wetting 28.4 24.5 48.3 42.5 13.8 13.0 -0.2 2 29.0 29.5 medium 0 3 g / l 0 55.3 56.6 14.3 13.5 - 30.5 CHN 80.0 g / l 1 30.4 24.2 -0.4 -2.4 2 22.5 (NH ₄ I ₂ HPO ₄ 2.0 1 g / i 30.4 23.7 55.1 46.0 14.6 9.8 0 3 29.0 14.5 110 I b 3 31.1 24.1 59.2 48.0 12.5 11.7 -0.4 -3.5 2.5 34.0 25.5 UF 400.0 g / l 10 -5.7 NH ₃ (25%) 204, 20th 25.7 27.1 52.4 43.7 13.8 11.9 _ -5.7 _ 14.0 26.5 Wetting 36.5 25.3 59.2 58.9 14.6 13.4 -0.6 3- 24.0 34.4 medium 0, 2 g / l 0 27.3 73.1 16.2 15.8 _ 40.0 1 36.5 25.1 -0.2 -1.4 2- 25.0 1 g / i 36.5 24.5 73.4 35.8 13.7 5.9 +0.2 2+ 37.5 17.5 110 II a 3 36.5 24.7 56.0 34.6 13.6 6.7 -0.6 -3.0 3- 41.5 18.5 UF 300.0 g / l g / i 10 -6.3 NH ₃ (25%) 153, 20th 20.3 25.0 69.0 44.0 11.8 6.6 _ -7.2 _ 17.5 17.0 Wetting 0 23.0 25.1 62.1 44.4 13.4 9.0 -0.8 - 3- 18.0 16.5 medium O, 1 82.1 56.0 10.5 9.1 -3.5 15.5 CHN 100.0 g / l 3 27.7 24.8 0 0 17.9 6.1 -0.4 -3.9 2 16.0 16.5 (NH ₄ ) 2HPO ₄ 2.0 10 30.4 24.1 +5.3 -0.3 18.6 8.8 -1.0 -5.5 3- 17.0 18.5 Untreated 20th 30.4; 23.8 +3.9 -3.3 18.4 9.4 -1.4 -6.2 3- 17.0 15.5 - 18.2 -3.6 -3.8 16.5 10.0 - - 17.0 15.0 7.4 - -0.7 -8.4 17.0 10.2 -1.7 2+ 18.0 13.0 6.8 - -1.2 2 15.5 6.8 - -0.8 2.5 15.0 6.8 - -1.7 2.5 14.5

CO NJ -ΡΟΗ

The effect of the acidity of the finishing solution was determined by regulating the pH of the various solutions using Ammonia so that the value was 7.5 tested. The finishing treatment was carried out as above, and the tissue

be washed once. The weights per m, tensile strength and "LOI" values of the tissues were determined. The results are given in Table 4 below.

Table 4 Effect of the acidity of the finishing solution

recipe
(pH = 7.5) b Weight
growth
% "LOI
% Il Tensile strength
waste %
k 1 , 9 46.5 Elongation at break%
k 1 8th ,8th 109 II b 29.7 23, 6th 46 , 9 43.7 15.5 12th ,8th 110 I. a 35.1 24, 7th 46 , 3 39.1 15.4 6th , 4 110 II 25.0 24, 3 54 14.9

According to the test results can be neutralized with ammonia Urea phosphate solution can be used as a finishing agent to make cellulose fibers washable (dye washing, Household washing powder) and to make them fire-resistant. The required amount of the fire retardant (additive) is 25 to 30% depending on the weight of the fabric or material, the "LOI" values are 27-25% and the tensile strength drop is 4 5 to 55%. When resin of the methylol melamine type is added to the finishing solution, the Wash resistance of fire resistance as well as tensile strength, shrinkage resistance and the handle (flexural strength) of the tissue improved.

If the finishing solution is made somewhat alkaline with ammonia (pH 7.5), the fire resistance deteriorates and the tensile strength does not become either improved to a noticeable extent.

Investigations into the use of other aminoplasts, such as "DMOHEU", "DMEU", "DMDHEU" or "DMEU" in the mixtures according to the invention instead of melamine resin showed that this was insufficient Produced wash resistance. The fire resistance of the samples disappeared with the first wash.

The method of the invention for refractory of cellulosic fibers can be used in other ways than by Immersion of the product in the solution can be applied. The solution can be through nozzles or the like can also be sprayed on.

The embodiments can vary within the scope of the patent claims.

Claims (6)

Claims 1. Mixture of chemical compounds, specially determined for the treatment of products containing or consisting of cellulose fibers or the like, such as B. textiles, fabrics, carpets, boards, etc., to improve their fire resistance, the composition contains urea phosphate diluted in water and ammonia, characterized, that the main components of the solution are preferably 15 - 50% by weight urea phosphate, 0.01-0.05% by weight of one preferably non-ionic wetting agent and 7 - 23% by weight are ammonia diluted in water. 2. Mixture of chemical compounds according to claim 1, which contains melamine resin, characterized, that they also have about 4-10% by weight (solids) melamine resin or the like, 1-4% polyethylene solution and 0.1% by weight of diammonium phosphate either individually or contains two or all of these substances. 3. Mixture of chemical compounds according to claims 1-2, characterized, that it consists of two phases, the partial mixture of phase I of claim 1 and the partial Mixture of phase II of claim 2 corresponds. 4. Process for treating products containing cellulose fibers or the like with a mixture chemical compounds according to claims 1-2, in order to make the product fire-resistant or his To improve fire resistance, the process also including heat treatment, characterized, that the product is immersed in the solution, the excess solution is squeezed out and the product is dried over
is condensed. nis dried and preferably at about 170-220 ° C 5. Process for treating products containing cellulose fibers or the like to make them fire-resistant to make or to improve their fire resistance, using a mixture of chemical compounds according to the Claims 1-3 is used, the method also including heat treatment, characterized, that the treatment is carried out in two successive phases, in the first phase the product in a 15-50% urea phosphate, 0.01 0.05 % Wetting agent and 7-23% solution containing 25% ammonia water is immersed, after which the product dried and roasted and in the second phase in about 4 - 10% melamine resin or the like, 1 - 4% polyethylene solution and a solution containing about 0.1% diammonium phosphate is immersed, whereby the product is dried and roasted after each dip. 6. The method according to claim 5, characterized, that applied during drying and roasting temperature in the first phase is about 170 - 220 ⁰ C and the second in the Phase 120-160 ⁰ C. Method according to claims 5 - 6, characterized, that the drying and roasting can be carried out in the second phase is at least twice, with the temperature at the first time about 170-220 ⁰ C and the second time from 120 to 160 ⁰ C.