DE1544707A1 - Process for the production of plastic films, fibers and fabrics with improved adhesive properties - Google Patents

Description

Process for the manufacture of plastic films, fibers and co-weaves with bad adhesion properties.

***************************************** The main ones used today Film base foils consist of cellulose triacetate, polyester, e.g. B.

Polyglycol terephthalate, polyether ester, e.g. B. Cokondenaat from diglycol terephthalate and p-oxybenzoic acid in the ratio 9: 1 and polycarbonate, e.g. Kon-Rdensat aua 4, 4'-Dioxydiphenyldimethylmethane and carbonic acid diesters. Polyamide Folion has been made for photographiache Purposes hardly used, since the water absorption and the monomer proportions are su high. Higher polyamides than film raw materials such as polyamide 11, 12 or 13 could lead to a change here. Polypropylene and polyvinyl chloride are not yet used as a basis for film documents in practice, as well Polyimide (H) films, e.g. polycondensates of pyromellitic anhydride and aromatic Diamines. In any case, the fully synthetic ones can be expected in the future Folion will gain in importance at the expense of the modified natural substances like Cellulosestery With this change comes the demand for suitable adhesive layers for the new folion. Simultaneously with this change, e.g. in the silver emulsion field, a development that is linked to the quality of the Hafstbus rate particularly high requirements. In the transition to thin-density emulsions with low gelatin content and highly hardened emulsions may affect the quality of the adhesion the pad does not let up. On the other hand, it is known that just the generation sufficient @@ - don adhesion to plastic films such as polyester, polyether ester, Polycarbonate, polyamide, polypropylene, polyvinyl chloride and polyimide gans bosonders is difficult.

The production of good adhesion properties on substrates, e.g. for light-sensitive layers, this is done by wetting a suitable one Foil in sinon or more work steps with so-called substrate solutions, the an often complicated composition moussent around after the immediately following Drying process of the photosensitive layer to be applied enjoying adhesion to lend. The substrate solution normally contains a combination of liquids, which have a dissolving, swelling and non-loaond effect on the su bonetzende base film. In most of the cases a solid is still present. Is it about Gelatine, organic acids and hardening additives are still necessary. Beateth The solids made of synthetic polymer substances are often several work steps execute, depending on the chemical character of the folio with aggressive and toxic substances as solvents / swellers, e.g. trichloroacetic acid, phenols and Phenol derivatives, in other cases with strong acids or alkalis must be.

To achieve sufficient adhesion between the hydrophobic backing film and hydrophilic photosensitive gelatin layer are the same as those known heretofore procedure notait, the ObortlEcho of the foil to annul or to swell, so that the solid substance of the substrate solution has the opportunity,. enough in anchor to the underlay sheet. The solver / source / non-solver Syatem must then removed from the slide.

Forner is known from the patent literature, film supports made of polyether ester, Using polyester, polycarbonate, polypropylene, polyamide and polyvinyl chloride of adhesive substrates, e.g. chromic acid, chromic anhydride, trichloroacetic acid, contain chlorulfonic acid, phenol, cresol, phenol ester, nitrocellulose and peroxide.

Many of these subbing processes work in several stages, partly using radioactive bsw. UV radiation or in the ozone stream. The harmful one Effect of these substances or mentioned radiations and of ozone on the underlay film and the light-sensitive layers is known as well is the execution of several Operations disadvantageous with regard to the cleanliness of the finished film.

The process according to the invention described below provides some significant advantages over the known systems; it allows z. B. Work in sine work, use only a non-toxic, no distressing smelling liquid, does not need to use don systems solver / squalor-nonsolvent, no application of radioactive or UV radiation, brings koinê damage to the Auagangatolia, and increases the homogeneity of the backing sheet.

The working method according to the invention is not limited to the above ala Example orwahnto application in the film industry is noticeable. Rather, the aem Processes foils of all kinds, fabrics, fibers and the like. Subjected and so with increased tone Adhesive properties are provided. The treated materials are thereby z. B. denatured adhesion for emulsions and printing pastes, for example polyacrylamide, Polyvinylpyrrolidone and alginate, improved dyeability and the like. At the same time, an advantageous anti-tarnishing effect is achieved. The treatment## however, films and transparencies represent an essential case of application of the present invention Method. In the following description, therefore, "films" or "foils" are often used as the Talk, but with aonatige basic materials such as fibers, fabrics and the like. From the relevant Auadruck ala are also to be considered, is the subject of the present invention thus a process for the production of plastic films, fibers and-Gewebon with improved adhesion properties, which is characterized in that one a carrier material provided with a gelatine-free synthetic resin adhesive layer a temperature above the freezing temperature of the carrier material Subjects to heat treatment.

According to the invention, the anchoring takes place de adhesion-promoting Fast bodies in the film surface take place solely through the action of heat. The surface the material to be treated is loosened at the temperature used and is in a morphological transformation, because enough anchoring takes place.

For the present method suitable basic or.

Carrier materials are polyether esters, polyesters, polycarbonates, polyolefins such as polypropylene, polyvinyl chloride, polyamide types and polyimide.

The adhesive layer consists of one having the appropriate properties Synthetic resin; Copolymers with maleic anhydride have proven to be particularly advantageous, and mixed polymers of maleic anhydride and vinyl compounds are particularly preferred. Its suitable combination is based, for example, on a vinyl methyl ether-maleic anhydride copolymer.

Gelatien is unsuitable on conventional adhesive layer materials, as this is not applicable to the temperatures used in accordance with the invention ttaftung su bring and is also subject to incipient thermal degradation.

The heat treatment takes place in a conventional manner with heated Air. The duration of the treatment is not critical, but there are minimum periods of time of three minutes each proved to be expedient. You can add heat once or interrupt the heat treatment, e.g. a three-minute treatment in zoites of Divide three times a minute.

It turns out that after 1 to 2 minutes the adhesion still insufficient, but after the third stage it works well, although that with the adhesive layer material applied solvent evaporates within the first minute.

According to the invention, the warm obstruction takes place above the freezing pressure of the carrier material. Below the "freezing temperature", the also ale s softening temperature can be referred to, in the present description, temperature ranges are understood, which can be explained as follows: In the solid state there are amorphous thermal poles hard; the mobility of the Fadenomlekül e is frozen. With increasing temperature the stiffness of the Markromoleküllverbandes, and In the transition temperature range, the functionality and elongation change within a few Temperature degrees that can be set with the above ranges. One miserable When the temperature rises, one does not use the softening temperature range, if you measure when the temperature is falling, it is called the freezing temperature range, The upper limit for the temperature treatment according to the invention varies according to the invention Schmalzen the materials in question set. In general it could be recommended to work below the flow temperature (or the flow temperature range).

The optimal treatment temperatures can be set for each @rundmaterial easily ascertain as shown belowt olycu. tzrF3tb '. i r. xd e. he wa; . . arebn: n.

Treated temperature for about 5 minutes and then the adhesion opposite Gelatin emulsion tested: temperature nose dry without warmth unsatisfactory @ end unsatisfactory approx. 130 ° C insufficient insufficient approx. 140 ° C insufficient insufficient approx. 150 ° C insufficient good to adequate to sufficient or the like. 160oC, good enough to about 170 ° C good enough to sufficient very good approx. 180 ° C good to sufficient very good The twooioaUa rent temperature office thierecait170C.

If pollen is treated for 3 minutes, the following temperatures are obtained Proven to be useful @ polyether ester approx. 170 ° C polyester approx. 170 ° C polycarbonate approx. 150 ° C polyamide approx. 150 ° C polypropylene approx. 120 ° C polyvinyl chloride approx. 120 ° C polyimide (II) approx. 120 ° C.

The temperature treatment is preferably carried out within the crystallization area of the carrier material.

The adhesive layer is generally applied with a substrate solution, which the synthetic resin dissolved in a common solvent en @@ klt. After evaporation The heat treatment according to the invention is then performed on the solvent. The application of the Sutstrat can be done on erect or unjust material. It is preferable to spray onto stretched material. dries and then leads the Heat treatment. However, it is also possible to apply the adhesive layer to the unstretched @ round and @@@@@@@@, to @@@@@@ ingen, wor @@@ f in this case getrooknet and then in one operation the stretching and the inventive Heat treatment can be made. Instead of a substrate solution, the adhesion-promoting material can also be applied evenly in fine powder form.

The concentration of the adhesive used in the application of the adhesive layer Solutions is not critical. The concentration of solids necessary to achieve optimal adhesion is approx. 1-2% by weight. By means of a solution or suspension or by powder coating The amount to be applied must in any case be so great that a monomolecular one becomes Can form layer on the carrier material. Usually, however, larger quantities are used The method according to the invention leads to an improvement in the product quality or to films, fibers and fabrics with improved adhesive properties However, no tendencies to clogging show, such as block value checks with both sides subbed foils after de. known regulations. Besides that, too economic benefits achieved.

Reductions are made due to the one-step process, by recovery of the solvent used and on the basis of simplicity the heat treatment according to the invention.

So far used Bubstrier recipes are often so complicated composed that a recovery of the solvent is not possible, this However, it has been removed from the machine exhaust air through condensation or combustion have to. @is @ ier for necessary appliances are very expensive and cause their use ongoing, substantial Costs. Avoiding eventuallor healthier Damage de Maachinenperaonala also offers advantages that should not be underestimated.

81n disadvantage of the well-known subatriation systems for films is the occurrence of locally poor adhesion.

This defect has its origin in surface irregularities, which are caused by the production method of the Folle. Other irregularities occur through the well-known fact of loyal electrostatic differences. The proposed mode of operation overcomes these difficulties, as for example at a temperature of approx. 170 ° C for polyglyoclterephthalate a defined transformation takes place over the entire surface or the entire film substance, without any local preference and dependence.

Desgloichen does not find any local electrostatic at this temperature Landing more instead. The maximum rate of crystallization with polyglycol terephthalate is at a temperature of oa. 190 ° C reached, at a temperature @r of approx. 165 ° C the crystallization rate constant is about 2 5 of the optimum Worth. The temperature of approx. 190 ° C is the transition point for polyglycol terephthalate, at which the length of the crystalline long period changes from 110 A to 190 1.

Whether other Uroaoben or possibly aind, the success will be of attributed to the following process according to the invention: s The e for a polyester The treatment temperature of approx. 170 ° C described can be used at the beginning of a physical Period of transformation of the morphological system of polyglycol terephthalate gologists @t should be considered in a convenient location, which cannot be influenced under normal conditions. In order to the uniformity of the surface properties of the film is also given Is a prerequisite for uniform adhesion. All listed foil raw materials have the property that the content of crystalline increases with increasing temperature and amorphous fractions in the sense that with increasing temperature the kriatallinen Ante lower, the amorphous major. the increasing thermal movement of the molecules t @@ @@@ the loosening of the structure by solver and source can be compared and made possible the anchoring of the hydrophobic adhesive layer. Evidence for the described The process was easy to carry out: a polyester film coated according to Example 1 is first dried to remove the solvent at approx. 80 ° C and then exposed to heat treatment at approx. 170 ° C for long periods of storage at normal temperature. The adhesion test after the first step erg & b Meder wet or dry adhesion, after the heat treatment, wet and dry adhesion are good.

An advantageous implementation of the method according to the invention consists in the following: the application of the subatrate solution and the application according to the invention Turns on heat treatment for a storage time at 20 ° C.

Daduroh Can the whole process be divided into two independent workflows divide up what can be of importance from a machine-technical point of view, e.g. in a machine only coated, not heat treated, or the heat treatment only for a certain one slower speed than the subbing can be made. At gendgend long heat zone are speeds of approx. 18 m / min. achiever. d @ the process not tied to exposure times of lpsern and swellers, nor from removal same dependent iat. Only the time of exposure to heat is decisive, whereby su beaorkan is that the warm-up time @ the foils xxxxx depending on the used Strength / and the evaporation time of the solvent are short.

The present invention will be further elucidated by the following supplement See example 1; Approx. A4 sized piece of a stretched polyglycol terephthalate film in the strength ven approx. 100 m. is in a solution of 2 g vinyl ethyl ether-malic acid anhydride copolyer, 100 grams of Acsteon soaked and at approx.

70 - 100 ° C freed from solvent. then the polie a heat treatment of @ minutes at 1700.

The foil treated according to this method has a good dry adhesion and wet or developer adhesion to a gelatinous emulsion.

Example 2: Stretched polyglycol turephdhalate polie in the strength of approx. 125 mU is in a Löoung a. including 2 grams of vinyl methyl ether-ma.luinear anhydride copolymer, 100rAootone immersed and subjected to three heat treatments of approx. 1 minute each at 170 ° C, whereby the film assumes normal temperature during the two interruptions.

Unchecking of gelatine emulsions showed the following Values ! Adhesion Zoi, ......!? Po '' *. 00 "" s 1 x approx. 1 minute 170 ° C insufficient insufficient 2 x oa. 1 minute 170 ° C insufficient insufficient 3 x approx. 1 minute 170 ° C good example @@ Mine polyether ester film - stretched film made of terephthalic acid diglycol ester - p-oxybenzoic acid coconde mat (9 @ 1) - with a strength of approx. 100 mu is converted into a solution immersed in 2 grams of vinyl methyl ether-maleic anhydride copolymer and 100 grams of Acoton and then exposed to heat treatment at 170 ° C for 3 minutes.

The rafting compared to Gelstinesmulsicenen is wet and dry euto A so-benadeleite foil is also written on with black ink. The ink cannot be removed by intensive rubbing with the fingernail.

Example 4a @ Sine stretched polyglycol tersphthalate film in starch of approx. 100 mu is converted into a solution of 2. iiry. c: hJ 1 4tn r-,. ; ~ rL r. . ryriri - v r. l;, a tci 100 gr Aoeton getsucht and and @ hil @@: @ s @ nd @ Min @ ten land one n @@@ ebuhandlung from 17 :)% @@@@@@@@@@@@@.

The attitude towards: @@@@@@@@@@@@@@@@@@@@@@@ and Druckpaston @st nose and dryness good.

For comparison, a @@ gender experiment was carried out: about DIN A4 large stick direr @ straight polyglycol terephthalate film in the thickness of ce. 100 @@ is converted into a solution of 2 g vinyl @@@@ thyl @@ -ther-maleic acid anhydride copolymer and 10 @ gr acetoin dipped and left to dry at approx. 20 ° C. The Nans and Trocan attachments @ ogenüber Geltinoemulsion sit ung @@ uügen @, Example 4b: An approx DIN 4 A large piece of a stretched poly. ester film made from the polycondensate of Terephthalic acid and 1,4-dihydroxymethylcyclohexane in a strength of about 100 mU in a solution of 2 g vinyl methyl ether-maleic anhydride copolymer and 10U gr Acoton dipped and then subjected to a heat treatment at 170 for 3 minutes C exposed.

The adhesion to oil emulsions is good and trooken.

Example 5: An approximately DIN A4 sized piece of unstretched polycarbonate film from a polycondensate of 4,4'-dioxydiphenyldimethylmethane and phosgene in the Strength of approx * 100 mU is dissolved in a solution of 2 grams of vinyl methyl ether-maleic anhydride copolymer and 100 gr methyl-ethyl-ketone dipped and anechlieaaend for about 3 minutes Subject to heat treatment at 150 ° C. The adhesion to gelatin emulsions is wet and dry good.

Example 6: A stretched polyamide 11 film made from the polycondensate of # -amino-undecanoic acid in the strength of about 100mU is in a Löoung of 2 g vinyl methyl ether-maleic anhydride copolymer and 100 gr of acetone dipped and then oa. For 3 minutes exposed to a heat treatment of 150 ° C. Adhesion to gelatin emulsions is nses and trooken good.

Example 17s A stretched polyamide 12 film made from the polycondensate # -amino-dodecanoic acid in the strength of approx. 100 mu is in a solution of 2 gr vinyl methyl ether-maleic anhydride copolymer and 100 gr acetone dipped and then approx.

Heat treatment at 150 ° C for 3 minutes.

The adhesion of goeenuber gelatin emulsions is good wet and dry. pep), St Bine stretched olypropylene film in the 8th thickness of approx. lu0 mu is in a Solution of 2 grams of vinyl methyl ether-maleic anhydride copolymer and 100 grams of acetone immersed and then subjected to a heat treatment of 120 ° C for 3 minutes. The ventilation against gelatine emulsions is sufficient when wet and dry.

Example 9: a piece of stretched polyvinyl chloride film about DIN A4 in size in the strength of 100 mU is in a solution of 2 g vinyl methyl ether-maleic anhydride copolymer and 100 g of aoeton thawed and then heat treated for 3 minutes exposed to 120 ° C. Liability versus gelatin emulsions lot haoo and trooken enough.

.

Example 10: A polyimide (H) film made from the polycondensate of pyromelliteal anhydride and an aromatic diamine in the strength of approx. 25 mu is in a solution of 2 grams of vinyl methyl ether @ aleinsäureanhydri @ copolymer and 100 grams of acetone dipped and then subjected to a heat treatment at 120 ° C for 3 minutes. Liability compared to gelatin emulsions, wet and dry are good.

Example 11: A greckto polyglycol terephthalate film in thickness from Os. 76 mu is converted into an idaung of 2 grams of vinyl methyl ether-maleic anhydride copolymer and 100 Kr acetone dipped and repeated for a treatment at 170 ° C for approx. 3 minutes each long exposure, keeping the film between each heating interval cools down to normal temperature. The Naaa and dry adhesion to gelatine emulaions Lot in all PUllen good.

Example 12s Stretched polyglycol terephthalate film in the thickness of Approx. 100 mu is in aine Ldoung of 2 g vinyl ethyl ether-maleic anhydride copolymer and 100 grams of acetone dipped and exposed to heat for about 3 minutes at 170 0C switched off.

Example 13: Stretched polyglycol terephthalate film in the thickness of 100 mU is added to a solution of 2 grams of vinyl-2-chloroethyl-ether-maleic anhydride copolymer and 100 gr of acetone dipped and exposed to heat at 170 ° for about 3 minutes C exposed.

BeiMi.l14 Gereokto polyglycol terephthalate film in the StUrko of 100 mU is dissolved in a solution of 2 g vinyl isobutyl ether-maleic anhydride copolymer and 200 gr of acetone and dipped for 3 minutes under a heat effect of 170 ° C.

Beiauiel s Cureokte polyglycol terephthalate film in the thickness of 100 mu is in a solution of 2 g vinyl acetate-maleic anhydride copolymer and Dipped 10 () gr acetone and exposed to heat at 170 ° C for 3 minutes.

Baippet6t Gereokto polyglycol terephthalate film in the thickness of approx. 100 sU is added to a solution of 2 g vinyl chloroacetate-maleic anhydride copolymer and 100 grams of acetone immersed and exposed to heat for 3 minutes auootzt at 170 ° C.

With the products gomäaa examples 12 to 16 aind wet and dry adhesion very good compared to gelatin amulaion and printing patents.

The following experiment was carried out for comparison; An oa. D1N A 4 large pieces of stretched polyglycol orephthalate film with a thickness of approx. 100 mu is in a solution of 2 g vinyl chloroacetate-malsic anhydride copolymer and 100 gr Aoston dipped and left to dry at 20 ° C. The wet and dry adhesion compared to oilatine emulsion is insufficient.

Example 17: A piece of stretched polyglycol terephthalate film about A4 in size A coronary discharge is exposed to a strength of approx. 100 mU and then in a solution of 2 grams of vinyl methyl ether-maleic anhydride copolymer and 100 grams of acetone immersed and subjected to heat treatment at 170 ° C for 3 minutes. Liability compared to a gelatin emulsion, it is very good in the wet and dry.

For comparison, the following experiments were carried out a) A cae DIN A 4 large piece of stretched polyglycol terephthalate film with a thickness of approx. 100 aU becomes one Coronary discharge suspended and then benched with a gelatin emulsion. No liability whatsoever can be registered. b) A piece of stretched polyglycol terephthalate film about DIN A4 in size in the strength of approx. 100 mu is subjected to a coronary discharge and then into a Solution of 2 grams of vinyl methyl ether-maleic anhydride copolymer and 10 grams of acetone dipped and troubled. The adhesion to a gelatin emulsion is quick and easy dry completely insufficient.

Example 18: A case DIN A4 large 9tUok of a stretched polyglycol terephthalate film in the strength of approx. 100 mu is in a solution of 2 g vinyl methyl ether @ aleic acid anhydride copolymer and 100 gr of acetone dipped, the solvent allowed to evaporate at 20 ° C and after short storage for 3 minutes heat-treated at 170 ° C. Wet and dry adhesion are good.

Beiapiel19i Stretched polyglycol terephthalate film in the thickness of approx. 100 mu is in a solution of 2 g vinyl chloroacetate maleic anhydride copolymer and 100 grams of acetone dipped in the loaunga agent and left to evaporate at approx. 20 ° C and heat-treated for 3 minutes at 170 ° C after short storage. The wet and dry adhesion is good.

As the above examples show, a prolonged one deteriorates or repeated heat treatment will not affect the adhesion result. Shorter treatment times On the other hand, they are only possible to the extent that the desired * surface changes are made It also showed that there was a further improvement in adhesion the heat treatment is possible if the backing film before wetting a electrical pretreatment (corona discharge) is subjected to.

Claims (8)

P t c n t a n s p r U c h e ********************************************** 1. Process for the production of plastic films, fibers and fabrics with improved Adhesion properties, characterized in that one with a gelatin-free Kunsthars-Haftachicht worohonos carrier material at a temperature above the freezing temperature The temperature of the carrier material is subjected to a heat treatment. 2. Verfahron according to claim 1, characterized in that the adhesive layer from copolymers with maleic anhydride content. 3. Verfahrsn according to claims 1-2, characterized in that the Adhesion includes copolymers including maleic anhydride and vinyl compounds consists. 4. The method according to claims 1-3, characterized in that the Heat treatment at a temperature below the flow temperature of the carrier material Temperature takes place. 5. The method according to claim 1, characterized in that one subbed Films, fibers or fabrics made of polyether ester, polyester, polycarbonate or polyamide subjected to a heat treatment at 150-180 ° C. 6. The method according to claim l, characterized in that one subbed Films, fibers or fabrics such as polypropylene, polyvinyl chloride or polyimide Subjected to heat treatment at 120-150 ° C. 7. Verfahron naoh one of the preceding claims, characterized in that that the treatment time is at least 3 minutes. 8. The method according to claim 7, characterized in that the duration of the exposure the heat treatment divided into several Hinzelperiods let.