DE2310039A1 - FOAM PREVENTION AGENT FOR THE CARPET AREA - Google Patents

Description

PATENT LAWYERS

DR. I. MAAS DR. F. VOITHEiMLEITNER

8 MUNICH 40 SOtIJSSHtIMER ST. 299-TE. 3592201/203

Case DC 1918

Dow Corning Corporation, Midland, Michigan / USA

Antifoam agents for carpet dyeing

Direct and indirect losses from fire run in the billions of dollars each year. These losses occur in property, personal accidents and human lives. Much effort has been made to find ways and means to prevent this loss and damage. In the United States of America, Federal Standard DOC-FF-1-70 requires that all carpets manufactured after April 15, 1971 pass the Methenamine Tablet Test for carpet fire hazard. This test is generally referred to in the industry as the "(bitter) pill test ¹¹ ". In the following, this test is simply referred to as the "pill test" based on the American terminology.

During the dyeing of carpets in their manufacture, it is necessary to use an antifoam agent to prevent the To regulate foaming that occurs in the dye bath. Antifoam agents that differ from various polydimethylsiloxanes derive were used for this purpose. When the first reports appeared indicating that the Silicone antifoam used in dyeing processes for polyester

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are used, increase the fire hazard of carpets, they were not believed. An investigation of the problem showed that the silicones currently used as antifoam agents are used that are inert per se and not flammable; however, there were plausible mechanisms as to why s; le to the increased fire hazard of polyester carpets could contribute. There has therefore been a difficulty in finding a material or a composition which would be an effective antifoam agent is in carpet dyeing processes that do not stain or streak the carpet and which does not in any way adversely affect the fire hazard of the carpet, i.e. the carpet has to pass the pill test.

The invention is an antifoam agent that essentially contains

(1) a siloxane-glycol copolymer,

(2) a foam control agent and

(3) a hydroxyl end-blocked polydimethylsiloxane.

This composition is valuable in carpet dyeing processes and is particularly useful for dyeing polyester carpets.

The agent according to the invention contains essentially

(1) A composition consisting essentially of 30 to 90% by weight of a siloxane-glycol copolymer of the general type Formulas

(A) R _a Si [(0SiMe ₂ ) _n (0SiMeG) _b 0SiMe ₂ G] ₄ _ _a

(B) R _a Si [(OSiMe ₂ J _n (OSiMeG) _c 0SiMe ₃ ] ₄ _ _a

(C) GMe ₂ Si (0SiMe ₂ ) _n (dSiMeG) _b 0SiMe ₂ G and

(D) Me ₅ Si (0SiMe ₂ ) _n (0SiMeG) _c 0SiMe ₃ where

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R is a hydrocarbon group free of aliphatic multiple bonds with 1 to 10 carbon atoms,

Me is a methyl group,

G is a group of the formula -D (OR ') A

where D is an alkylene group with 1 to 30 carbon atoms, R ^{1 is} an alkylene group with 2 to 10 carbon atoms, m is at least 1 and A is a protective group or end group (capping group),

a has a value of 0 or 1, η has a value of at least 1, b has a value from 0 to 50 and c has a value from 1 to 50,

(2) 5 to 35% by weight of a foam control agent consisting essentially of 85 to 96 parts by weight of a liquid triorganic silyl end-blocked polydimethylsilo-

o xans with a viscosity of at least 20 cSt. at 25 C, 4 to 12 parts by weight of silicon dioxide and 0 to 3 parts by weight of a siloxane resin which essentially contains SiO ₂ units and (CH ₃ ) .jSiO ^ units, the ratio of (CH ₃ ) ^ iO ^ units to SiO ₂ ~ units in the range from 0.4 / 1 to 1.2 / 1 and

(3) 5 to 35% by weight of a liquid hydroxyl end-masked or end-blocked polydimethylsiloxane with a viscosity of 50 to 200 cSt. at 25 ° C. '

The first ingredient of the present invention is a siloxane-glycol copolymer of the general formulas (A), (B), (C) and (D) as given above. In these formulas R can be any hydrocarbon group free of aliphatic multiple bonds and having 1 to 10 carbon atoms mean, such as a methyl, ethyl, propyl, isoproDyl, Butyl, hexyl, decyl, phenyl ^, tolyl, benzyl, XyIyI-, methylcyclohexyl-, cyclohexyl- ,. Cyclopentyl, ß-phenylpropyl or ß-phenylethyl group.

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Specific examples of alkylene groups D that make up the glycol part from G to the silicon atom are methylene, ethylene, propylene, isopropylene, butylene, octylene, Decylene, octadecylene and myricylene groups. D preferably contains 1 to 18 carbon atoms.

In the above formulas, R · denotes any alkylene group containing 2 to 10 carbon atoms. -R ¹ can thus be an ethylene, propylene, isopropylene, butylene, hexylene, octylene or decylene group. Most preferably R ¹ contains from 2 to 4 carbon atoms. It should be noted that. R · can be derived from a single glycol or from a mixture of glycols, ie for example OR ¹ can only mean ethylene oxide units, propylene oxide units or butylene oxide units, or OR ¹ can represent a combination of such units.

The symbol m representing the number of OR 'units in the glycol part of the molecule can have a value as low as 1 and it can range up to 1000 or be bigger. In general, m will have an average value in the range from 10 to 100.

The glycol or polyoxyalkylene unit contains group A as a terminal group or is terminated by group A. The specific nature of this group is not critical to the present invention. The glycol can through a hydroxyl group (A means a hydrogen atom) through an ether group (A means a monovalent hydrocarbon group such as a methyl, butyl, vinyl or phenyl group), by a carboxyl group, by the salt or ester of a carboxyl group, or by a carbonate ester group or terminated by an isocyanate group.

The symbol n representing the number of dimethylsiloxane units in the molecules, can have a value of at least 1

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sit and can range up to 1500 or higher. It is believed that the number of dimethylsiloxane units in the molecule in relation to the glycol containing G units should be at least 10: 1 for the best results. The upper ratio of OSiMep units to units containing G can be 50: 1 or more.

The siloxane-glycol copolymers that are useful for this are well known, commercially available materials. For those unfamiliar with these compounds, refer to US patents 3 402 192, 3 518 288 and 3 637 783 are pointed out, where the making of these compounds and other details are explained.

The siloxane-glycol copolymer may range from 30 to 90 wt.% Of the composition constituting ·

The second component of the agent is the foam control agent. This agent can constitute from 5 to 35 parts by weight of the composition. The suds control agent contains essentially from 85 to 96 parts by weight of a liquid triorganosilylene terminated polydimethylsiloxane having a viscosity of at least 20 cSt. at 25 ⁰ C, from 4 to 12 parts by weight of silicon dioxide and from 0 to 3 parts by weight of a siloxane resin, consisting of (CH,), SiO ^ / ₂ units and SiO2 units, where in the resin . * the ratio of (CH,) · SiO _1/2 -Einheiten.zu the SiOg units in the range of 0.4: is 1: 1 to 1.2.

The liquid triorganosilyl end-blocked polydimethylsiloxanes are well known compounds and are commercially available from many places. You can go through different Processes such as joint hydrolysis and subsequent condensation of triorganomonohalosilanes and dimethyldihalosilanes or by cracking and subsequent condensation of the pimethylcyclosiloxanes. the

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Organic end-blocking (= masking) groups can be any of the well-known hydrocarbon groups, but it is preferred that they contain from 1 to 6 carbon atoms. The trimethylsilyl end masking group is likely the one that is common in commerce. Dimethylphenylsilyl and dimethylvinylsilyl groups are also quite common. Examples of other organic groups include ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, allyl and octadecyl groups. In order to obtain a noticeable antifoam or defoaming effect, the viscosity of the triorganosilyl-end masked polydimethylsiloxane must be at least 20 cSt. at 25 ° C. The upper viscosity limit of this compound is not critical and can range up to 1,000,000 cSt. his or higher as determined It is believed that to get the best results when the viscosity of the triorganosilyl endmasierten polydimethylsiloxane is in the range of 20 to 2000 cSt at 25 ⁰ C.. is at 25 ⁰ C.

The siloxane resin that can be used in the composition is also a standard compound that is commercially available available from various sources. It can be produced by cohydrolysis and condensation of (CH,), SiCl and SiCl ^ or by reaction of (CH,), SiCl with acidic silicon dioxide sol can be obtained. Its preparation is described in detail in many references and is therefore in the present application is not explained in more detail.

A silica airgel is a type of silica that can be used in the composition. Such In short, materials are made by putting the water in a silica hydrogel or silica hydrogel displaced with a low-boiling organic liquid such as ethyl alcohol, the treated gel in an autoclave heated to about the critical temperature of the organic liquid and then the vapors of the organic Lets liquid escape from the autoclave, whereby

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excessive shrinkage or breakage of the cellular ones Structure of the silicon dioxide or the silica is avoided. The details of this procedure are in Described literature and silica aerogels are commercially available. Other silicas or silicas that are used are precipitated silica, silica xerogels, fumed silica and treated Silicas containing organic silyl groups on their faces can also be used. These and others Silicas that can be used are all well known and can be readily selected by those skilled in the art will.

The third main component of the composition is a liquid hydroxyl endmaskiertes polydimethylsiloxane having a viscosity of 50 to 200 cSt.bei 25 ⁰ C, which, in the composition in an amount of 5 to 35% by weight may be present. This ingredient can be prepared by well known methods such as hydrolysis and condensation of dimethyldichlorosilane or cracking and subsequent condensation of dimethylcyclosiloxanes. It has been found that it is necessary that this third ingredient be soluble in ingredient (2), the foam control agent, in order not to adversely affect carpets which are to pass the pill test. . · = It has been found that the materials which have a viscosity in the range given above have the required solubility.

The composition according to the invention is prepared by simply putting the three ingredients together in the correct Mixed proportions. As far as is known to date, there is no particular order in which the ingredients are mixed Need to become. As far as we know today, the best method for producing the mass according to the invention is in adding the hydroxylated dimethylsiloxane to the siloxane-glycol copolymer and mixing well. Then it will be

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the foam control agent is added and mixed well and finally the composition is passed through a colloid mill passed through.

The amount of the composition of the invention that is used depends on the particular system in which the foam is being used should be controlled from and to the extent that the consumer wishes to control the foam. Thus the Amount will vary depending on whether the composition is in an alkaline soap solution, when evaporating alkaline Paper black liquid, in the concentration of synthetic rubber latices, in steam distillation of styrene-butadiene emulsions, in the refinery of sugar, in the dyeing of textiles, in the treatment of waste for To be thrown away or used in other procedures. In general, 20 to 150 ppm of that according to the invention are sufficient Composition based on the volume of the system in which the foam is to be controlled for most applications the end. The compositions of the invention can be used as any type of foam control agent, for example can be used as defoamers and / or as antifoam agents. Defoaming agents are generally considered to be Agents that reduce suds whereas antifoam agents are generally considered to be anti-suds will. As already indicated, the compositions according to the invention can be used for one or both uses will. It should be noted that the compositions of the present invention are available as 10056 solids, i.e. pure, can be used, or one can prepare and use emulsions or solutions thereof in suitable solvents, if this simplifies handling and addition to the system.

The following examples illustrate the invention without restricting it. All parts and percentages are through the

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weight is printed out and all viscosities are determined at 25 ° C, unless otherwise stated.

example 1

A composition is prepared that, essentially contains

(1) 5096 of a siloxane-glycol copolymer of the general formula

(CH ₂ ) ₃ O (C ₂ H ₄ O) 3

(2) 2596 of a foam control agent, which consists essentially of about 88 parts of trimethylsilyl-end masked polydimethylsiloxane with a viscosity of about 1000 cSt., About 10 parts of silica airgel and about 2 parts of a siloxane resin, which consists essentially of Si0 ₂ units and (CEs) ₃ SiO contains _1/2 units in a ratio of 1: 1.2 are available, and: 0.4 to 1

(3) 2596 of a hydroxyl end masked polydimethylsiloxane with a viscosity of about 75 cSt.

The above composition is prepared by adding the ingredient (3) to the ingredient (1), mixing well, then add ingredient (2) to the reaction mixture, mix well again, and then pass the mixture through a colloid mill once at a low speed and a setting of about 381 / u (15 mils) and an exit temperature of conducts about 55 ° C.

This composition is used to control foam in a polyester carpet dyeing process. the Composition is diluted with cold water and added approximately in an amount of 0.02-6 solids to the carpet dyeing basin added. During the usual staining cycle was the

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- ίο -

Good anti-foaming effect. The different types of carpets that colored in the presence of this antifoam agent tested for flammability using the Methenamine Tablet Test Procedure.

The pill test procedure is as follows: Eight samples the carpet to be examined is cut into 9 inch squares and placed in a drying oven, in which there is free air circulation. They are dried for 2 hours at 105 ° C and then in cooled in a desiccator room for at least 1 hour. The carpet samples are then removed from the desiccator with the Gloved hands are removed and the stack is brushed in a vertical direction. He will is placed in the test chamber and a steel ring, 8 inches in diameter, is placed on top of the samples. One methenamine tablet is placed on the samples in the center of the ring and ignited with a match. When the area of the Carpet that is burned does not extend up to 2.5 cm (1 inch) to the steel ring (7.6 cm in any direction), the sample passes the test. Six out of eight samples must pass the test for the carpet to meet government requirements Fulfills.

Test results when dyeing carpets with the invention Composition are given in the following table:

Pill attempt

Type of carpet number of samples, number of samples,

they pass the fail

Viceroy - 8 0

Duvol 8 0

Shag (raw cloth)

5 cm thick 8 0

colored carpet 4 4

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⁺ For comparison. This carpet was not rinsed with cold water after the end of the dyeing run. It is believed that the cold water after dyeing will cause the antifoam agent to be removed from the carpet while ensuring that the silicone does not add flammability to the carpet and thus enabling it to pass the pill test.

Example 2

A composition was prepared as described in Example 1, except that it was made up of essentially 70% ingredient (1), 15% component (2) and 15% component (3). This agent was used under operating conditions as an antifoam agent used in a jet dyeing textile process. The composition was made in four different jet dye machines used at concentrations of 0.91 kg / device. Excellent foam control was achieved in each case throughout the staining cycle. No dye or silicone stains were observed on the textile materials. These trials were conducted using burgundy, black, and light yellow tones colored, three of the most difficult types of dyeing. If you use one of the commercially available silicone antifoams that are specially designed for the Jet dyeing processes have been determined, so are these Shades 2.27 kg. • Antifoam per device required to regulate the foam at the critical vent level.

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Claims (8)

Claims 1. Means containing mainly (1) 30 to 90% by weight of a siloxane-glycol copolymer the general formulas (A) R _a Si [(OSiMe ₂ ) (OSiMeG) J ₃ OSiMe ₃ G] ^ _ _a (B) R Si [(OSiMe ₀ ) (OSiMeG) OSiMe,], _m (C) GMe ₀ Si (OSiMe ₀ ) (OSiMeG). OSiMe ₀ G and £ c Xi D Δ (D) Me ₃ Si (OSiMe ₂ ) _n (OSiMeG) ₀ OSiMe ₃ R is a hydrocarbon group free of aliphatic multiple bonds and having 1 to 10 carbon atoms, Me is a methyl group, G denotes a group of the structure -D (OR ¹ ) A, in which D denotes an alkylene group with 1 to 30 carbon atoms, R "denotes an alkylene group with 2 to 10 carbon atoms, m denotes a value of at least 1 and A denotes a protective group, a has a value from 0 to 1, η has a value of at least 1, b has a value from 0 to 50 and c has a value from 1 to 50, (2) 5 to 35% by weight of a foam control agent which essentially contains 85 to 96 parts by weight of a liquid triorganosilyl-endmasked polydimethylsiloxane with a viscosity of at least 20 cSt. contains at 25 ° C, 4 to 12 parts by weight silicon dioxide and 0 to 3 parts by weight of a siloxane resin containing ₂ ~ units and (CH _{3) 3} Si0 _1/2 units consists essentially of SiO, wherein the ratio of (CH ₃ ) ₃ SiO./ ₂ ~ units to SiO ₂ ~ units is in the range from 0.4 / 1 to 1.2 / 1, and 40982 77 0919 (3) 5 to 35% by weight of a liquid hydroxyl endmasked Polydimethylsiloxane with a viscosity of 50 to 200 cSt. at 25 ° C. 2. Means according to claim 1, characterized in that the component (1) in an amount from 50 to 70 wt.% Is present and has the general formula (D), and that the component (2) is present in an amount of 15 to 25% by weight is present and that the triorganosilylene end-masked polydimethylsiloxane has a viscosity in the range from 20 to 2000 cSt. and that the component (3) is present in an amount of 15 to 25%. 3. Agent according to claim 2, characterized in that (1) is present in an amount of approximately 50% and has the general formula Me ₃ SiO (OSiMe ₂ ) ^ ₇₅ (OSiMeG) ^ ₇ OSiMe ₃ , where G - (CH ₂ ), (OC ₂ H ₄ ) ^ ₂₄ (OC ₃ H ₆ ) ^ ₂₄ OOCCH ₃ means (2) is present in an amount of about 25% and consists essentially of about 88 parts of a trimethylsilyl-endmasked polydimethylsiloxane with a viscosity of about 1000 cSt., about 10 parts of silica airgel and about 2 parts of a siloxane resin consisting essentially of (CH ^) ₃ SiO ₁ / ,, units and SiO ₂ units, the units in a ratio from 0.4 / 1 to 1.2 / 1 and wherein (3) is present in an amount of about 25% and a viscosity of about 75 cSt. owns. 4. ~ Agent according to claim 2, characterized in that (1) is present in an amount of about 70% and has the general formula Me ₃ SiO (OSiMe ₂ ) ^ ₇₅ (OSiMeG) ^ ₇ OSiMe ₃ , where G - ( CH ₂ ) ₃ (0C ₂ H ₄ ) <~ ₂₄ (0C ₃ H ₆ ) ^ _{24 means} OOCCH ₃ ), (2) is present in an amount of about 15% and consists essentially of about 88 parts of trimethylsilyl-endmasked polydimethylsiloxane a viscosity of about 1000 cSt., about 10 parts of silica airgel and about ^ 2 parts 4 0982770919 consists of a siloxane resin which consists essentially of (CH ₃ ) ^ SiO ₁ Z ₂ - and SiO ₂ units, the units being present in a ratio of 0.4 / 1 to 1.2 / 1, and (3) is present in an amount of about 15% and has a viscosity of about 75 cSt. owns. 5. Agent according to claim 2, characterized in that (1) has the general formula Me ₃ Si (OSiMe ₂ ) ~ ₇₅ (OSiMeG) ^ ₇ SiMe ₃ , wherein G - (CH ₂ J ₃ (OC ₂ H ₄ ) ^ _{24 means} (OC ₃ H ₆ ) ^ ₂₄ OOCCH ₃ , and (2) consists essentially of about 95 parts of trimethylsilyl end-capped polydimethylsiloxane and about 5 parts of silica airgel. 6. Use of the agent according to one of claims 1 to 5 as a foam regulating agent in a process at which the foam is to be checked. 7. Use of the agent according to any one of claims 1 to 5 as a foam control agent in a carpet dyeing process . 8. Use of the agent according to claim 1 as a foam control agent in a carpet dyeing process in which a foam control agent is used and in which rinsing with cold water after completion of the procedure. . 409827/091 9