DE1669204A1 - Aqueous vinylidene chloride copolymer dispersion - Google Patents

Description

^Γ ~ ^Η ^ KALLE AKTIENGESELLSCHAFT

Us »r · Ζ · Ι * · η Tag Blaff

K 1713 PP-Dr.Wi-eg January 9, 1967

description
to register the
KALLE AKTIENGESELLSCHAFT Wiesbaden-Biebrich
for a patent
concerning

Aqueous vinylidene chloride copolymer dispersion

The present invention relates to an aqueous vinylidene chloride copolymer dispersion for the production of coating layers on films made from regenerated cellulose hydrate en with an additive that increases the speed of the formation of a firmly adhering bond between the coating layer and the carrier after application and drying of the Dispersion increased.

The copolymers of vinylldene chloride with acrylic esters and / or unsaturated acids or their anhydrides are good film formers. The films produced from them have good sealability, and they are for gases and water vapor little durchlassigt For this reason, the aforementioned copolymers of vinylidene chloride for the production of coating layers on films from regenerated cellulose

109809/1927

KALLE AKTIENGESELLSCHAFT 1669204

J - Unsar · Z *) di * n day sheet

K 1713 PP-Dr.Wi-eg Jan 9, 1967

Losehydrate is used because it has the properties mentioned are not sufficiently own. It is also known the copolymers of vinylidene chloride mentioned in the form of aqueous dispersions on the cellulose hydrate film to avoid the use of flammable and usually expensive organic solvents.

Since films applied in this way show poor adhesion to the carrier material, it is necessary to take »measures to improve adhesion. This can be done by putting a thin layer on the cellulose hydrate film brings a material that is good to both cellulose hydrate and polyvinylidene chloride copolymer Shows liability. Phenoplasts and aminoplasts are suitable for this purpose.

In order to avoid the application of this additional adhesive layer, it has already been proposed to use dispersions, which contain an adhesion-promoting additive. As additives

are according to the German patent specification (K 57 829

IVc / 22h) Formaldehyde condensation products such as phenoplasts and aminoplasts are suitable, preferably in aqueous Mixtures with diglycol were condensed. Now a solid one is made by the aforementioned means Binding of the layer on the cellulose hydrate film achieved,

109809/1927

KALLE AKTIENGESELLSCHAFT 1669204

3 Under · Ztiditn day sheet

«^, -> FP-Dr.Wi-eg Jan 9, 1967

however, it always takes a more or less long time until the maximum adhesion is reached. This can be done in some cases take up to several days. In order to accelerate the formation of adhesion, it was therefore proposed that to subject the coated and dried film to post-heating for a short time.

According to another proposal, "the speed with which the adhesion is established is increased by the fact that one of the vinylidene chloride copolymer dispersion one or more substituted ones dissolved in an aqueous alkali-ammonia mixture ortho-Hydroxybenzophenone and / or ortho-Hydroxy chalcones as accelerators adds. A suitably composed Dispersion is described in the German patent (K 57 830 IVc / 22h). Disadvantageous The thing about these accelerators is that some of them are difficult and slow to release.

The object on which the invention is based was therefore to further develop the adhesion between a vinylidene copolymer layer and cellulose hydrate film to find accelerating substances that do not have this disadvantage demonstrate.

The aqueous vinylidene chloride copolymer dispersion according to the invention for the production of coating layers

109809/192 7

KALLE AKTIENGESELLSCHAFT 1669204

| ~ Our «sign day sheet

K 1713 PP-Dr.Wi-eg January 9, 1967

Films made from regenerated cellulose hydrates, which can optionally be provided with an adhesion-promoting additive can, is characterized by a content of o, ol to 2 wt .- $, based on the vinylidene chloride copolymer, at least one compound, soluble in an aqueous alkali and / or ammonia mixture, which in its molecule carries one of the following atom groupings:

-CN- -CN II I II I

OH SH

-C-N- -C-N-

II I ill

0 NO - N H

and in that the dispersion is made alkaline.

Substances which are effective as accelerators and have one of the atomic groupings mentioned may include, for example, the following: Maleimide, Biuret, Triuret, Hydantoin, Kalonyldihydrazide, Benzoic acid amide, ο -Valerolactam, ^ .- Caprolactam, N.N-Dimethylglycine hydrazide, Acethydrazid-pyridiniurnchlorid, Acethydrazid-ammoniumchlorid, 2-Amino-5-benzoyl-aminophenol, Haleinic acid monoureide, * 1.4'-bis (p-aminobenzoylamino) -stilbene-3.3-disulfonic acid, Thiourea, dithiobiuret, degraded casein, lactalbumin, peptone, N-methyl-N-nitroso-urethane and condensation products of cyanuric chloride with organic ones

109809/192?

KALLE AKTIENGESELLSCHAFT 1669204 Under · Ζ · ΐΛ · η Tag Matt

K 1713 ° PP-Dr.Wi-eg Jan 9, 1967

Amines, such as products I and II, whose constitution is shown in the formula on a separately enclosed sheet is. The production of such condensation products is described in the German Auslegeschrift 1 o9o 168. The product of the formula I is used as an optical brightener.

The accelerator substances mentioned must be dissolved in an aqueous mixture of alkali and aranonia. You use at least enough alkali that the substance just goes into solution. This alkaline solution is then stirred into the aqueous dispersion. After the accelerator solution has been added, it must have a pH value above 7, preferably between 8 and 10.

Particularly favorable results are achieved if not only aqueous alkali and ammonia are used to dissolve the accelerator , but also water-soluble, primary, secondary or tertiary, acyclic, nitrogen-substituted or unsubstituted amine and / or water-soluble quaternary acyclic ammonium base and / or water-soluble cyclic ammonium base Compounds with an N atom in the ring. For example, "N-oxethylpropanediarain-1 * 3 ·" 2-dimethylamino-ethanol, 2-dimethylamino-ethanol and especially acetaldehyde ammonia are particularly suitable. The use of organic amines or organic ammonium compounds as additional

109S09 / 1927

KALLE AKTIENGESELLSCHAFT 1669204

ζ * Our · sign day sheet

K 1713 FP-Dr. Wi-eg Jan. 9, 19 67

alkalizing substances is described in the German

Patent Specification (K I6ooa). The weight ratio

from accelerator to acyclic amine and / or ammonium salt and / or cyclic amine is advantageously in the range from 1: Io to 1: 2o. The concentration of the accelerator within the specified limits somewhat depends on its solubility. Since the substances to be used according to the invention however, they are usually relatively readily soluble, especially when organic amine is added, it is usually possible in the the specified concentration range to set any concentration. The stability and storability of the Vinylidene chloride copolymer dispersion is not affected by the accelerator.

The dispersion according to the invention can be brushed onto the carrier and dried in the usual way, like a dispersion without the addition of accelerators, without additional process steps being necessary . The addition of accelerator makes itself extremely noticeable in the drying time, after which good anchoring has been achieved. In extreme cases, the drying time could be shortened to less than 1/200 of the drying time of an otherwise identical dispersion, but without an accelerator. The higher the accelerator content of the layer, the faster the layer reaches maximum adhesion. With the same drying time, the accelerator-containing

109809/1927

KALLE AKTIENGESELLSCHAFT 1669204

K 1713 Ir ^ -DrIt -?! 9 eg ^T 3fen.l967

Layer has a higher adhesion than the layer without accelerator. Often the maximum adhesion of the layer is all the more higher, the higher the amount of accelerator added. Significant The water content of the film at the end of drying is also important for the adhesion to be achieved. With a constant content of The lower the accelerator in the vinylidene chloride copolymer layer, the better the adhesion of the layer Water content of the coated and dried film. The same adhesion is achieved with a constant water content with an accelerator-containing layer in a shorter time than with an accelerator-free layer.

The accelerators cause an increase in speed, with which the adhesion is established, irrespective of whether the dispersion besides the accelerator solves one: contains or does not contain adhesion-promoting additive. However, the accelerating effect is particularly noteworthy in the case of dispersions, which contain an adhesion-promoting additive

according to the aforementioned German patent.

(K 57 329 IVc / 22jb. There are water-soluble phenoplasts and aminoplasts, which are made from formaldehyde and phenol and / or amine by acidic precondensation and alkaline post-condensation obtained in a mixture of water and completely miscible organic solvent with water will. The same amount of these phenoplasts or aminoplasts is added to 100 parts by weight of vinylidene chloride copolymer

109609/1927

BATHROOM OFIiGINAL

KALLE AKTIENGESELLSCHAFT 166920 *

ti Our · Zaldien day sheet

K 1713 FP-Dr.Wi-eg January 9, 1967

How from O ₃ oil - 1 part by weight of amine and / or phenol is formed by condensation with formaldehyde. The effects of the accelerators according to the invention are particularly great here, so that such a mixture is preferably used. An infrared post-irradiation of the layer dried in hot air, as is otherwise usual, is usually unnecessary here.

With the dispersion according to the invention, however, can also Cellulose hydrate films can be successfully coated, which already have an adhesion-promoting intermediate layer. Here, too, the accelerator substances accelerate the anchoring and improve the adhesion of the copolymer the surface of the film.

During layers of vinylidene chloride copolymers without the addition of accelerators if they are about 2.5 µm thick and about Io see dried at 13o C, usually within 3-5 minutes in boiling water from the mat The cellulose hydrate film has to be removed in the case of accelerator-containing layers, which under otherwise identical conditions have been applied, the coated foils - often hold in boiling water for up to 12o minutes before settling removes the layer from the base.

The technical progress of the invention vinylidene chloride copolymer dispersion adopted cei ^ t below ol: 109809/1927

BAD O & 'S-iftA

KALLE AKTIENGESELLSCHAFT 1669204

Qk Uni »r» sign tag sheet

K 1713 "FP-Dr .NJrL-eg Jan. 9, 1967

example

Three solutions were used: an aqueous vinylidene chloride copolymer dispersion, an aqueous-alkaline accelerator solution, an aqueous melamine-urea-formaldehyde condensation product solution.

The vinylidene dichloride copolymer was obtained by polymerizing vinylidene chloride, butyl acrylate, methyl methacrylate and itaconic acid. The vinylidene share amounted to about 9o percent * ■%. The aqueous dispersion consisted of about ² % dry matter.

The aqueous accelerator solutions were prepared by adding 1 g of accelerator substance in 80 g of water and 10 g 22% strength by weight ammonia solution and 10 g 40% strength by weight Potassium hydroxide solution were dissolved. In addition, aldehyde ammonia was added in the amounts as mentioned in the table added.

The aqueous solution of the formaldehyde condensation product was obtained by adding 0.25 g of toluenesulfonic acid and 0.25 g of ammonium chloride and 0.1 kg of finely ground melamine to 2.1 kg of diglycol heated to 70 ° C. The melamine was suspended with vigorous stirring. After about 3 min. O _f o8 kg pure urea was added, as well. In a casting solution, 1.5 kg 4o by weight formaldehyde after about a further 2 min with stirring.

109809/1027

BATH ORIGINAL

KALLE AKTIENGESELLSCHAFT 1669204 Our Z * lch * n day sheet

K 1713 PP-Dr.Wi-eg January 9, 1967

After exactly 30 see a solution of 0.1 kg was found Potassium hydroxide run in 100 ml of water and then stirred 1 3M more hours long at 60-65 C. looo g of this solution contain the formaldehyde condensation product from 25 g melamine and 2o g urea.

The coating dispersion was prepared from the aforementioned solutions and the vinylidene chloride copolymer dispersion by mixing. Tables I-III show which accelerators and mixtures are involved. The coating dispersions were then applied to the surface of a film of regenerated cellulose hydrate or to the surface of a film of regenerated cellulose hydrate provided with an adhesive layer with the aid of a conventional feeding machine. The coated amount was always chosen so that the dried layer thickness was about 2.5 fi. It was dried in a drying tunnel with moving air at 13 ° C. The drying time was 8 seconds. In all cases the water content of the coated films was between 7 and 9 parts by weight

In the case of the coated films produced in this way, the adhesion between film and layer was determined by the Times up to the detachment of the layer in boiling water, the so-called boiling adhesion times, were determined. These are listed in the right column of the following tables,

(Ätti KALLE AKTIENGESELLSCHAFT 1663204

/ Under «Zatdian day sheet

K 1713 PP-Dr.Wi-eg January 9, 1967

Table I.

Serial No . Boil Adhesion Accelerator

in minutes

1 - 3-5 2 ο, Ι% maleimide Io 3 ο, Ι % biuret 15th 4th ο, Ι % peptone 6o 5 ο, 2 % peptone 12o 6th ο, Ι % malonyl
dihydrazide 6o 7th ο, 2 % halonyl
dihydrazide 12o

Unprepared hydrate cellulose; the accelerators were used together with 1 % aldehyde ammonia.

109809/1927

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KALLE AKTIENGESELLSCHAFT

P Unier · character day sheet

K 1713 PP-Dr.Wi-eg January 9, 1967

Table II Cooking adhesion times
in minutes Serial no. accelerator 3-5 8th - 12o 9 0.1 % maleimide 12o Io o, l % ■ peptone 7o 11 0.1 % malonyl
dihydrazide

Unprepared cellulose hydrate film; the accelerators were used together with 1 % aldehyde ammonia and 1 % melamine / urea formaldehyde condensation product.

109809/1927

KALLE AKTIENGESELLSCHAFT 1669204

/ 1/1 Uni »r» Ztfdian day malt

K 1713 PP-Dr.Wl-eg January 9, 1967

Table III Cooking adhesion tents Serial no. accelerator in minutes Io 12th - 2o 13th o, l % pepfron 14th 0.1 % malonyl 2o dihydrazide

Cellulose hydrate film having an adhesive layer of a melamine-formaldehyde condensation product (Accobond '^' 3800 from American Cyanamid Corp.); the accelerators were used together with 1 % aldehyde ammonia.

109809/1927

^ ... · 'Vd' original

Claims (6)

KALLE AKTIENGESELLSCHAFT 1669204) Umw »ZaMiM Tag Matt K 1713 π PP-Dr.Wi-eg 9.Jan.1967 Patent claims 1. Aqueous vinylidene chloride copolymer dispersion for the Production of coating layers on film from regenerated cellulose hydrates, optionally with a Adhesion-promoting additive, characterized by a content of o, ol to 2% by weight, based on the vinylidene chloride copolymer, at least one in an aqueous Alkali and / or ammonia mixture soluble compound which has one of the following atom groupings in its molecule wearing: -C-N- -C-N-OH • SH -C-N- -C-N- I I * I 0 NO - N H and in that the dispersion is made alkaline. 2. Aqueous vinylidene chloride copolymer dispersion according to Claim 1, characterized »that its pH is increased by the addition of aqueous alkali and / or ammonia a value between 8 and Io is set. 109809/1927 - BAD CFJGjjyjAL KALLE AKTIENGESELLSCHAFT 1669204 > l J Unier · Zddien day sheet K 1713 'FP-Dr.Wi-eg 9 January 1967 3. Aqueous vinylidene chloride copolymer dispersion according to Claims 1 and 2, characterized in that the Dispersion additionally has at least one water-soluble, primary, secondary or tertiary, acyclic, am Nitrogen unsubstituted or substituted amine and / or at least one water-soluble quaternary acyclic ammonium base and / or at least one water-soluble cyclic compound with a nitrogen atom contains in the ring. 4. Aqueous vinylidene chloride copolymer dispersion according to Claim 3, characterized in that the weight ratio of compound added by the Claim 1 formally characterized species to acyclic Amine and / or ammonium salt and / or cyclic amine in the range from 1: Io to 1: 2o. 5. Aqueous vinylidene chloride copolymer dispersion according to claims 1 - ¹ I _3, characterized in that it also contains a water-soluble phenoplast and / or aminoplast which is made from formaldehyde and phenol and / or amine by acidic precondensation and alkaline post-condensation in a mixture was obtained from water and completely miscible organic solvent with water. 1 098.09 / 1 9 2 7 KALLE AKTIENGESELtSCHAFT 1669204 / \ To ·! · Ztttian act K 1713 PP-Dr. M.-eg January 9, 1967 6. Aqueous vinylidene chloride copolymer dispersion according to Claim 5, characterized in that there is as much phenoplast for every 100 parts by weight of vinyl chloride copolymer and / or aminoplast can be used, such as from o, ol -l, o parts by weight of amine and / or phenol by condensation with formaldehyde. KALLE AKTIENGESELLSCHAFT 109809/1927 KALLE AKTIENGESELLSCHAFT Wi «ebad * n-Biebrich Pat "ntann" ldunfc K 1713 of January 9, 1967 22g 3-74 ATi 01/12/1967 OTi 02/25/1971 II .O-Z f O GQ υ - ζ χ υ ο-ζ ο — ζ te «Η ο «3 X O (M υ ι CM XO X O , o_ ζ-, o ₌ z ' _2_ / Λ ir * · : | hfe * ORIGINAL INSPECTED