DE1546894A1 - Vinylidene chloride copolymers as coatings for films made from regenerated cellulose - Google Patents

Description

BERLIN 23, «MUNICH 27

Auguste -Viktori.-Str.Be K Df. - I tig. H AN S RUSCHKE

£ * Dipl.-In ». HEINZ AGULAR ^Plt

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The Dow Chemical Company, Midland, Michigan-, V "8t" A.

Vinylidene chloride copolymers as coatings for films made of regenerated cellulose

The invention relates to moisture-resistant, heat-sealable, flexible transparent films and in particular the manufacture of a film from regenerated cellulose which with a moisture-resistant, heat-sealable, pliable, clear coating of an organic polymeric material is coated on the carrier film itself under conditions strongly adheres to high humidity

According to the invention, improved coated films made from regenerated cellulose are obtained by coating a carrier film or sheet made from regenerated cellulose with a coating agent which has a copolymer which is obtained by polymerizing a mixture of (1) about 80-93% by weight vinylidene chloride, (2) about 4.5 to 19.5 parts by weight of a copolymerizable 9ε mojaoäthylenisch-unsaturated monomers of the type described below, and (3) from about 0.5 - 2.5 wt _e - $ glycidyl acrylate or methacrylate or a salt of the Vinylbenzylamine

BAD OBSGlNAL 909851/1471

or of 2-Aminoäthy! methacrylate, with the exception of carboxylic acid salts, has been obtained as an anchoring agent

In accordance with the invention useful copolymerizable monoethylenically unsaturated monomers is acrylonitrile _r alkyl esters of acrylic acid or acrylic acid Metlw 1 - 18 carbon atoms in the Alkylrruppe, or vinyl chloride. ..

'■' hen the copolymerizable monoäthyleniöch-unsaturated monomers in an amount of less than &, 5 wt '-' is used, the copolymer decreased solubility, while the use of more ala ^as: ■ 19.5 Gevi, - ^r 4 leads to a, poor quality assurance chain: leads to «·. . - ·

Venn vieniger. as 0.5 lev;, - 'of the anchoring agent, the resulting copolymer has ^{unsatisfactory anchoring under conditions:} high humidity, while copolymers obtained from a reaction mixture contain more than 2.5 wt. -7 of the anchoring agent are not sufficiently soluble. . ... "■■

For the production of the copolymers which can be used according to the invention the monomers can be copolymerized by any known method, e.g. the copolymerization can be carried out in aqueous emulsions, including a catalyst such as potassium persulfate and any of the well known emulsifying and / or dispersing agents contain. According to another embodiment, the

9 098 5 1 / U71

BATH ORIGINAL

- D-

Copolymers by polymerizing the monomers in Hate to be produced without adding a solvent, or the monomers can be reacted in a suitable organic solvent as the reaction medium «,

Here is the order in which the various ingredients are added of the monomer endmix to be polymerized insignificant "Kine comfortable", 'eise to carry out the procedure consists in the anchoring agent with the remaining monomers in an aqueous medium that contains the catalyst contains, to mix «, The various components of the Honomerengemisches to be polymerized can also conveniently .eise previously mixed with one another and then added the wakri.fpn medium, which contains the catalyst and acid, are given",

TSi e according to the invention copolymers are applied to the carrier film of regenerated cellulose by any suitable method and can be applied in the form of a solution in an organic solvent or in the form of an aqueous solution. _C

The following examples, in which all parts and percentages relate to weight, serve to illustrate the invention.

example 1

The following batch was made into a reaction vessel Glass brought:

9 0 9 8 5 1 / U 7 1 BAD OrtiGINAL

Water ■ -. "." 200 Potassium persulfate o, 24 Diisopropyldixanthogen ■ / '
- 0.38 Dioctyl ester of sodium sulfosuccinic acid 0.16 Acrylonitrile 8th Vinylidene chloride 72 Glycidyl acrylate 2

The batch was polymerized by heating to a reaction ^{temperature of 60 ° C.} and maintaining this temperature for a period of 16 hours. The polymer emulsion was then coagulated overnight by allowing it to freeze, after which it was thawed, filtered off and dried *

"The copolymer obtained in this way was dissolved in such an amount of tetrahydrofuran that a varnish with about 20% by weight of the copolymer and about 80% by weight Tetrahydrofuran was obtained. The lacquer was then applied to a sheet of regenerated cellulose film a thickness of about 0.03 mm using a film applicator rod wrapped with a thin stainless steel wire applied «

The sheet made from the coated film of regenerated cellulose was then placed in an air circulation at 121 ^° C. for 3 minutes. Then the covered FiIa was 16 hours

Conditioned temperature of 25 ° C.

those at a relative humidity of 50 % and one

5 ° C conditioning
909851 / U71

Test specimens were then produced by inserting a fiber material strip about 19 mm wide and 15 cm long ^; Both the coating and the regenerated cellulose film were applied, after which the sheet was cut into strips corresponding to the dimensions of the area covered with the fibrous strip Tension tester and subjected to a peel test at a crosshead speed of 25.4 cm per minute under constant conditions of 65 '·' · relative humidity and a temperature of 22 ^° C. The adhesive strength was measured in grams of force required to peel the coating from the regenerated cellulose. The force required was 56 <r ".

For comparison purposes, another similar approach as above, but which did not contain glycidyl acrylate, polymerized, the polymer dissolved to form a paint and the Varnish as a coating on a film made of regenerated cellulose. applied, after which the film as described above on the Adhesion strength of the coating was tested «The peelable force required of the coating was 13 g

Example 2

In each of a series of experiments, the following batch was placed in a glass reaction vessel:

909851/1471

200 ? 4 ο, 38 0, 16 ο, 16 64

'• / he ate

Potassium persulfate jiisopropyldixanthogen

Dioctyl ester of sodium sulfosuccinic acid

Vinyl chloride vinylidene chloride

For each of these approaches, 2 g of one of the following Table I mentioned glycidyl esters with stirring given «,

The process for the production of the corresponding polymer emulsions, the Lackeys used for coating systems and the individual coated test specimens made of regenerated cellulose as well as the test methods for determining the Force in g to pull off the vinylidene chloride polymer coating required from the regenerated cellulose film were the same as in Example 1.

- ■■ - ■■■■■■■■ Table .- ■■ - ·· ■ ' u ..ff Force required to separate the

'"° Glvcidvlester Vinylidenchloridpolymerisat -.... ixiyciayiesxer coatings of the FiI ^ made of regenerated cellulose; are required.

1 no glycidyl ester. . _: 5

2 glycidyl acrylate. 40

3 glycidyl methacrylate 72

909851 / U7 1

Example 3

The following batch was placed in a glass reaction vessel:

30% hydrogen peroxide

Dihexyl ester of liatric sulphinic acid

200 ,8th 0 • 36 1 , 72 0 8th 72

Vinyl idenehloriä

In making the above approach it is advantageous first of all the dihexyl ester of sodium sulfosuccinic acid dissolved in the water and using the resulting solution adjusted by nitric acid to pH = 3.5, after which the remaining constituents are added and the polymerization of the batch compiled in this way is carried out is by heating to a reaction temperature of 60 C. and maintains this reaction temperature for 16 hours The polymer emulsion was then subjected to freeze coagulation overnight, after which it was thawed, filtered and was dried.

The preparation of the coating solution, the application and the tests were carried out in the same way as in Example. The force required to peel off the coating was 31 g.

For comparison purposes, a similar approach, which contained no 2-aminoethyl methacrylate hydrochloride, was prepared

909851 / U7 1

BATH

represents and polymerizes, the polymer obtained dissolved to a paint, the paint on a film of regenerated Cellulose applied and the coated film checked, everything as οVen described pie to peel off the coating required force was 13 g.

Example 4.

"The following approach was put into an Olas reaction vessel given:

., "a 30% V ai -! 3 peroxide

iihexyl ester of sodium sulfosuccinic acid

iron (III) nitrate P-aminoethyl methacrylate hydrochloride Vinyl chloride vinylidene chloride

The methods for producing the polymer emulsion, the lacquer coating agent and the coated test specimen made from regenerated cellulose and the test methods for determining the force in g required to peel the vinylidene chloride polymer coating from the regenerated cellulose film were the same as in the examples 1 and 3β The force required to peel off the coating was 67 g «

A similar approach, but not 2-Aminoäthylmethaerylat-hydrochloride contained, was produced and

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BATH ORIGINAL

20C ,8th 0 , 36 1 , 72 0 1 16 64

polymerized, the polymer processed into a lacquer, the lacquer applied to a film made of regenerated cellulose and the coated film tested as described . The force required to peel off the coating was 5 g «

Similar results can be obtained using a salt of vinylbenzylamine, with the exception of carboxylic acid salts, can be achieved as anchoring means «,

The acids which can be used for the preparation of the salts of vinylbenzylamine or of 2-aminoethyl methacrylate are they are those which are able to neutralize the basicity of the basic groups of the monomer. Preferably the acid and the basic groups form an oil-soluble one Neutralization residue, since it has been found that if the amino group-containing monomer is in the form of a water-soluble Incorporating salt into the polymerization batch, the process cannot be carried out because of the interpolymerizability is changed and the self-anchoring properties of the polymer coating are reduced.

The acid is preferably used in an amount equivalent to the basic groups of the monomer, although a slight excess of acid can be tolerated, W If less than equivalent amounts are used, the remaining unneutralized basic groups can be used a breakdown of the halogen ethylene units of the polymer chain, cause·

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BAD OWGtN ^AL

Specific examples of acids which can be used for the purposes according to the invention include, among others. the mineral acids, such as Z ₀ E. sulfuric acid, nitric acid and hydrochloric acid, and the oil-soluble organic sulfonic acids, such as methanesulfonic acid, eenzenesulfonic acid, toluenesulfonic acid and 2-naphthalenesulfonic acid. Carboxylic acids, such as 2.K. Ks Ki ? ^r v> acid and benzoic acid, whatever the phenols have proven to be unusable »

- patent claims -

909851 / 1.471 ^

BAD OWQINAt

Claims (4)

} 'a t ο η t a η s ρ r ü c h e · 1. bersogener ^ iIm made of regenerated oil, characterized in that the coating is a copolymer of about Bg - 9 ^ wt. Vinylidene chloride, etv / a 4.5 - 19 »5 wt ,, - ^ unites? with polymerizable mono-ethylenically unsaturated monomers Ui: d e.twa u, 3 - L ', 5 wt .-'. '· Glycidyl acrylate or methacrylate or a salt of vinylbenzylamine or 2-aminoethyl methacrylate, with the exception of carboxylic acid salts. 2. ^r ilm according to claim 1, characterized in that the Ddechpolymcrisbaren mono-ethylenically unsaturated monomers is acrylonitrile or vinyl chloride » "3β curing cure production of a coated, transparent . Carrier filines made of regenerated cellulose, thereby characterized in that a copolymer of about 80-93 Gewe-r '. Vinylidene chloride, about 4.5-19.5% by weight: of a copolymerizable monoethylenically unsaturated monomers and about 0.5-2.5 wt. glycidyl acrylate or methacrylate or one Salt of vinylbenzylamine or 2-aminoethyl methacrylate, Except carboxylic acid salts, dissolves in an organic solvent, the TiIm from regenerated cellulose with the obtained!, solution coated and to remove the solvent dries. 4. The method according to claim 3, characterized in that? the copolymerizable mono-ethylenically unsaturated one used Monomers is acrylonitrile or vinyl chloride. 9 0 9 8 51/14 71