DE2358957A1 - PROCESS FOR BINDING SHEETS WITH A HYDROPHOBIC SURFACE - Google Patents

Description

Pat-s nt on cotton wool
Dr. Day. A. va ^ s slar

S1 Hamburg ΘΟ -

WiVstorfer StCßSe 32

. 25.3.0.06

UGB, S.A. Saint-Gilles-lez-Bruxelles / Belgium, 4, avenue "de Gharleroi

Method for binding leaves with hydrophobic surface

Priority: November 29, 1972, United Kingdom, No. 55H5 / 72

The invention relates to a method for integrating Leaves with a hydrophobic surface and. also the bound products thus obtained.

A leaf with a hydrophobic surface is understood to mean: ', (I) a leaf, which leads to the larger rope made of hydrophobic Material consists, and

(II) a leaf, which for the most part consists of hydrophilic Material. Consists, but of a skin with hydrophobic is covered over the surface "

Examples of sheets of type (.1) are synthetic papers, produced using plastic materials based on homo- and copoXymeres of ethylene, propylene, butylene, isobutylene, butadiene, isoprene, styrenes and the like. and their mixtures, which can also contain other substances, such as acrylic resins, acetal resins, phenolic resins, antioxidants, stabilizers against heat and light, optical brighteners, pigments, dyes, mineral pullers (calcium carbonate, titanium dioxide, barium sulfate, kaolin, etc.), antistatic agents, lubricants and the like «, ^ '

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Examples of sheets of type (II) can be mentioned The papers are based on cellulose fibers, the surface of which is hydrophobic due to the application of a membrane have been done. This membrane can be formed by plastic materials such as those which have been mentioned for the sheets of type (I), or also by other plastic hydrophobic materials such as the copolymers of vinyl acetate, vinyl chloride, vinylidene chloride, Nitrocellulose, silicones, urea-formaldehyde resins, Melamine-formaldehyde resins, or by others water-repellent materials such as rosin or chromium stearate complexes. Another type of leaf of type (II) is the one obtained by adding water-repellent substances to the pulp of cellulose fibers, before it is converted into paper by rollers on the paper machine.

The synthetic papers of types (I) and (II) are becoming increasingly important because of their inherently advantageous properties Properties that are missing from the gelulose paper. The synthetic papers have good impermeability for water vapor and other gases, they show good resistance to water and fats, their dimensional Stability is remarkable in the case of very strongly fluctuating atmospheric conditions, etc. Therefore replace They advantageously use ordinary paper for the 'production of items such as road maps, topographical Maps, tourist cards, official documents such as driving licenses, hunting licenses, fish licenses, forms, catalogs, posters exposed to the weather, children's books that can be washed off with water, transistor paper, hand containers for vehicle lubricants and care products, self-adhesive labels resistant to oils and fats, and the like.

However, one drawback of synthetic papers of types (I) and (II) is that they do not bind let according to the methods used for binding conventional cellulose paper. For integrating Cellulose paper is used for aqueous, liquid glue

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Of natural origin (dextrin, starch, gum arabic, isinglass, bone glue, etc.), or of synthetic origin (latex from polyvinyl acetate or from ssirar synthetic rubber and the like.)., which by means of a brush, a Roller or the like * can be applied. Ordinary there Gelulose paper has a hydrophilic character, it immediately absorbs the water of the glue and allows up In this way, in a few minutes, a coherent adhesive film between the sheets at the location of the binding to obtain. On the other hand, because of the hydrophobic character of synthetic papers, this absorption of water occurs the glue does not apply and a much longer drying tent is required (from several hours to a month) for the elimination of the water. In addition, the mechanical Properties of the binding formed in this way are clear worse than those made with ordinary cellulose paper to be preserved.

In order to remedy this drawback, it has been proposed to use heat-melted adhesives which are adhesives which become liquid when heated and which are applied to the binding area in this state the adhesion between the sheets taking place as the adhesive solidifies upon cooling. This gluing method has the disadvantage of requiring expensive and familiar equipment How the glue is applied using a brush and Roller dispense with mass. It would therefore be of great importance Interested in being able to bind sheets made of synthetic paper in accordance with the usual gluing procedures, how they are used for binding cellulose paper. This requires the discovery of liquid adhesives, which make it possible to produce at least as robust bindings with synthetic paper as those which do with aqueous foodstuffs on ordinary cellulose paper be generated. This is precisely the aim of the present invention. "■" '"■ ..

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The invention thus aims at a method for incorporation of sheets with a hydrophobic surface, in which an adhesive is applied to one of the edges of the stacked one on top of the other Applies leaves, and it is characterized by the fact that the adhesive is a curable material - Composition is which is liquid at ordinary temperature and is selected from the group consisting of the end

(1) alkyl-2-cyarloacrylates

(2) epoxy resins and

(3) polyurethane resins.

(1) The alkyl cyanoacrylates contain the alkyl radical

1-18 carbon atoms. It is to quickly cure liquid compounds, which have the property (in 0.5 to 5 minutes) at ordinary temperature in the presence of a trace of water, _r atmospheric water vapor or alcohol. For further details on this category of adhesives, reference is made to the work by IRVING SKEIST, "Handbook of Adhesives", Reinhold Publishin Corporation, New York, Chapman & Hall, Ltd., London, '1962, pages 409-414.

(2) The liquid epoxy resins useful for the invention are derived from epichlorohydrin and bisphenol A, where this latter completely or partially replaced by other alphatic cycloaliphatic or aromatic diols or triols can be, in particular by bisphenol F (derivative of phenol and formaldehyde), tetrachlorobi ^ phenol A, etc.

They are curable by amines and polyamines, anhydrides of Polycarboxylic acids, monocarboxylic acids, polyamides, polyisocyanates, and by catalysis with alkalis or Lewis acids (Boron fluoride and the like). These liquid compositions can contain thinners, reactive or inert substances, which are intended to reduce the viscosity, "for example tall oil, dibutylpwalat, 2,3-epoxyoctane, styrene oxide or the like., to discontinue »

(3) The liquid polyurethane resins are prepared by going out you liquid compounds which contain reactive hydrogen atoms that react with Isocyanaten-

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can., and of di- or polyisocyanates «Examples these liquid compounds, which are reactive Containing hydrogen atoms, are

(a) Polyester with terminal hydroxyl groups, obtainable starting from a dicarboxylic acid (adipic acid, phthalic anhydride, dimerized linoleic acid and the like) and a glycol or polyalcohol (ethylene glycol, propylene glycol, butylene glycol-1,2 and -1,4, hexanediol-1, 6, glycerine, trimethylolpropane, hexanetriol-1,2,6, u _e like _e ) | '

(b) Polyether of a glocol or polyalcohol with terminal ends Hydroxyl groups, generally producible by the addition of Alkylenoxyäsn (ethylene oxide, propylene oxide u.dglo) on glycols or polyalcohols, di- or'Polyamines or through the polymerization of tetrahydrofuran!

(c) castor oil and its derivatives. Transesterification of Castor oil j, Uo dgl §

(d) Diamines (ethylenediamine, propylenediamine, hexamethylenediamine, ^ like j

(e) hydroxylated polythioethers, Z ₀ B ₀ the addition products of thiodiglycol and ethylene oxide, propylene oxide, etc. o

Examples of di- and polyisocyanates are the toluylene diisocyanates-2,4 and -2,6 and their mixtures _s the 4 _s 4'r DiphenylmethandiisQcyanat, the 4,4 ^I 4 "-TriphenylmethanriisocyanatjUodgloρ (the products of dimerization, trimerization-Uodglo these Isocyanateo dii.e addition products to terminal 100 groups, as obtained by reacting an excess of di- or polyisocyanates with i $ i- or polyhydroxylated compounds, Tladglo

I am the integration of leaves with a hydrophobic surface by means of liquid adhesives according to the invention to accomplish, you stack the sheets on a regular Pile, keeping it under pressure in the usual way and applying the adhesive to one of the edges of the

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pressed stack by conventional methods (brush, rfalze, spalel, etc.) · on. The amount of adhesive varies according to the type of adhesive used; it is usual to which 50 to 500 g / m ² of the surface einzubindenden '", preferably 100 to 400 g / m ^2.

The type of application of the adhesive varies according to its type Type (1), which are always in hermetically sealed containers are packed in place of the tape by touching the emptying opening of the container and spreading of the liquid food applied over the entire edge of the sheets to be bound, with the adhesive is ejected from its container either by gravity or by pressure, if the container is one by pressure Has deformable wall. The alkyl cyanoacrylate adhesive hardens in a few minutes in contact with atmospheric moisture.

In the case of the epoxy resins of the type (2), the epoxy resin is mixed with the compound in the desired proportions, namely 1-200 parts and preferably 2-150 parts of hardener per 100 parts of the epoxy resin, and if necessary, the Viscosity by adding a thinner.

The polyisocyanate adhesives of type (3) are mixed the di- or polyisocyanate and the liquid compound with active hydrogen atoms at the time of use in the desired proportions (ICO / OH ratio of 0.2 to 2, preferably from 1 to 1.5) and one adds to this mixture if necessary, add an accelerator for the polyaddition if rapid curing is desired (0.001 to 5 Gew./, preferably 0.02 to 2 & ew "$) j you can also if necessary, add an inert thinner to adjust the viscosity of the mixture thus obtained «

Whatever the liquid adhesive used according to the invention, the hardening can take place for a period of time, which depends on the type of adhesive. This duration varies approximately from 1 minute to 24 hours, preferably from 2 meows to 12 hours _or more

one can harden the adhesive with relative long hardening time due to massive heat treatment "accelerate (blowing with heated air, infrared radiation etc.). Of course, the temperature reached in this way must in any case be below the softening point and the deformation of the synthetic paper remain, which should be integrated. Generally should the heating temperature should not exceed approx. 60 0.

Once the binding has solidified enough, the bound sheets will be pulled out of the press.

The binding process just described is the one carried out by hand by the bookbinder. However, the liquid adhesives according to the invention can also be used in modern bookbinding machines which work with liquid adhesives. For these machines you can see in the case of adhesives of type (1) a single storage and supply container for the adhesive before because these adhesives no additive for hardening benStigen _o In contrast, in the case of the other inventive adhesive must be a special container for the agent, That is to say, one for the resin and one for the hardening agent. These containers fill a homogenizing vessel in which the ingredients are intimately mixed and then sent to a suitable automatic distributor, which applies the adhesive to the location of the binding.

If the. Sheets of synthetic paper, which by means of the inventive - ^ food are involved, by a cover, linen cover ο "the like" should be protected, you can also use the same adhesive for this purpose Effect of the connection between the lid? the linen cover ο «, the like« and the association = however according to an advantageous embodiment of the invention Procedure one takes the leaves' out of the press before the Hardening of the adhesive is complete, that is to say the point in time at which the adhesive already has a firm bond of the sheets among each other guaranteed, but still

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a certain adhesiveness "owns. One then puts the lid, or the like to Leineneinband under pressure. on the still-adhesive-bonded part and lets the whole harden _o This procedure thoroughly allows time un Rohstoffersparnisο

The following examples explain the invention without them ζ restrict.

example 1

This example, not according to the invention, is given to show that the aqueous glues which are generally used for The binding of sheets of cellulose paper can be used, opt for sheets of synthetic paper using hydrophobic surface not suitable.

The sheets to be bound consist of the synthetic paper according to Example 1 of BE-PS 752 917 of the applicant and it consists of 50% by weight of a high-density polyethylene with a melt index of 1 dg / minute, 15% by weight of a mixture of type " choc polystyrene "made of 90 ° polystyrene and 10% polybutadiene with a melt index of 3 dg / minute under a pressure of 7 kg / cm, 20 wt. fo a mixture of 50/50 polyethylene-polyisobutylene with a melt index of 0.2 dg / minute, 10% by weight of titanium dioxide which passes through a 50 micron mesh screen, 4% by weight of precipitated calcium carbonate which passes through a 50 micron mesh screen, and 1% by weight of paraffin oil.

A latex is used as an adhesive for the cover commercially available polyvinyl acetate (ADHBSIF A 22 from HENKEL) in an amount of 150 g / m 2 to be bound Surface. After 24 hours the drying has not yet ended and the binding has not yet solidified After one month of drying at ordinary temperature, the adhesive has solidified, but the one obtained in this way The binding is so weak that it will come off when you pull it weakly, while the same adhesive, if for binding sheets of cellulose paper used, results in a very solid cover.

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If you do this "attempt with replacement of the mentioned-synthetic Paper through a cellulose paper with a coating made of low-density polyethylene repeated £ d = 0.9-15), one makes the same observations. '

Example 2 '■ ^:

Sheets of cellulose paper with a coating of polyethylene (d · = 0.915) and as a liquid, according to the invention are used The adhesive is methyl-2-cyanoacrylate (GYANOLIT of the company Etablissements REMY ", Belgium). The applied The amount of adhesive is 100 g / m.

The adhesive is in contact in less than 5 minutes completely hardened with the humidity and you can Remove the bound sheets from the press. The quality of the binding is excellent.

Example 5 -

The synthetic paper used for this example is commercially available. POLYART (BX Plastics Ltd.} known and consists of olefin polymers. As a binder A liquid epichlorohydrin bisphenol A adhesive (Araldite AW 116 A der Company CIBA-GEIGY) and a hardener of the type one aliphatic amine (HV 953 U from GIBA-GEIGY) with a weight ratio between resin and hardener of 100 parts / 60 parts. The amount of liquid applied Adhesive is 200 g / m.

6 ^; Hours after the adhesive has been applied, the bound sheets can be removed from the press.

If you put the .POLYART paper through the papers with hydrophobic Replaced the surface as used in Example 1, a sturdy cover is also obtained for 6 hours after applying this adhesive.

Example 4 . . . ,. .,. ...

^Man: dieter used for seeking the synthetic paper of the ^3eispiels: f der IE-PS 75 ^ 917V ■ '■' - ■ '' - '' ■ '

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An adhesive made of liquid polyurethane, consisting of a mixture of 100 parts by weight of a hydroxylated polyester of adipic acid and diethylene glycol (DESMOCOLL 22 from Farbengabriken Bayer AG _n ) and 20 parts by weight of 4,4'-diphenylmethane diisocyanate ( DESMODUR VL from Farbenfabriken Bayer AG). One brings 180 g of this mixture to m ^{2 of} surface to be bound on »

After 8 hours in the press at ordinary Temperature you can take out the leaves, which are completely bound.

Example 5

This example corresponds to example 4 with the modification that the curing is accelerated by heating using an infrared lamp (ELSTEII FSR, 250 W, 220/230 Y).

After 4 minutes of irradiation, the bound sheets are removed from the press, although the hardness' medium is still sticky. A protective cover of the same is placed on the edge of the bound leaves synthetic paper, presses the cover against the one and allows the hardening to take place at ambient temperature complete. After 8 hours the cover adheres completely to the surface of the cover.

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Claims (10)

Claims 1. A method for binding sheets with a hydrophobic surface, wherein the sheets are stacked in a regular pile, pressed and an adhesive is applied to one of the edges of the sheets stacked in this way, characterized in that the adhesive is a composition of curable material that is liquid at ordinary temperature and from the group consisting of ^y (1) alkyl-2-cyanoaerylates' (2) epoxy resins and (3) polyurethane resins ■ ■ is selected. ' 2. The method according to claim T, characterized g e k e η η -. records that the alkyl-2-cyanoacrylates 1 to 18 Carbon atoms contained in the alkyl group and that they ■ hardened by atmospheric moisture. 3. The method according to claim 1, characterized in that g e k e η η - ζ e i c h η et that the epoxy resins are derivatives of epichlorohydrin and at least one polyhydroxylated compound dung, selected from. the group consisting of aliphatic, cycloaliphatic and aromatic diols and triols, and that they are selected by compounds from the group of amines, polyamines, anhydrides of polycarboxylic acids, monocarboxylic acids, polyamides, the Polyisocyanates, the alkalis and the acids of the Lewis type, are hardened. . ■ · 4. The method according to claim 3, characterized in that one of the polyhydroxy11erten compounds is bisphenol A. 5. The method according to claims 3 and 4, characterized ge k e η η'ζ e i c h η e t that the epoxy resins too Thinner included. " 409 8 22/082 6 _O method according to claim 1, characterized in that the polyurethane resins starting from liquid compounds with a content of reactive hydrogen atoms, which with. Isocyanates can react and are produced from di- or polyisocyanates. 7. The method according to claim 6, characterized in that the liquid compounds with a Content of reactive hydrogen atoms, which with the isocyanates can react, from the group "consisting of polyesters with a content of terminal. hydroxyl groups, from polyethers containing terminal hydroxyl groups, from castor oil and transesterification derivatives of castor oil, made from diamines and polythioethers with a content of terminal hydroxyl groups. be chosen. 8. The method according to claims 6 and 7, characterized in that the polyurethane resins by a polyaddition accelerator hardened. 9.Verfahren according to any one of claims 1 Ms 8, characterized characterized in that the adhesive is in a Amount of 50 to 500, preferably clay 100 to 400 g / m 2, the surface to be bound is applied. 10. Leaves with a hydrophobic surface, bound after a method of the preceding claims 1 "to 9. 409822/0928