CS241131B2 - Method of hydrophilic surfaces soaking and/or adhesive poperties modification - Google Patents

Description

( ^{54 * * * * * * * * * * * * * * * * * * * 73} ) Patent owner

ALJOŠI zsolt; BÍLINT GYULA, HORVÁTH GYULA; HORVÁTH LÁSZLíW; KO (Js JÁNOS; SÚMEGI MIHÍLY dr., * TURNER LAJOS / VÁRSZEGI GYULA, DUNAUJVIRS / MLR /

ALKOTÓ IFJUSÍG EGYESÚLÍS, BUDAPEST (MLR) (54) A method of modifying the wetting and / or adhesive properties of hydrophilic surfaces

The invention relates to a method for modifying the wetting and / or adhesive properties of hydrophilic surfaces of cellulose-based packaging materials, such as. . of paper and paper products, pressed fibreboard and particle board.

In this method, 0.1 to 30.0 g of a substance which is a natural resin, paraffin, atactic polypropylene, montan wax or an emulsion mixture thereof is applied per square meter of surface. of an oil-in-water type comprising an emulsifier and a stabilizer, which are present in the emulsion medium and / or are formed during emulsification and / or apply solid particles of an inorganic substance, not more than 50 µm in weight amount of 1-35 t %, based on the emulsified substance, after which the aqueous medium of the applied emulsion is removed by drying, preferably at a temperature above 100 ° C.

By means of the method according to the invention, the coefficient of friction can be varied within a wide range. the water resistance is good, and due to the special structure of the resulting surface layer, they can be glued well with aqueous adhesives.

AND

The invention relates to a method for modifying the wetting and / or adhesive properties of hydrophilic surfaces of cellulose-based packaging materials.

In many industrial areas, for example in packaging, it is desirable to provide an inner surface of the packaging composition resistant to the moisture of the goods and an outer surface resistant to external moisture due to, for example, climatic conditions.

Packaging means, such as corrugated board, pressed fibreboard and particle board, normally meet the requirements for packaging in terms of uniformity, protection of goods and economy, when the goods themselves are not damp or do not come into contact with the surface of the packaging, or even when the packaging material itself is not exposed to any climatic effects, such as rain, snow, cold storage, etc.

If all this cannot be guaranteed during the conveyor chain, then the packaging means _{f is} made of a material which repels moisture itself, or the resistance of the packaging materials which are not themselves moisture resistant increases.

The water resistance can be increased when auxiliaries are added to the mass during the production of said types of packaging means or the auxiliaries which are added are applied to the surface.

To increase the water resistance of the corrugated board, for example, deposition or impregnation with inexpensive paraffin melts, which are available in corresponding amounts, is widespread.

The use of paraffin or paraffin-based substances, both by adding it to the mass in the manufacture of the product and by applying it to the surface, not only increases the surface's resistance to water, not only gloss but also its slip and smoothness.

This, in turn, makes it difficult to transport, store the processed material, further process the packaging means and adversely affect the storage and transport of both empty and filled products.

A further problem is that processing of packaging materials naturally hydrophilic, for example by melt coating or melt-impregnation, is itself an additional process step. Waste that is lost in the manufacture of packaging materials, such as cardboard waste in the manufacture of cartonboard - and spent packaging material such as corrugated cardboard that enters the collection of waste paper can only be reused as a raw material for paper production after complicated processing, for example after paraffin removal in any way, most often with high energy and chemical consumption.

Problems also arise in the gluing of impregnated or coated surfaces, aqueous dispersions, for example in the manufacture of cartons, their sealing, labeling etc. In these cases considerably more expensive, often organic and therefore more dangerous and harmful adhesives have to be used.

These disadvantages have been eliminated in the method of modifying the wetting and / or adhesive properties of the hydrophilic surfaces of the cellulose-based packaging materials of the invention, which comprises depositing 0.1 to 30.0 g of a substance selected from the group of square meters per surface area. including resins, paraffin, atactic polypropylene, montan wax and mixtures thereof, in the form of an oil-in-water emulsion containing an emulsifying and stabilizing agent, wherein they are present in and / or are formed in the emulsion medium and / or The emulsion is applied to the surface by solid particles of an inorganic substance of a maximum of 50 microns, in a quantity of 1 to 35% by weight, based on the emulsified substance, and the aqueous medium of the emulsion is removed by drying, preferably above 100 ° C.

Cellulose-based packaging material is understood herein to mean cellulose-containing substances, such as wood, shives, hulls, processed cellulose-containing natural materials, such as sawdust, wood fibers, wood abrasion, and chemically treated cellulose-containing substances, such as cellulose, semi-cellulose, paper waste.

Preferably, rosin and / or talc resin is used as the emulsion.

The solid particles present in the emulsion medium and / or resulting from the emulsification are preferably iron hydroxide and / or silicic acid and / or aluminum hydroxide and / or lead hydroxide and / or tin hydroxide and / or antimony hydroxide, and the fine particles to be metered are bentonite and

or b) kaolin and / or diatomaceous earth and / or barium sulphate and / or calcium sulphate and / or calcium carbonate and / or magnesium carbonate and / or titanium dioxide.

By the method of the invention, the hydrophilic packaging materials have achieved the water resistance required by the packaging technique so that the surfaces to be treated are no more slippery than untreated and, if desired, less slippery.

The production of surfaces of the desired wettability and friction properties does not need special equipment or other working processes, but is feasible on commonly used equipment without interfering with further production.

The waste that is lost in the manufacture of the packaging means and the consumed packaging means is reusable without being prevented by a surface treatment to improve water resistance.

The gluing process does not require any special adhesives. Adhesives consisting of aqueous dispersions provide the necessary bonding strength.

In the process verification of the invention using conventional techniques, without additional machines and without further processing steps, a spraying device was installed in the corrugated board manufacturing machine and the board surface was sprayed with a paraffin emulsion.

The emulsion medium was then removed after drying. It has been found that surface particles surrounded by hydrophilic emulsifiers and stabilizers that adhere to the surface of the corrugated board reduce the wettability of the surface with water. .

This effect before using the method according to the invention did not originate because when the emulsion of this quality has been added to the mass, decreasing the wettability of the paper with water only "if the emulsifiers and stabilizers with character alkali metal salt converted into the salts with multivalent metal ions, such ^RIK la ^d Ca ²⁺ , Al ³ '

If the emulsion contains not only associated and lyophilic macromolecules, colloidal emulsifiers and stabilizers, but also fine solid particles - such as Pickering's. emulsion - then the water-resistant surface produced by the method according to the invention - even if it retains shine and glitter - is not slippery.

Conversely, friction may be even higher than that of the original surface. This effect is even more marvelous, since the presence of hydrophilic emulsifiers and stabilizers present in the emulsion medium and surrounding the paraffin particles is not observable on the surface, the water resistance does not deteriorate, the effect of the fine solid particles surrounding the paraffin particles, respectively. they are present in the emulsion medium but are detectable; the smoothness of the surface is reduced.

Another advantage is that, despite the water resistance, it was not necessary to use organic or so-called hot-melt adhesives, but also that the aqueous dispersions provided sufficient tack. Good editability of the edge waste which is lost during the production of corrugated board, waste in the production of cartons and spent cartons in conventional waste paper treatment facilities

Even the industry was another unexpected effect. All this must be seen in the context of the particular structure of the layer formed.

The coating technology according to the invention thus eliminates the adverse effects of the treatment of the lydophilic surfaces and, on the contrary, brings new advantageous effects.

A detailed description of the process according to the invention is given in the following examples.

Example 1

Of 350 g paraffin, 14 g casein, 1 g sodium hydroxide and 11 g in the Diels-Alder synthesis at 100 mol%. maaeinizované higher aliphatic carboxylic acid with the usual way of making ^p s 90 ° C ^if 1 ≤ t ≤ r ^p ara ^{fi newly} emdzi.

From this was applied imnoství 50 ml / m * by means of rollers to the surface přítaačných bodies ^p oužívanýc ^h at productions ^runs vini ^ ^l ^ e ^ ^p en ^{ky. p p} s of drying 10 ⁰ C as measured ^by a concave marginal ^for a'konvexní destncna hei ^ ^dy in Neu ^p Raven -a upaveném ovrc ^{p h p} for PA handbook at ²⁵ ° C L ^P Omoo> rentzen-meter edge Wettresový ehii, which is provided with a conditioning chamber providing 100% relative humidity (see: Pappripari an ^y savizsgálat, Muuzaki KonyvkiadJ, Budapest, 1980). '

Konkáwií marginal ⁱⁿ HEL and ^the 95 ° convex combi TOEL ^by 26 ° and in the untreated ^ o ^ PPIRM prováděio measurement 1 minute after the instillation, the modified paper b ^y l concave edge angle? 120 °, the angle of the convex edge 8 ^{O 9.}

Souu ^ b -ntel adhesion surfaces ^yl meter measurements will prepare working on a similar basis as the drawing Mříč angles according Buzágha / see: Buzágh A: A kolloidika Praktikus, TMkonnykiadó,. Buda ^p pšť, 1962 /.

The instrument name is Plane Fricticm Tester. δο ^ ΐη ^ οΐ the adhesion of the raw paper is 0.33. Related to the adhesion of the treated paper to the untreated surface but 0.20.

Example 2

The procedure of Example 1 was followed, except that 25 ml of marketable water glass was charged instead of 1 g of sodium hydroxide in the preparation of the paraffin emulsion. The reaction of the waterglass and the maineized higher aliphatic carboxylic acid produced silica acid in situ over a period of days.

Z t ^s This emulsion was ^p ovrc ^HP Apiro us ^ i ^ n 1 mL / ^m2. After drying ^p s ¹¹⁰ ° C, the same tests hilarious ^y I s ^{to comm} ice ^with one concave edge angle b ^yl 104 ° ^to onvexní edge ^diagonals 92 ° el, а ^ ^ т е! The adhesion of mm 2 treated and untreated with paper was 0.29.

Example 3

Example 1 was followed by adding 122.5 bentonite containing a maximum particle size of 50 microns to produce the paraffin emulsion. This emulsified substance was applied to the surface in a 75 ml / m paint roller.

After drying ^p s 1 ² 0 ° C it was tested by pHkJLadu 1, such as the landing acquires a ^y ^^ ^y values ^P ro 108 ° and ⁹⁶ ° konkároí ^P ro úhhl convex edge, and ^d or the adhesive součiin ^ el mmzi upavený untreated surface b ^y l 0.27.

Example '4

The procedure of Example 1 was followed except that 550 ml of a 50 g silicon acid sol of 50 g (l) was produced using a cation exchange synthetic resin. Buzagh A ·:

A practicum colloidics, Tankonyvkiado, Budapest, 1962 / and this was used as an environment for paraffin emulsion instead of water. 5 ml / m of the emulsion thus prepared was sprayed on ovrch ^{p p} and ^pi ru. Higher ^alkyl ed ^l ^ k test of ^Ex range of 1 ·. Otoajový ^diagonals el: ^{kon ka} HV ^{and 11} 8 ° ^to onvexní 106 °, the coefficient of adhesion between untreated and surface treated was 0.36.

A number of solid particles (e.g. kaolin, rutile, bauxite, calculus, etc.) which increase the coefficient of adhesion of the treated surface are also within the scope of the invention; Mixtures of paraffin and atactic polypropylene, rosin and tall resin may also be used as organic components of the water-in-oil emulsions.

Furthermore, it was found that as emulsified component a substance produced by emulsifying agents are suitable, rain ^IL alkylated ou p a ^{d s of 25} ° CA ^ky axis ^{P and} I TuJ ^kk on ^the ATC ^{for even} the 90 ° / see: Wol ^f ram e .: account not ^{kt d} Vese ^DE and ^K ad ^e m ⁱ n ⁱ ^ AclO which when applied as a film and is moistened ^to onvexní ^to Rájov ÚHE ^greater than ^L in Budapest, 1971 /.

the effect of the fine solid particles does not primarily depend on the quality. In addition, it has been found to cast. but rather on the shape and size of the particles. This makes the range of both groups of substances very large. The following exemplary embodiment serves to support what has been stated.

Example 5

Starting from Example 1, with the difference that 550 ml of 10 g / l aluminum hydroxide sol was produced by dialysis (see: Busag A .: A kolloidika praktikuma, Tankonyvkiado, Budapest, 1962) and this was used as an emulsion medium such as emulsified substances were used rosin and montan wax in a ratio of 1: 1, instead of sodium hydroxide was dosed with 10 ml of water glass, which reacted with both maleicized higher aliphatic carboxylic acid and with rosin and silicic acid formed.

Then, 5 g of calcium sulphate with a particle size of at most 50 micrometres were added to the emulsion. An amount of 20 ml / m 2 of this emulsified substance was sprayed onto the paper surface, drying was carried out at 160 ° C.

Concave ^and peripheral ^{diagonals would l} e l ^{2% to} 11 onvexn ^d of ^{the diagonals} Rájová b ^l e 1 ^{-yl 04} °, Nam Measured Holota ^measured adhesion coefficient was 0.34.

In the process according to the invention applied to the surface, preferably by spraying, painting or printing ^alkyl acrylate containing fine solid particles obtained by emulsification, an oil in water.

As used herein, the term "emulsified" means that it is a system that at least can consist of at least two non-miscible components at the manufacturing temperature, or themselves. they may contain several components and in which the liquid phases have been produced by dividing the fine droplets of one of the phases into the other phase in the environment and stabilizing them against foaming or settling or re-agglomeration on the phase.

For stabilization, emulsifying and stabilizing agents are used which, by coating the surfaces of the particles, create good conditions for their wettability in said environment. For example, in a fat-oil organic substance such as paraffin, rosin, bitumen, emulsifiers made from resin acids, higher carboxylic aliphatic acids, sulfonates and sulfates with higher aliphatic alcohols, as well as hydrophilic macromolecular stabilizers such as dermal glue, alkaline casein solution, sodium carboxymethylcellulose hydrophilic surface of the oil droplet and contribute to its good wettability with water by surrounding it.

At room temperature, however, the particles of the substances obtained by emulsification may be in a solid state, such as paraffin or rosin (see: P. Becher: Emulsion, Muszaki, Konyv kiado, Budapest, 1965).

In the description of the macroscopic surfaces viewed as hydroxy ° filníf if the value konkáwního edge angle, measured at room temperature with destifov <my water increased and the ^k ovexní ^h the edges ^ O ^U HLU less than 90 deg / see WO- ram E .: Kootakt nedvesedés, Académisi Kiadó, Budapest (1971).

Claims (3)

SUBJECT OF THE INVENTION 1. A method for removing the wetting and / or adhesive properties of the hydrophilic surfaces of cellulose-based packaging materials, characterized in that 0.1 to 30.0 g of a substance selected from the group consisting of natural resins is applied to a mmtr square surface. , paraffin, atactic polypropylene, mellt wax and mixtures thereof, in addition to the oil-in-water emulsion, containing and stabilizing agent, are present in and / or during emulsification in the emulsion medium. and / or solid particles of inorganic material of a maximum of 50 microns in size of 1 to 35%, based on the emulsified substance, are applied and / or applied to the surface simultaneously with the emulsion, after which the emulsion is removed by drying, preferably above 100 Deň: 32 ° C. 2. A method according to claim 1, wherein the substance applied in the form of an emulsion is a rosin and / or a draw resin. 3. Process according to claim 1, characterized in that the solid particles present in the emulsion medium and / or formed during the emulsification are iron hydroxide and / or silicic acid and / or aluminum hydroxide and / or lead hydroxide and / or tin hydride and / or hydroxide. the antimony, and dosed fine particles are bonton nt and / or kaolin and / or diatomaceous earth and / or barium sulfate and / or calcium sulfate and / or calcium carbonate and / or magnesium carbonate and / or titanium dioxide.