DE1951746C3 - A method for uniformly distributing a resinous material on a glass fabric - Google Patents

Description

- N = C

N =

contain, in which the free valences are saturated by hydrogen or lower alkyl, phenyl or other aryl radicals, used, the dyebath using an organic volatile acid to a pH of 2.5 to 6, preferably 4 to 5, and for Coagulation of the resinous material on the glass fabric heated it to a temperature of at least 121.1 ⁼ C.

2. The method according to claim 1, characterized in that the dye bath used additionally contains a reactive aminosilane.

3. The method according to claim 1 or 2, characterized in that the dye bath used in addition contains an epoxy compound.

4. A method for the aftertreatment of the material colored according to one of claims 1 to 3, characterized in that a customary top-finish treatment, optionally after a matting treatment is carried out with oxalic acid.

The invention relates to a method for dyeing glass textiles by applying a Pigment, a cationic fixative and an aqueous dispersion of a coagulable resinous Material as a binder containing dye bath on a glass fabric and subsequent heating.

In known processes for dyeing glass textiles pigments are used which are dispersed in resin emulsions, these dispersions can be applied to the textile fabric by padding. Such a known method is e.g. B. U.S. Patent 3 108 897. A dyebath containing an anionic resin binder is used for this purpose and contains a undocked pigment. After the dye bath is padded onto the glass fabric has been, the glass fabric is heated to cure the resin, which causes the pigment on the Glass fabric is attached.

It has already been recognized that it is desirable, when dyeing glass textiles, e.g. H. Glass fabrics or yarns made of glass fibers or threads, each thread of the textiles with pigmented Resin should be coated to achieve a uniform coloring effect.

The method just described and other methods, e.g. B. that in the German interpretation 1 146 473 described method for dyeing "nd Finishing of glass textiles does not result in a uniform color within the glass textiles because the pig. ments and resins that are on the glass yarn begin to migrate during the drying stage incline the surface of the glass textiles. This migration of the pigments and resins has the consequence that the Gaps in the textile and the inside of the thread bundles of the individual yarns remain undyed. When the yarns are shifted in the fabric, e.g. B. by abrasion during normal use or during washing, then the undyed parts of the fabric or yarn may be exposed creating an undesirable effect.

There are already various means, such as. B. cellulose ethers or esters, natural rubbers, acrylic polymers etc., used to control the migration of pigments in the coloring process bring. These agents counteract the migration effect by increasing the viscosity of the clumping liquid raise. However, if the viscosity of the padding liquid is increased in this way, a corresponding result results Decrease in the penetration force of the padding liquid, i.e. the higher the viscosity of the padding liquid is, the weaker become in inner surfaces of the fabrics and the yarns by the pigmented liquid covered.

The invention is therefore based on the object of avoiding these disadvantages, so a method for to provide uniform distribution of a resinous material on a fabric or yarn, in which a pigment migration avoided and thus an increased uniformity of the distribution of the coloring material is achieved through the entire fabric to be colored, without other disadvantages, such as having to accept a lower through-coloring effect.

According to the invention, this object is achieved in that one fixative in the resin-containing Incorporates the dye bath. During a heating stage that follows padding in a dye bath and which is usually used to harden the resins present in the dyebath, the fixing agent, whose flocculation properties were neutralized by the addition of volatile acid, again returned to its original state and the pigment-resin dispersion. fixed. Such a fixation The pigment-resin dispersion fixes the position of the pigment within the fiber bundle, creating a subsequent Pigment migration is avoided.

The method of the invention is therefore characterized in that the fixing agent used is low molecular weight, water-soluble polyamine acrylamides or reaction products of formaldehyde with dicyandiamide or similar compounds which the grouping

, N =

N =

contain, in which the free valences are represented by hydrogen or lower alkyl, phenyl or other aryl radicals are saturated, used, the dyebath by means of an organic volatile acid to a pH of

2.5 to 6, preferably 4 to 5, adjusts and coagulates. The binder is usually a resinous junction of the resinous material to a temperature material such as e.g. B, a polyacrylic latex, a silicone, heated to at least 121.1 C. Polyvinyl alcohol or polyvinyl acetate, etc. In addition to the term "polyamine acrylamide" here are resin-like materials that can be used in the cation-active polyelectrolytes or cationic processes according to the invention, resin-like compounds are meant, which are an amino in US Pat 897 stated,
function. _{It has been found that it is very advantageous to melt} into these compounds chemically as a lower block composition a silicone crosslinking molecular water-soluble polyamine acrylamide containing reactive groups, such as, for. B. work uas reaction product from an io. The function of this crosslinking agent low molecular weight polymethacrylate or polyethylene is to acrylate the resin on the glass surface with a polyamine, such as. B. Triethylene anchor. However, the silane also serves additionally tetramine, which has two or more amino groups, anchoring agent and as a catalyst for that, at least one having a primary amino subsequently applied top finishing binder system. group is. This type of reaction product is described in US Pat. No. 2,675,369. Molecular is an aminoalkyltrialkoxysilane, the kulargewichte in the range of 2000 to 5000, at least one amino group and up to 10 carbons can be coagulated explanatory, although products with material atoms, the carbon atoms of the higher molecular weights, such as. B. 10,000 or alkoxy groups bonded to the silicon atom through it can also be used. 20 are, not in the specified number of 10 carbon. Other cationic resinous compounds, which are included in the calculation, and where any alkoxy can be used here, the water group contains 1 to 3 carbon atoms. The best soluble cationic condensation products from results are available with aliphatic silanes, formaldehyde and from dicyandiamide or the like which contain one or more secondary groups or both compounds which contain the grouping primary as well as secondary groups. Ty-

J ^, _ pical examples of such compounds are those the formula

~~ ^{N = C v} · - R ₁ HN (CH ₂ ) _m NH (CH ₂ ) "Si (OR). ₁
N =

30 wherein m and η are integers from 1 to 4, preferably

contain, in which the free valences are represented by water 2 to 3, R is alkyl with 1 to 3 carbon or lower alkyl, phenyl ν, -ier other aryl atoms, R _{1 is} hydrogen, methyl or ethyl radicals are saturated. A typical example of means. A particularly preferred silane is such a condensation product which is useful here N- (2-aminoethyl) -3-propylaminotrimethoxysilane is methylolguanidine. ₃₅ structural formula

The fixatives used of the above be, _, ^ _(ru \ \ iurru \ ουλ, -η ι

written type can by adding a strong η ₂ ιν ^ η ₂ ) ₂ ινη ^ η ₂ ) ₃ ;> ι ^. CM ₃ J ₃ .

volatile organic acid under such conditions- A reaction product of acrylic acid with the final

conditions that the implementation of the fixative with permanent NH ₂ group of N- (2-aminoethyl) -3-pro-

favor the acid to be neutralized. In all- 40 pyl-aminotrimethoxysilane, in addition to gamma-amino

These materials generally react with space propyltriethoxysilane as an exemplary useful one

conditions, but heating to a silane temperature can be mentioned.

from 37.8 to 48.9 ⁰ C for 1 to 5 minutes. It has also been found that it is advantageous to use a

preferred. The final product should have a pH within the epoxy resin and / or epoxy oil compounds

a range from 2.5 to 6 and preferably internally pigmented coating composition

half of a range from 4 to 5. Acetic acid work. Epoxy resins are general for this purpose

is the preferred neutralizing agent, but suitable, but the preferred epoxy resins are the-

Formic acid and those that react with the silane crosslinking agent can also be used in place of these

Acrylic acid as well as other strong and volatile ones can. Examples of suitable epoxy resins are

Acids that reduce the primary amino groups in the 50 resins of the bisphenolepichlorohydrin type and epoxy

Neutralize fixatives can be used. dated oils, such as B. epoxy soybean oil and the like

Before the fixatives are neutralized, that used for the method according to the invention they have the ability to flocculate pigments the coagulation of the binding resins in the dye bath is stable, d. i.e., the pigments must have the to support. Withstand these flocculation and coagula hardening temperatures without change tion properties of the fixative can be through. Examples of inorganic pigments that deserve The neutralization stage prevented, but these can be reversed, are the oxides, sulfites and Shaft can be regenerated if the neutralized sulfate of cobalt, chromium, iron, zinc, cad product is heated, the acid and the fixative, etc. Examples of organic pigments are the funds are regressed. In general 60 diazo coupling agents, anthraquinone, phthaloists it is preferred that the neutralizing acid be white, cyanine and indanthrene vat dyes, as well as carbon black, etc. evaporated during the heating or fixing step. The dye bath generally contains about 0.5 will. The neutralized fixy pigment will work up to 5 percent by weight, but it can too Medium at any acidic pH, but a pH of 4 more or less pigment used as desired to 5 is preferred. Turn 65. The pigment is usually in the form of a

When dyeing glass fibers, an aqueous dispersion is usually used that contains water and pigment Binder used to provide physical adhesion and contain a dispersant as is used in the art between the colorant and the glass is too common knowledge.

5 16

The glass fibers treated here can be any of the lauryl sulfate or other organic ones

have conventional composition. Typical pigment dispersants containing dispersants ίο η

Suitable fibers are those which have been added to the mixture from a glass with vigorous stirring.

with the following approximate composition, and then more water was added,

are made: 5 um the dyebath mixture on the final

Silicon dioxide .... 52 to 56 parts by weight «?» "« ^To »™ & ⁿ (total solids content 9 parts

Calcium oxide 16 to 25 parts by weight ^ tToC paint bath was then on the hot

iXJz '' η r νΕίίπ ^l ° ^d ann using sufficient heat for

Natnumoxyd ..... Obs IGewchse dried (171 ° C during

Magnesium oxide ... 0 to 6 weight position 2Mt Γ '"""* ^ew

Other suitable glass compositions are after the fabric is in contact with the dye bath.

for example in the USA patents 2 582 919 and settlement, it was a top

3 011 929 stated. is finish granted. The additive used for the top finish

Presumably the heating stage caused a composition was as follows:

Evaporation of water and acetic acid from the _{10 /} silane crosslinking agent,

Textile material, whereby the pH of the remaining go / acrylic resin emulsion

Liquid rises rapidly on the fabric. On _{g0 /} 'epoxy oil emulsion,'

Reason for the loss of acetic acid with the resulting 20 ₃ ", epoxy resin emulsion,

resulting regeneration of the primary amine - ,,, V of a chromium complex according to the USA,

groups in a free state is the cationic - 'Patents 2 356 161 and 2 272 040,

Nature of the polyelectrolyte restored and watered down to 100 ° /

causes coagulation of the resin and / or "" °

flocculation of the pigment within the thread bundle 25 This finish was also applied to the textile fabric

of the glass yarn. This coagulation and / or padded, dried and hardened,

flocculation prevents the migration of the resin and it has been found that according to the above

any pigment present in the following process, dried glass fabric has a good color

Treatment, resulting in a leveled dye in penetration, good color fixation and good color fastness

every single glass yarn in the fabric is achieved. 30 during repeated washing.

The invention is illustrated by the following examples. The process of the invention also effects one

explained in more detail in which all parts and percent- preventing the migration of unpigmented

data are expressed in weight, unless there are resins that have been applied to the glass textiles.

other is indicated. the.

. 35 Before the

Example 1 Application of the top finish with oxalic acid a mat

A glass cloth was first hot cleaned, with animal treatment being given. This mat.

the treatment disclosed in U.S. Patent 2,970,934 gives the fabric a desired one

Procedure was used. The degree of dullness or opacity. This treatment

method of USA.-Patent 3,012,848 also improves the abrasion resistance and the 40 could

can also be used with equal success. Tear strength of the dried fabric. the

The hot-cleaned glass fabric was then subjected to a matting treatment on the fabric

a dye bath is immersed, which is produced as follows, but before the top finish is applied

had been: applied.

For a small amount of water the following 45 were added added: components in the dye bath vary over large areas,

V ₂ -V ₀ silane crosslinking agent, ^from " ^the dyebath generally contains approximately

1 ° / _{0 of} a low molecular weight polymethacrylate with ² _n ^bl *. ^l5 , weight percent B.nderharz and approximately

two or more amino groups, of which ^{- 0} J bls] percent by weight pigment. The used

at least one is primary, according to the USA, 5 ° amount of the pigment, is only due to the absorption

Patent specification 2,675,359 (with acetic acid limited to the ability of the resin system, if larger

nH 5 neutralized) amounts of pigment are to be used, then im

4V,% acrylic resin emulsion (commercially available), generally an increase in the resin content of the dye

1% epoxy ^{resin emulsion bads not |} S · ^{Elne such increase in} resin content

4% epoxy soy emulsion, 55 in the dye bath affects the handle and drape

2 "/ o acetic acid (final pH of bath 4). Ability of the final product.

The amount of neutralized fixative that

The neutralized polyamine acrylamide was used in the dyebath, varies within

made by that it is with a sufficient half very wide areas. It will in general

Amount of acetic acid has been reacted so that a final 60 prefers to use an amount which is im

reaction product with a pH of 5 was obtained. unneutralized state an excess over the

The reaction occurred at atmospheric pressure by representing amount necessary to flocculate the pigment

3 minutes of heating of the mixed material in the dyebath is necessary, but a larger excess

materials to a temperature of 43.3 ° C. All above this preferred minimum amount of neutral

Percentages in these examples relate to 65% fixative that can be used. in the

the final weight of the dye bath. In addition to the above general, it is preferred that the used

Mix then 1% of an aqueous hematite (Fe ₂ O ₃ ) - amount of neutralized fixative within the

Dispersion added. Range from 0.5 to 1.5 percent by weight, based

1 on § w 1 Ben C. who λ it \ sioi stat 1 get Size Hey

on the (dye bath. lies, but it is pointed out that that this Ueieich is only the most desirable Area and in no way represents a restriction.

Since the neutralized polyamine acrylamide is preferably used at a pH of 4 to 5 it preferred. F'igmentdispcrsioncn and llar / cinulsionen should be used that are stable at these pH values for best results.

Be by the crfiiulufigsgemüMc procedure dried (ilastextile fabrics that have a good (iriff, an excellent wash cleanliness, an excellent Ilemline abrasion resistance and an excellent

Penetration through the entire fabric be seated. When the drawers in the textile materials are shifted, there are no undesirable un-dyed heals, as is the case with conventional dyeing processes. (An examination of the yarn dyed in accordance with the curling shows that the dye-resin mixture has completely penetrated the yarn bundles and the textile. Furthermore, the dye-resin mixtures which have penetrated the yarn bundles show no noticeable wandering the hardening stage, whereby a product ¹ with excellent pigment distribution is achieved

Claims (1)

Patent claims: 1. Process for dyeing glass textiles by applying a pigment, a cationic Fixing agent and an aqueous dispersion of a coagulable, resinous material as a binder containing dye bath on a glass fabric and subsequent heating, thereby marked that one as Fixiefungsnuitei neutralized low-molecular, water-soluble polyamine acrylamides or reaction products of formaldehyde with dicyandiamide or similar compounds that form the group