DE1769708B2 - METHOD FOR TREATMENT OF GLASS FIBERS BY USING ORGANOSILICON COMPOUNDS - Google Patents

Description

1 2

The invention relates to the treatment of monomers and siloxane-alkylene oxide copolymers

Glass fibers to make this one better, i. H. stronger seeds used to coat glass fabrics,

To give grip. In addition, they are created in this way, which gives the glass fabric a particularly soft feel

traded glass fibers water-repellent, puckered and what is achieved for the production of laminates

crease-resistant and crease-resistant. Also, having 5 is very useful.

they have good wash resistance. The aforementioned Belgian patent specification is therefore

According to the invention, a method for handling according to a different task than the invention

Treatment of glass fibers by means of organosilicon compounds according to the claimed method, their

gen claimed, which is characterized in that solution through the use of other organosilicon

one aqueous dispersions, the io compounds is achieved.

(1) 100 parts by weight of liquid, in the terminal, ^The glass fiber hand units used according to the invention containing hydroxyl groups contain three essential components, thylpolvsiloxane component (1) is mainly composed of siloxane

'units of the formula (CH ₃ ) ₂ SiO built up. In these

(2) 5 to 70 parts by weight of silanes of the general ₁₅ polymers, however, small amounts of formula of other siloxane units can also be present, such as

R ₇₁ SiRV * units of the formulas R " ₃ Si0 _{l / 2} , R" ₂ SiO, R "SiO _3/2 and

in which R is optionally substituted carbon SiO ₂ , in which R "is in each case an optionally halogenated

hydrogen radicals with 1 to 20 carbon atoms, R 'denotes hydrogenated hydrocarbon radical. Generally

Drolyzable radicals, with the exception of halogen- ²⁰ , these other units can be expressed in men-

atoms, and η has a value of 0 or 1 gene of less than 5 mol percent, based on the

and total number of siloxane units and preferably

, ", - ,,, _c .., ■ _rJ - ■ ^ - in amounts of less than about 2 mol percent to-

(3) catalysts for the condensation of Si-bound _{against his Dk} organopolysiloxanes (1) _übIichen known method can be prepared by Dener hydroxyl ^.

contain, to which the glass fibers are applied and the siloxanes, however, they are advantageously made by emulsion poly-

then hardens on the glass fibers. merization according to the in the German patent specification

In recent years, the use of glass 1,037,707 and Canadian patent 765,453 fibers for textiles is becoming increasingly important. described method obtained. The advantages of Here, however, some problems had to be overcome, there are organopolysiloxanes polymerized in emulsion which consisted in giving the fabric a good grip, in that the production of the invention was good Water-repellent effect, thereby facilitating crimped and creased aqueous dispersions durability, crease resistance, abrasion resistance, they are also better to handle and toughness and to impart dyeability. the more stable in normal rolling processes. So far

The viscosity of the polymer has already taken several routes to achieve these properties. But often the solution wasn't a critical issue. In general, however, it is advantageous for one of these problems only at the expense of the rest to adjust the viscosity of the liquid polymer properties. For example, sats would be at least 100cSt / 25 ° C. It is particularly stated that, in general, with decreasing preferred polymers are those whose viscosity, thickness of the glass fibers, the abrasion resistance of 40 is about 100,000 cSt / 25 ⁰ C; such connection of undeveloped tissue increases. These increases in genes are commercially available. It should be noted in this connection to abrasion resistance, however, at the expense of grip that all specified of the fabric. Viscosities relate to the polymers per se

A particular concern of the present invention and not its solutions or emulsions,

is therefore the treatment of glass fibers, which 45 The second crucial component of the inven-

gives a firmer grip, without the other proper treatment agents, silanes of the other

to influence the properties of the tissue. In addition given formula in which R, R 'and η the given

are of importance with the treatment according to the invention.

good water-repellent effect, crease-resistant - examples of radicals R are alkyl, alkenyl, alkynyl,

speed, improved crease resistance and good washing 50 aryl, aralkyl, alkaryl, cycloalkyl or the

availability achieved. These advantages are particularly evident in the case of speaking substituted radicals within the

Glass fiber fabrics achieve a yarn count of the given definition. Specific examples are

0.25 denier. Methyl, ethyl, propyl, butyl, amyl, hexyl,

The treatment according to the invention is particularly suitable for heptyl, octyl, decyl, dodecyl, hexadecyl, octa-

Glass fiber fabric suitable for the production of 55 decyl, eicosyl, vinyl, allyl, hexenyl, cyclo-

Rainwear, ski equipment, jackets, suits, hexenyl, cyclohexyl, phenyl, xenyl, tolyl, xylyl,

Bed covers, upholstered furniture covers, bath equipment - benzyl, 3-chloropropyl, 3,3,3-trifluoropropyl, di-

genes and draperies are used. chlorophenyl, α, α, α-trifluorotoryl, cyanoethyl, carb

For each of these uses a solid oxyphenyl, 3 - mercaptopropyl, mercaptophenyl,

The grip of the fabric is very important, which is expressed in it, 60 3-hydroxypropyl, 3-aminopropyl and such

that by clumping together in the closed of the formulas

Faust caused wrinkles when letting go of possible- H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ -

lets jump apart quickly, as in the examples H ₂ NCH ₂ CH ₂ NHCH ₂ CH (CH ₃ ) Ch ₂ -

with reference to the crimping and crease resistance ER _n

is purified. 65 , _x

In contrast, the Belgian patent / _{HrH n} , _pH . ,

script 686 489 mixtures of silanes or mixed ^{poly- CHa} ~ uitM, u (tH ₂ ) _{3 and a}

merisates of these silanes with unsaturated organic CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ -

3 4

R is preferably also a hydrocarbon radical. The decisive factor that is responsible for the properties given to 1 to 6 carbon atoms, including methyl and glass fabric, phenyl radicals are particularly preferred. By definition, it is the amount of siloxane solids that can accordingly be present in the silanes after treatment with the aqueous dispersion; however, it is preferred that a radical R has been deposited. That depends in part, that is, the index η can be 0 or 1; Preferred of the amount of siloxane solids in the aqueous way, however, η is 1. Dispersion from and on the other hand from the glass examples of hydrolyzable radicals R ', with the exception of the amount of aqueous dispersion atoms absorbed by halo tissue, are alkoxy- and alkenyl - sion. Generally speaking, there should be at least 0.5 geoxy, aryloxy, cellosolveoxy, glycoloxy, oxime weight percent of the siloxane solids on the glass or acyloxy residues. Specific examples of this ^ are tissue to be knocked down and for economic-methoxy, ethoxy, isopropoxy, butoxy, 2-ethyl borrowed reasons usually not more than 3 Gehexoxy, vinyloxy, allyloxy, phenoxy, acetoxy, weight percent. The amount is of course determined by the propionoxy, H ₂ N, SCN, (C ₂ H ₅ ) (CH ₃ ) C = N - O-, special properties that make the final pro-CH ₃ OCH ₂ CH ₂ O- , C ₂ H ₅ OCH ₂ CH ₂ - and HOCH ₂ CH ₂ O- 15 product should have.

Leftovers. R 'is preferably an alkoxy radical with 1 to In the following examples the crimp and 4 carbon atoms, of which the methoxy radical is particularly preferred for crease resistance due to agglomeration of the sample. ben in the closed fist and then the third component of the inventive spreading of the fabric on a flat surface treatment agent is the siloxane condensation catalog. An excellent ripple and wrinkle lyser. As far as is known up to now, any resistance is achieved for this if all folds or for the condensation of Si-bonded hy- fort burst apart. The spray test values, which can be used with known hydroxyl groups, measure of the water-repellent finish of the product as long as they represent the stability of the aqueous dispersion fabric, were in agreement with the non-interfering influence. Examples of Suitable Test Methods AATCC Test No. 22-1961 determined.
Catalysts are mineral acids such as hydrogen chloride, hydrogen bromide, nitric and sulfur Example 1
acids, strong bases, such as sodium, lithium and

quaternary ammonium hydroxide and dialkyltin- 300 moles of water were mixed with a few drops of ice-

diacylates, such as dibutyl tin dilaurate and dibutyl tin vinegar, then 5 ml of methyltrimethoxy

diacetate, the latter especially preferred silane being added with stirring and

are attached. stir until the solution became clear. Afterward

The aqueous dispersions from the invention were 35 g of a neutral anionic emulsion,

Ingredients used may be limited to any of the 35 weight percent of a liquid in the final

Way to be made. For example, standing units can contain hydroxyl groups

separated, compatible emulsions from the polymer dimethylpolysiloxane with a viscosity of about

and the catalyst are prepared, this contained at- 100,000 cSt / 25 ° C, which by emulsion poly-

finally mixed and added with the silane merization had been produced, with stirring in

the. Another option is to have the silane entered the solution. Then were stirring

and the catalyst simply the dispersion of the poly 4 ° 0.3 g of a 20 weight percent emulsion of di-

add merisats, which is added by emulsion polymer butyl tin dilaurate. Eventually it became so

sation has been established. After this procedure a lot of water is added that the total weight of the

a uniform aqueous dispersion or solution was 500 g.

get a single treatment bath. In order to achieve the best results in the aqueous dispersion thus obtained, however, it is advantageous to use a two-45 20.3 x 20.3 cm piece of glass fabric (manufactured bath system. Such a system is made of threads with a degree of fineness 0.25 denier is also ideally suited for loading under rolling conditions and yarn with a fineness of approx. 300 denier). In the two-bath system, the first is immersed, then squeezed out by hand, and the bath consists of an aqueous dispersion of polymer between rollers with a pressure of 2.8 kg / cm ² and silane, and the second bath contains an aqueous 5 ° squeezed. The wet glass fabric, which is a wet dispersion of the catalyst. During the treatment, the uptake was about 40 percent by weight, the glass fiber fabric was passed through the first bath, then hung on a drying device and then through nip rollers to remove the excess siloxane by heating the dispersion for 3 minutes, then it is weave hardened to 177 ° C. The treated fabric dries and then through the second treatment bath 55 had an initial spray value of 100; one carried out, finally it is crease recovery recorded at the curing temperature and one extraordinarily dried of the siloxane. resilient handle, while the same fabric before, if necessary, other conventional glass treatments only exhibited poor crease recovery and fiber treatment agents, such as hand detergent additives, exhibited a poor, slack handle.
Pigments, pigment binders in the first bath disper- 60

sion can be incorporated as long as they point to the same e 1 s ρ 1 e

do not have a disruptive effect. Six different silanes were added to

The concentration of the aqueous dispersions would be from 10 g of silane to 89.5 g of water and 0.5 g

not critical, you just have to use the usual requirement sodium dodecylbenzenesulfonate and then

requirements with regard to ease of preparation and bath homogenization of the mixture dispersions.

stability is sufficient. In general it was found provides.

that an aqueous dispersion containing about 2 to 5 weight- Then 10 g of each of the di-

percent of siloxane solids, the best results are dispersion instead of glacial acetic acid and methyl tri

methoxysilane used in the preparation of the treatment dispersion according to the method described in Example 1.
The six different silanes were as follows:

(A) CH ₃ Si (OCH ₃ ) ₃

(B) C ₃ H ₇ Si (OCH ₃ ) ₃

(C) C ₆ H ₅ Si (OCHa) ₃

(D) CH ₈ Si [OCH (CHj) J ₈

(E) Si (OC ₃ H ₇ ) ₄

(F) Si [OCH ₂ CH (C ₂ H ₅ ) CH ₂ CH ₂ CH ₂ CH ₃ J ₄

With these six aqueous dispersions, glass cloth was described in the same manner as in Example 1 treated.

In all cases, the treated glass fabric exhibited excellent wrinkle recovery and had one very good grip compared to the fabric treated above. The handle of the with the compositions, containing silanes (A) to (D) was slightly better as the handle of the fabric treated with the compositions containing silanes (E) and (F).

Example 3

Six aqueous dispersions were prepared containing different amounts of methyltrimethoxysilane, on a dimethylpolysiloxane having hydroxyl groups in the terminal units a viscosity of about 100,000 cSt / 25 ° C, which had been produced by emulsion polymerization and Contained dibutyl tin dilaurate as a siloxane condensation catalyst. The preparation of the aqueous dispersions was carried out by mixing compositions (1), (2) and (3) in different proportions. Composition (1) was a solution containing 30 weight percent methyltrimethoxysilane, 1.5 weight percent Sodium dodecylbenzenesulfonate and 67.5% water, composition (2) was a neutral one anionic emulsion containing 35 weight percent of the dimethylpolysiloxane. Composition (3) was a 20 weight percent emulsion of the dibutyltin dilaurate. The six aqueous dispersions contained this composition in the following percentage amounts:

(1) (2) (3) water (A) 1 8.1 0.7 90.2 (B) 2 7.7 0.7 89.6 (C) 3.5 7.0 0.7 88.8 (D) 5 6.4 0.7 87.9 (E) 7th 5.6 0.7 86.7 (F) 10 4.3 0.7 85.0

With these six aqueous dispersions, glass fabric (made from threads with a degree of fineness of 0.25 denier and yarn with a fineness of 300 denier) in the same way as described in Example 1, treated. In all cases the fabric had excellent hand and was exceptional crease resistant. In general, a slight improvement in grip could be observed, as the ratio of the methyltrimethoxysilane to the dimethylpolysiloxane increased.

A second series of the six aqueous dispersions were then prepared which were identical in all respects to the described above were identical except that the dimethylpolysiloxane used was one Viscosity of 1,500,000 cSt / 25 ° C. The treatment the glass fabric with these dispersions led to practically the same results as with the first six dispersions.

B e i s ρ i el 4

Six aqueous dispersions were prepared containing 7 percent by weight of various neutral anionic Emulsions contained each made up of 35 weight percent of in the terminal units

ίο Dimethylpolysiloxanes containing hydroxyl groups with different viscosity, from 3.5 percent by weight of a solution of 30 percent by weight methyltrimethoxysilanes, 0.1 percent by weight of glacial acetic acid and water to 100%, from 0.7 percent by weight of a 20 percent by weight Emulsion of the dibutyl tin dilaurate and consisted of 88.8% water. The viscosities the dimethylpolysiloxanes used in the six aqueous dispersions were as follows:

(A) 100cSt / 25 ° C
(B) 1080cSt / 25 ° C

(C) 4660cSt / 25 ° C

(D) 15.810 cSt / 25 ⁰ C

(E) 33,900 cSt / 25 ° C

(F) 100,600 cSt / 25 ⁰ C
25th

With these six aqueous dispersions, glass fabrics were in the same manner as described in Example 1, treated. In all cases the treated fabric showed excellent wrinkle recovery and had a very good handle compared to the untreated fabric.

Example 5

In this example a two bath system was prepared. The first treatment bath consisted of 60% Water, 0.1 weight percent glacial acetic acid, 1 weight percent methyltrimethoxysilane, 7 weight percent one neutral anionic emulsion containing 35 percent by weight of a liquid in the terminal units hydroxyl groups containing dimethylpolysiloxane with a viscosity of about 100,000 cSt / 25 ° C and which had been prepared by emulsion polymerization, 5% by weight of a commercially available one Acrylic acid based hand wash additive, 4 percent by weight of a blue pigment, 0.2 percent by weight a commercially available pigment binder of the formula

CH ₃ COOCH ₂ CH ₂ NHCH ₃ CH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ and water ad 100 ° / ₀ .

This first treatment bath was prepared as follows : First the acetic acid was added to the water, then slowly to the methyltrimethoxysilane stirred in and stirring continued until the solution had become clear. Then the polymer emulsion, the hand detergent additive and the pigment are stirred into the solution, and finally the pigment binder and the remaining amount of water were stirred into the mixture.

The second treatment bath was

6c mix of 0.7 weight percent of a 20gewichtsprozentigen emulsion of dibutyl tin dilaurate and produced 99.3 ° / ₀ water.

Glass fabric (made from threads with a fineness of 0.25 denier and yarn with a fineness of fineness of 300 den) was treated by padding the first bath, this was about 1.2 percent by weight Applied siloxane solids based on weight of wet tissue; then it became

Fabric dried, then the second bath has been padded, and finally the fabric was heated for 3 minutes 205 ⁰ C to cure the deposited on the fabric siloxane. The fabric treated in this way had an initial spray value of 100 and, after ten washes in the washing machine, still had a spray value of 100. The fabric was extremely crease-resistant and had a resilient handle. After ten machine washes, it showed little wash wear. The color wash resistance was also very good.

Example 6

An aqueous dispersion was prepared which contained 7 percent by weight of a neutral cationic emulsion made from 35 percent by weight of a dimethylpolysiloxane having hydroxyl groups in the terminal units and having a viscosity of about 11,000 cSt / 25 ° C., which had been prepared by emulsion polymerization, 1 percent by weight methyltrimethoxysilane , dilaurate dibutyl tin 0.7 weight percent of a 20 ° / ₀ emulsion of and was 91.3 ° / ₀ water.

With this aqueous dispersion, a 30.5 x 30.5 cm piece of glass fabric (made from threads with a fineness of about 0.25 denier and yarn with a fineness of about 300 denier) was prepared in the same way as described in Example 1, treated, with the exception that the curing was carried out at 205 ⁰ C. Immediately after the treatment and after five machine washes, the fabric showed excellent crease resistance, a good handle and a spray value of 100.

Example 7

The procedure of Example 6 was repeated with the exception that the aqueous Dispersion a neutral anionic emulsion was used, which is a dimethylpolysiloxane with a Viscosity of 100,000 cSt / 25 ° C. Immediately after treatment and after ten machine washes the fabric treated with this emulsion had excellent crease resistance, a good grip and a spray value of 100.

Example 8

The procedure of Example 7 was repeated except that the dimethylpolysiloxane and the Silane was applied to the fabric from one bath and the catalyst from a second bath according to the manner described in Example 5. The treated fabric had excellent crease resistance, a good grip and a spray value of 100.

Example 9

The procedure of Example 8 was repeated with the exception that the treatment baths were used before Used for different periods of time. Tissues that have been treated with these baths after aging times of 1, 2, Treated for 3 days, 1 week and 2 weeks had excellent wrinkle resistance, one good grip and a spray value of 100.

B e i s ρ i e 1 10

The procedure of Example 7 was repeated with the exception that c ate in place of the methyltrimethoxysilane the following silanes were used:

(A) C ₂ H ₅ Si (OCH ₃ ).,

(B) H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) 3

(C) H ₂ C = C (CH _{3 ) COO (CH 2} ) 3 Si (OCH ₃ ) 3
O

(D) H ₂ C - CHCH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃

(E) CH ₂ = CHSi (OOCCH ₃ ) ₃

ίο tissue samples treated with these dispersions all had excellent wrinkle resistance and spray values of 100 even after ten machine washes. The tissue treated with (A) had immediately after the treatment and

1.5 gave a good grip after five machine washes, after ten machine washes the one treated with (A) had a good grip Tissue had a grip that could not withstand heavy use. Tissues treated with (B) and (C) had one immediately after treatment and after a machine wash good grip. After five machine washes, the fabrics treated with (B) and (C) had a feel that was not able to cope with any heavy use. Tissues treated with (D) and (E), had a good grip immediately after treatment and after ten machine washes.

Example 11

The procedure of Example 7 was repeated with the exception that the dispersion was applied to glass fabric was applied, which was made from threads with a fineness of 1 den and yarn with a fineness of 300 den. Direct after the treatment and after ten machine washes, the fabric had excellent crease resistance, a good grip and a spray value of 100.

Example 12

If the following silanes were used instead of the methyltrimethoxysilane from Example 1, they were practical achieved the same results:

(A) CH ₃ Si [ON = C (CH ₃₎ (C _ä H _{5] 3}

(B) CH ₃ Si (NH ₂ ) ,,

(C) H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃

(D) C ₂₀ H ₄₁ Si (OCH ₃ ) ₃

(E) CeHnSitOCH ^ H.OCH ^

Example 13

If the following siloxane condensation catalysts were used instead of the dibutyltin dilaurate from Example 5 used, practically the same results were obtained:

(A) Dibutyl tin diacetate

(B) Octadecyl trimethyl ammonium hydroxide

(C) benzyl trimethyl ammonium hydroxide

(D) potassium hydroxide
Hydrochloric acid

45

(E)

Claims (2)

Patent claims: 1. A method for treating glass fibers by means of organosilicon compounds, thereby characterized in that one aqueous dispersions that (1) 100 parts by weight of liquid, in the terminal 109 531/231 Dimethylpolysiloxanes containing units of hydroxyl groups, (2) 5 to 70 parts by weight of silanes of the general formula Rj ₁ SiR 4-B wherein R is optionally substituted hydrocarbon radicals having 1 to 20 carbon atoms, R 'is hydrotoryable radicals, excluding halogen atoms, and η has a value of 0 or 1, and (3) Catalysts for the condensation of Si-bonded Hydroxyl groups contains, is applied to the glass fibers and the siloxanes then harden on the glass fibers. 2. The method according to claim 1, characterized in that that one uses aqueous dispersions, the specified as component (2) silanes Formula in which R is hydrocarbon radicals having 1 to 6 carbon atoms, R 'is alkoxy radicals having 1 to 4 carbon atoms means and η = 1. 3- The method according to claim 1, characterized in that aqueous dispersions are used which contain as component (1) dimethylpolysiloxanes with a viscosity of about 100,000 cSt / 25 ⁰ C, as component (2) methyltrimethoxysilane or phenyltrimethoxysilane and as component (3) Contain dialkvlzrandiacylate-