DE1446609C - Process for the production of plastic-containing papers by adding plastic dispersions to the fiber material prior to sheet formation - Google Patents

Description

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It is known that for the production of. by refining mixtures of corresponding quaternary ammovers Papers the paper stock in a lenium compounds with corresponding olefinically non-variable The stage before the formation of the paper sheet is saturated in the presence of aqueous cationic compounds Kunststoffdispersiorieri add and the active and possibly also of not Plastic particles optionally by adding ionic dispersants in an aqueous dispersion Salts of polyvalent metals or other precipitation with the addition of suitable catalysts, such as water and fixatives on the cellulose fibers precipitate peroxide, polymerized

or can bind to the fibers. The cation-active dispersants suitable in this way are both

pretreated fiber is then subsequently converted into, for example, salts of fatty amines and oxyethylated

Usually, by dehydration to paper, additional fatty amines. Suitable non-ionic dispersing

processed. - · ·. agents are e.g. oxyethylation products of fatty

So far, anion-active and non-alcohols have been used for this purpose. and protective colloids, such as polyvinylpyrionic plastic dispersions, which, however, contain rolidon or polyvinyl alcohol,
Copolymers which can be used according to the invention can usually only be added to the pulp in small amounts. If larger proportions of the dispersions can also be added in suitable solvents, relative amounts are required, and then if necessary with the addition of appropriately large amounts of precipitants or fixatives, which are dispersants in water, are water-soluble and cationic, are required in order to or to precipitate C-vinyl-substituted aromatic and / or the dispersed plastic particles on the cellulose heterocyclic compounds in the sense of the inventive fibers. In addition, there are, for example, N, N, N-trimethyl-N- (4-vinyl-known processes for dewatering slightly benzyl) -ammonium chloride, N-vinylbenzyl-N, N-di-disorders due to the excretion of coagulated methyl-N -benzylammonium chloride, p-vinylbenzyl plastic particles at various points of the pyridinium chloride, 1,2-dimethyl-5-vinylpyridinium paper machine, for example on the screens, on methosulphate, l-methyl-2-vinylpyridinium methosulphate, the press rolls and by gluing the paper web 25 l-Methyl-2-vinylchmolirumethosulfat, 1-Benzylauf the drying cylinders. 4-vinylquinolinium chloride, N-vinyl-N'-methylimide, the plastic particles also often accumulate on one of the leaf surface azolium methosulfate, N-vinyl-N'-benzylimidazolium surfaces, which may be added to the subsequent chloride and 1-vinyl-3-methylbenzimidazolium metho calenders Gluing the paper web to the sulfate.

Rolling caused. Due to too coarse and unevenly 30 Insoluble olefinically unsaturated in water

moderate deposition of the plastic particles are the compounds within the meaning of the invention are exemplary

Furthermore, papers mostly more or less inhomogeneous. wise the esters of unsaturated carboxylic acids, such as

All of these difficulties are "likely to be methyl, butyl, or acrylic acid and methacrylic acid

caused by the fact that the hydrophobic synthetic -cyclohexylester; Vinyl esters such as vinyl acetate and

Particulate matter itself has no affinity for paper fiber 35 vinyl propionate; Vinyl halides such as vinyl chloride

and form conglomerates during precipitation. and vinylidene chloride as well as acrylonitrile, styrene, a-Me-

Improved processes are also known, in the case of ethylstyrene, butadiene, 2-chlorobutadiene, isoprene and esters, in which plastic dispersions are used which contain maleic and fumaric acid or additionally vinyl cation-active water-soluble dispersants. ethers, such as vinyl isobutyl ether. In addition, the plastic 4 ° copolymers can also be deposited on the fibers in amounts of up to about 10 percent by weight of water-soluble olefinic substances, even without the addition of precipitants, but the plastic deposit is very unsaturated monomers such as acrylic and methacrylic compounds irregular and coarse. This leads to special acid amide, polymerized in,
The proportion of N- or C-vinyl-substituted aro-disorders, as described above with regard to the use of anion-active dispersions with regard to the use of 45 matic and / or heterocyclic ammonium dung, is similar with larger plastic additives. connections in the copolymer is appropriate

It has now been found that plastics containing moderately between 1 and 15 percent by weight. He can

Papers can be produced advantageously by adding 20% and more, as far as only the

The copolymers relating to the fibrous material present in aqueous suspension are difficult in water

Plastic dispersions of practically 50% soluble in water and easily dispersible in it,

insoluble cation-active copolymers from The addition according to the invention of such cation-

N- or C-vinyl-substituted aromatic and / more active dispersions can after the usual Aufoder heterocyclic compounds in the core. beat the cellulose fibers and, if necessary, look up

or in side chains at least one quaternary nitrogen atom whose grinding to the relatively high concentration

Contain, and in water sparingly soluble oil tration 55 present fiber, for example in

finically unsaturated compounds and Dutch are mixed.

This mixture is then used in the papermaking process. The quantity ratio between plastic and usual way drained. Such mixed poly fiber material can be selected as desired within wide limits merisate draw from aqueous suspension to a large extent. According to the invention, in addition to papers very evenly and finely distributed on cellular 60 with only low plastic contents, including some loose fibers or cellulosic fibers on, and one produced in which the amount of plastic receives - without disturbing the above-mentioned the amount of cellulose fibers possibly far Type occur and without the addition of precipitation or exceeds. It is particularly surprising that the Fixing agents - very homogeneous papers, their polymer particles even with high plastic properties can be varied widely. 65 additions, e.g. B. in the case of a plastic-fiber material

Plastic dispersion ratio of 1: 1 which can be used according to the invention, generally complete and

Sions can advantageously be retained by the method of being evenly distributed on the fibers

USA. Patent 2,891,025.

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Since, accordingly, the water flows off practically clear when watered, it comes to room temperature. hard! polymers that .z. B. sieve, in the drainage system and on the presses made predominantly of styrene or vinyl chloride no disturbances, and the sheet formation has taken place, so you get more or less hard without difficulty. Together with the plastic 5 papers, the stiffness, hardness of sound and stable material particles, if necessary, added filling will show and for the production of e.g. and corrugated cardboard are suitable.

If plastic-rich papers are to be produced, the advantageous properties of such papers

So you can get the pulp dispersions with a 10 in general by a calendering, i.

Plastic content of 20 to 50 percent by weight, post-treatment under pressure and heating,

slowly add in portions. For production as is common in the paper industry,

On the other hand, it is advantageous for low-plastic papers, even better.

dispersions corresponding to the fiber material with a very high content of hard poly-

₀ add plastic content of about 3 to 10 ° /, merisaten 15, for example of more than 40 weight

In order to distribute the percentage of art as evenly as possible, the papers are heated to a higher temperature

to reach particles in the fiber. It can also be thermoplastically deformable. Will such papers

In some cases it may be advantageous to calender the fiber material before under sufficient pressure, so one obtains

Adding the plastic dispersion to dilute. transparent and film-like products that contain the

After a mixing time of around 10 to around 20, they have largely lost their paper character. the

30 minutes are the plastic particles in general. The required pressures and temperatures are from

mine drawn onto the cellulose fibers. Which depends on the type of polymer used and

Fibrous material can then be between about 5 and 10 atmospheres or between about 5 and 10 atmospheres in the usual way

machine. The pulp becomes about 80 and 180 ^° C. Dispersions of hard polymers produced according to the invention, ie from polyas paper, are also noticeable after pressing

merisates that soften at temperatures above 25 ° C are characterized by good wet strength.

added, it is generally expedient to add the parts given in the following examples

Fibers during the drawing up of the plastic are parts by weight,

particles or subsequently, for example, by _. .

Introducing steam into the Dutch or by 30 example!

Adding hot water to heat. With many 100 parts unbleached sulphate pulp used in

Copolymers of styrene or vinyl chloride in the usual manner in a Hollander with addition

Temperatures of around 3000 parts of ground and defibrillated water are usually sufficient for this

50 ⁰ C. As a result, the drainage at the was, one gives 400 parts of an approximately 50% igen

Sheet formation facilitated. In the case of soft polymers, an aqueous dispersion of an emulsion polymer

such annealing is generally not made from 80 parts vinylidene chloride, 20 parts acrylic

necessary. acid butyl ester and 3 parts of N-vinyl-N'-methyl-

The type and speed of absorption of the imidazolium methosulfate, the 3 parts of polyvinylpyr-

Plastic particles are apart from the structure of the polyrolidon with a K value of 30 as a protective colloid and 2 parts

Also, the type and quantity of the dispersion 40 diethyl dodecylammonium sulfate as cation-active

greedy dependent. For example, it contains dispersing agents. The pulp is left

drawing speed up to a certain point then 15 minutes with the grinding roller raised

with the amount of cationic dispersant; circulate in the Dutchman, with the plastic particles

on the other hand, as the amount increases, it absorbs virtually quantitatively on the cellulose fibers.

non-ionic dispersants and is ex- tra 45. Then the pulp is as usual on the

that dehydrated from the pre-treatment of the cellulose fibers paper machine. You get a paper

dependent. Also for the properties, especially that very soft and supple after drying

for the sizing of the finished paper, the type can be and this can be done in the usual way

of the dispersants and protective colloids used, satinage becomes oil and water-tight. It can be for example

be of importance (see. Example 4). 50 are used with advantage in the packaging industry

Depending on whether the fiber is turned according to the invention,
cation-active dispersions of hard or soft

Copolymers are added, Example 2 is obtained
Papers with very different properties. If one uses dispersions of at room temperature 55 to a mixture of 3000 parts of water, 50 parts of copolymers, one obtains soft sulphite pulp and 50 parts of bleached sulphate and optionally sized papers with elasticity pulp, each suitable for glassine production and suppleness properties like them So far, 80 parts of a 20% strength are given in the Holländer with the help of the known processes, for example plastic dispersion, which could not be made from 80 parts of acrylic by adding plasticizers, 60 butyl ester, 20 parts of acrylonitrile, 3 parts. Since, in contrast to the usual N-vinyl -N'-methyl-imidazolium-methosulphate and the process of plasticizing paper, this 1.5 parts of oxethylated tridecylamine as a dispersing effect is not based on the hygroscopic properties of the greases due to emulsion polymerization in 150 parts of plasticizer, remains the soft character len water was produced. The pulp of the paper is also preserved during the drying process. This is then thoroughly mixed for 15 minutes and papers of this type are partly processed into glassine in the usual way after the calendering with oil, and are watertight and can be used, for example, with A soft and pliable glassine, advantage in the packaging industry. which has a relative wet strength of about 25%.

(The relative wet strength was determined according to Brecht, Scientific publications of the Technical University of Darmstadt [1947], Vol. 1, Issue 2, p. 33 to 47, measured.)

Glassine produced in the same way without the addition of plastic has a relative wet strength of only 6% · It is much harder and brittle. It is made by adding glycerine or magnesium chloride plasticized as usual, its strength properties are thereby significantly impaired.

Example 3

100 parts of a mixture of bleached sulphite and sulphate pulp with addition of 3000 parts of water in a laboratory blender with 200 parts of a 40 ° / ₀ aqueous dispersion of a Emulsionsmischpolymerisats of 90 parts of styrene, 10 parts of butyl acrylate and 3 parts of N-vinyl-N ' -methylimidazolium methosulfate is added, which contains 3 parts of diethyl dodecylammonium sulfate and 2 parts of oxethylated sperm oil alcohol as a dispersant. From the pulp is then prepared in a conventional manner by a drainage box, which is pressed in a laboratory calender at 140 ⁰ C. The result is a very hard cardboard box with a scratch-resistant surface which, however, is not brittle and which has the sound hardness desired for playing cards.

Example 4

30th

100 parts of bleached sulphate pulp are made in a Hollander with the addition of 3000 parts Whipped water in the usual way and ground. The pulp will be slow and possible evenly in front of the grinding roller of the Holländers 55 parts of an approximately 4% aqueous Dispersion of an emulsion copolymer composed of 70 parts of butyl acrylate and 30 parts of acrylonitrile and 10 parts of N-vinyl-N'-methyl-imidazolium methosulfate, the dispersant 1 part diethyldodecylammonium sulfate and 3 parts polyvinylpyrrolidone contains a K value of 30, added. The pulp is then processed in the usual way dewatered on the paper machine. The result is a paper that is well sized against ink and that is cleaner is white as a paper produced in a known manner with the addition of resin size for comparison.

Example 5

In a Hollander, 200 parts of an approximately 35% aqueous dispersion are added to a suspension of 100 parts of bleached sulphate pulp with a freeness of about 40 (see Leaflet No. 107 of the Association of Pulp and Paper Chemists and Engineers) in 3000 parts of water with the grinding roller raised a copolymer of 70 parts of vinyl chloride, 30 parts of butyl acrylate and 3 parts of N-vinyl-N'-methyl-imidazolium methosulfate, which contains 3 parts of dimethyl dodecylammonium sulfate and 2 parts of oxethylated sperm oil alcohol as a dispersant. The pulp is then heated in the Hollander by adding hot water or by introducing steam to about 45 ° C and then dewatered as usual on a paper machine. A hard, largely paper-like, but thermoplastically deformable product of high stability is obtained. By pressing at about 120 ^° C. under a pressure of 20 to 40 kg / cm ² , a material can be produced therefrom that is largely transparent and has a similar density and surface hardness to a polyvinyl chloride film.

Claims (1)

Claim: Process for the production of plastic-containing papers by adding aqueous plastic dispersions to the fibrous material present in aqueous suspension, characterized in that that dispersions of known, practically water-insoluble cation-active copolymers are added to the pulp firstly from N- or C-vinyl-substituted aromatic or heterocyclic compounds, which contain 1 quaternary nitrogen atom in the core or in a side chain, and secondly in water sparingly soluble olefinically unsaturated compounds and then this mixture dewatered in the usual way in papermaking.