DE1720106C3 - Collagen-based coating compounds for the production of self-adhesive coatings on any substrate - Google Patents

Description

crystalline collagen salt - produced by loading The used according to the invention, in water

treatment of collagen with an aqueous acid- 65 insoluble, microcrystalline collagen salt, which in solution at a pH of 1.7 to 2.6 and in colloidal form consists of bundles grind the hydrolyzed material thus obtained combined tropocollagen units, their until at least 10% of the particles have a size between the length of the individual tropo-

collagen unit and can be up to 1 μ and coatings are self-adhesive and depending on the type of diameter between 25 and a few dogs, the substrate on which they are applied can be used for a wide variety of purposes. When using the coating according to the invention, such a coating is, for example, a processing compound for the production of coatings. and to damnSegende KoUagen-VememingsmiUeln like ζ. Β Alum, tensile surface of the substrate protects against oxidation, is used to give the coatings made from it, but it can also be a decorative layer to give particularly high wet strength or one that is used as an adhesive for numerous purposes A very good layer between fibers and a non-woven fabric is useful before using the acidic basic structure, such as paper, or as an intermediate dispersion of the water-insoluble, micro-layer for coating substrates with crystalline collagen salt in water Substances such as B. photosensitive hold free greasy materials as far as possible coatings on photographic films or Pa-Hch are removed therefrom. This can thereby be used, can serve or only a change can be achieved that cellulose fibers in the form of a smoothness of the substrate surface should be brought about
heavily bleached wood pulp for kraft paper or The inventive collagen-containing coating microcrystalline colloidal cellulose mixed in is suitable for the production of overgrowth in order to distribute the cellulose material within the trains that are evenly distributed on many substrate surfaces except collagen salt dispersion, ao quite good harder, and for specific ones By subsequently filtering the dispersions, the known coatings are far superior in many ways, for example using a conventional aspect. Thus, for example, the pressure filter method is conveyed using the invention, in hydrogen or cellulose layers between correspondingly insoluble microcrystalline colloidal collagen salts and perforated metal plates, which are used in accordance with the invention The paper fibers contained in the starting material are applied to these natural fatty materials. In another way, paper coated with a high wet strength method for reducing the content of those paper which is between 20 and 25 »/ 0 of the dry strength of the greasy materials to a minimum. By using a small amount of raw, undried animal hides with organic amounts of a collagen crosslinking agent, the liquids that can dissolve greasy materials can increase the wet strength of the paper up to 25 to 40 ° of such. B. acetone, leaching or the dispersion dry strength of the paper can be increased, under very high pressure through filters made of cellulose If the microcrystalline colloidal collagen salt as paper or tissue to be pressed. This filtration additive used to improve the wet strength also serves to reduce any small quantities that may be present. It can be produced in situ. In terms of other impurities, such as. B. Hair in this case, the shredded collagen starting or meat residues, which in the end product un- material, such as z. B. the skin substance are treated with a suitable amount of acid that is desired to be removed therefrom, and the skin substance impregnated with the collagen-containing coating according to the invention is mixed with the paper pulp for the production of coatings * °. The mixture is then subjected to a wide variety of comminution to a large extent under normal conditions in order to use the solid substrates. It is suitable for converting material into a product with colloidal particles, in particular for coating materials that are large. For this purpose, one can be solid at normal room temperature, e.g. B. conventional grinding device, as it is normally used for stone and other mineral materials in 45 grinding (comminution) of paper pulp in the form of fibers and in the form of is produced therefrom, are used.

th webs, masonry, plaster, glass and other Preferably, however, an aqueous dispersion of ceramic materials, metals, natural and the microcrystalline synthetic polymers used according to the invention, such as wood, wood fibers, colloidal collagen salt and the and other cellulose fibers and pulp from such 50 are prepared beforehand Structures in the form of webs made of fibers at any stage of production, added before they get into the grinder or the paper, paper products, cork, cotton, ramie, shredding device or in the headbox of flax and other natural cellulose fibers, paper making machine. For the back-synthetic cellulose materials, such as recovery of the macellulose, cellulose esters and cellulose ethers contained in the white water in the form of materials, the rinsing liquids of the first of fibers, threads, films and other form counter rinses can be reprocessed.
stands. Further Examples of Suitable Natural It is extremely surprising that the polymers are protein-containing substances in the form of collagen salt, which in itself have a relatively low level of wet leather, fibers, film, animal hair and gelatin. When used in a fibrous form for suitable organic polymers, paper has a wet strength of 20 to 25% methacrylates, polyesters, polyamides, polyolefins, which impart dry strength to the same. This has to do with polyvinyl resins, polycarbonates, and polyurethanes, obviously with the fact that, when mixed and synthetic elastomers and rubbers are mixed, they bond very firmly to the fibers and, for example, in the form of fibers, non-fibrous or thereafter extremely adherent . After the dry fibrous webs or films as well as other forms of the paper, the collagen salt is opposite to bodies. Relatively insensitive to water. The wet strength of the product can be increased by adding a small amount of a collagen-crosslinked-collagen-containing coating compound produced using the inventive method

up to a value of 25 to 40 ^c . the dry linem colloidal collagen salt in water is suitable

strength of the product can be increased. for the production of greaseproof papers. Gels with

The collagen salt used in accordance with the invention and formed in water at a concentration of only 1%

Insoluble, microcrystalline, colloidal collagen salt which on paper has a continuous fat density

not only improves physical properties 5 coating only 0.098 mm thick. This over-

The trains from collagen-containing fiber slurries exhibit excellent adhesion to the

manufactured products, but also has the radio paper substrate on it, are very flexible, strong and

tion of a dispersant. The thereby obtained permanently. You won't be handling it

Products have a very even distribution of brittle and are therefore ideal for the

of the individual fibers, it being sufficient if io the intended purpose.

only 0.5% by weight of the microcrystalline collagen. salts, based on the weight of the fibers, as the collagen salt dispersions or gels can also Dispersants for synthetic fibers, e.g. B. with conventional coating pigments and weighting polyamide fibers and polyester fibers, as well as of substances such. B. calcium carbonate, for production natural papermaking fibers into which the mill 15 of coated papers are mixed. the paper manufacturing plant. Coatings produced in this way have a This low level of collagen salt particles gives excellent adhesion and gives good support the prevention of fiber printable surfaces.

agglomerations which are suitable for polyamide fibers in the coating composition according to the invention

the conventional papermaking a particularly »o is not only suitable for the coating of fibrous

pose a serious problem. Railways, but also for the production of

The wet strength of the applied films is excessively low according to the intermediate coats or adhesion, although they are not suitable for the application of continuous film dipping and long-term residence in water. B. wet strength cellulose films, as the dissolve thereon. When immersed in water, water as from manufactured coatings is absorbed on the cellulose substrate and the film swells somewhat; it adheres excellently to the wet-strength and then stable in the swollen state. The wet strength trains, such as B. nitrocellulose coatings, applied speed can be increased by the fact that one can also firmly adhere to the collagen coating according to the invention according to the invention.
Admixing crosslinking agents. Such cross-linking points produced using the agents according to the invention can be added to the gel at any time before the coating of the substrate containing collagen-containing coatings. Substrate are applied, for example under

A more homogeneous distribution within the use of dip-coating, knife-based products is, however, achieved if the spreading and rolling-on devices. Although they have a wetting agent right at the start of the crushing high viscosity, the viscosity can be added by phase. Examples of satisfactory application of high shear forces very quickly reduced effective crosslinking agents are the various so that the colloidal salt dispersions, which look like formaldehyde-based crosslinking agents such as urine-stiff gels, are easily carried in the form of films of material-formaldehyde precondensates and melamine-40 be able. In addition, the er-formaldehyde precondensates, formaldehyde, glyoxal, inventive Beschichtungsm '"sen with stirring acetaldehyde, glutaraldehyde, potassium alum, chromium be heated to 8O ⁰ C, alum to its viscosity, to reduce iron alum, basic aluminum acetate, cadmium and to facilitate the application in the form of a mium acetate, copper nitrate, barium hydroxide and layer on a substrate,
water-soluble diisocyanates. The coatings produced using the specific crosslinking agents according to the invention are based on the intended use, to which the end product has the advantage that it is to be supplied from a natural protein source. The crosslinking reactions are derived so that no additives of toxic components are required during their production. This moderate heating is also then of 50 and therefore no problems with regard to the Toxi advantage, if higher concentrations of micro- city of the coatings or the resulting crystalline collagen salt are used, since allergies occur. The coatings produced according to the invention, which are somewhat reduced in the viscosity of the dispersion, are edible and can therefore be set. Under no circumstances should temperatures of more than 90 ° C be used in conjunction with food when driving while driving. As the complaints according to the invention. processing masses at a very low solids concentration

By using crosslinking agents, films can be formed, making it possible to work on extraordinarily

nen coatings with wet strength of up to 50 0/0 the most economical way to produce coatings what

Dry strength of the coatings can be achieved. In numerous technical applications of the

Use of certain crosslinking agents brings about 60 inventive collagen-containing coating

There are also additional advantages to the extent that it plays a major role.

by also improving the heat resistance. The microcrystallity used in the present invention the coatings can be achieved. Namely, it is line, colloidal collagen salt can be made beforehand possible the shrinkage when heated as well as and by adding the growth of bacteria the resistance to discoloration can be made storage-stable by inhibiting agents. Turning of certain crosslinking agents clearly on In this regard, compared to other mate improvements, materials, especially in relation to wet strength

The dispersion of microcrystalline sets according to the invention, essential advantages.

7 8

The invention is further illustrated by the following examples of collagen salt in this type of use explained. The parts specified therein are coated on at least part of the fibers and then as ias weight based. Binder acts between the fibers. At the Her

Standard paper laboratory equipment was used to prepare the samples. The examination of the papers took place

. . according to the standard procedures of the technical association

^{Bei iel} P ^L of the Pulp and Paper Industry (TAPPI).

In the various examples there were 360 parts

A mixture of 10 parts of ground, frozen fibers slurried to a consistency of about dried skin collagen and 1000 parts of a 10 1 "/ o in a laboratory paper mill and 0.01N hydrochloric acid solution was mixed in a mixer using a for 6 minutes Apply 5 kg base coat by high shear force for 15 minutes at 25 ° C. The base coat was removed and mixed up. This gave a stable gel with a slurry finely ground for about 2 minutes. The apparent viscosity of 42,000 cP. To 750 parts of the slurry, about 10 parts of gel were added with 250 parts of isopropanol, 15 parts of alum were added to bring its pH to about 5, and the mixture was brought into the above for 20 minutes and grinding was carried out for 5 minutes Mixer mixed. This dispersion contained continued. Thereafter, a sufficient amount of 0.75% collagen and had a viscosity of a 2% microcrystalline collagen salt disperser-5600 cP. It was added 1 ⁰ O of the weight of the collagen sion in order to add the desired amount of microeines conventional melamine-formaldehyde resin or crystalline collagen salt, based on the weight of precondensate. the pulp. The microcrystalline

Collagen salt was produced by treating freeze-dried technical skin collagen with hydrochloric acid, as described above, and the application _{example 1 a5} mixture for about 15 minutes at 25 ° C. in one

High shear mixer.

If necessary, the pH value of Aufspiel 1 in the form of an approximately 0.013 mm thick layer of slurry was then adjusted to 5, and the fine was applied to 9 kg quality bonded paper. grinding was continued for 5 minutes. The mixture then spread out well and adhered evenly. Samples of the slurry were taken to determine whether it was moderately strong. The coated paper was produced at the usual hand samples. These were pressed at 21 ° C. and 50% relative humidity on a pressure of about 3.5 kg / cm ² , dried and cured around a smooth, flat surface. remove excess water, and 10 minutes the paper retained its original shape, long at a temperature of 121 to 135 ° C, distortions were not visible. 35 dries. In some of the examples a

The coated paper produced in this way had a melamine-formaldehyde precondensate and an acidic, glossy surface and an excellent fat-reacting catalyst (zinc nitrate). In impermeability. A drop of vegetable oil applied on the table below is the proportions of the surface, after a condensate and the zinc nitrate as percentages of the half hour at room temperature, gave no indication of the microcrystalline collagen salt,
detect penetration into the coating. With the in the application examples 2 and 3

repeated bending did not cause any cracks in the coating. The fiber was a very fine wood pulp, which the absorption and subsequent spreading as pulp to be chemically processed processing of ink applied to the surface is referred to under and in the production of PolyKontrolle held. +5 amide is used.

The fibers in Application Example 4 were produced by defibrating packing paper.
Example 2 ^ ^e fibers i ™ application example 5 passed

made of unbleached packing paper pulp.

A mixture of 750 parts of 0.01 N hydrochloric acid, 50% by weight of the fibers used in Application Examples 6, 7 and 8, 247 parts of isopropanol and 3 parts of 30% by weight of ge-formaldehyde 30 parts of freeze-dried foldable wrapping paper pulp and added to 50% by weight of skin collagen, and the mixture was mixed with polyamide fibers of 32 mm length and 1.5 denier in a mixer for 15 minutes. In these examples, the pulp was first in the stable Get gel. The temperature of the Mi- 55 paper mill was milled and the polyamide fibers during the dispersion were kept below 30 ° C that was added during the first fine milling. This gel was prepared according to a conventional method. In application example 9, the fibers passed

loan spraying on paper sprayed, and 85 wt ° / _e of polyamide fibers of 6.4 mm length to obtain a fettundurchlässiges glossy paper. and 1 denier and 15% by weight 6.4 mm long

60 acrylonitrile / vinyl chloride fibers. In this example

if there was no paper mill grinding, the fibers

. were merely finely ground, and the mill was

Application example 2 to 9 used _only ^ _1n mixing to get the fibers in the Thoroughly distribute slurry. The beginning

These examples show the production of fiber slurry - no alum was added products made with dispersions of a water-insoluble The composition of the hand samples and the

Borrowed, microcrystalline collagen set coated physical properties are in the following became. It is believed that the colloidal Table I indicated.

( 9 I. Fibers micro- 7 20 106 10 tensile strenght dry Tear resistance Burst Krist.
Callous
salt in kg / cm 2.80 was in g strength
in kg / cm ⁸ table (V ») wet 1.80 dry dry To whom-
diincs- Soluble pulp 5.0 MeI- Zn (NOj) ₂ 1.5 5.95 60 3.85 example
No. Soluble pulp 5.0 amine
Shape-
aldehyde 0.84 2.45 145 2.45 Wrapping paper 5.0 (Vo) (Vo) 2.1 1.05 130 8.40 2 Unbleached
Wrapping paper pulp 2.5 _ 0.56 1.50 55 3.22 3 50 ° / o bl. Wrapping paper pulp
50% polyamide 7.5 20th 2 0.28 1.26 200 1.75 4th the same
1 y 10.0 - - 0.49 1.75 120 2.00 5 the same 7.0 15th 1.5 0.455 240 2.24 6th 15% acrylonitrile /
Vinyl chloride 5.0 - - 0.49 230 7.00 7th
Q 85 «/ ο polyamide - - 8th 20th 2 9 - -

Application example 10

Polyamide fibers of 1.5 denier and 32 mm in length were placed in a laboratory paper mill at consistency finely ground by about 1% for about 15 minutes. The obtained slurry became Hand sample scooped. In the same way, further polyamide fiber films were finely ground in a paper mill and at the end of the milling process, a sufficient amount of a 2% dispersion of microcrystalline collagen salt is added to each 2.5%, 5.0% and 10.0% collagen salt, based on the weight of the fibers, to be incorporated into the mixture. Hand samples were drawn from these various mixtures. The composition of the Samples and the respective physical properties are recorded in Table II below.

Table II

sample

A.
B.
C.
D.

Microcrystalline Collagen salt

Ream weight in kg

2.5

5.0

10.0

Tensile strength in kg / cm *

wet

dry

no measurable strength values 20.86 0.27 0.014

21.32 0.43 o! Oi4

20.86 1.05 0.110

Tear resistance in g

dry

183
189 160

Berstt'estigkeitin kg / cm ^etc.

dry

0.35
0.70 3.36

Application example 11

A mixture of 50% polyacrylonitrile synthetic fibers (6.4 mm fibers), 50% polyamide fibers (6.4 mm fibers) and 10% microcrystalline collagen salt was placed in a laboratory paper mill at a Fiber consistency of 0.2 / finely ground. As in Application Examples 2 to 9, the microcrystalline collagen salt was added as a dispersion. the Slurry became a after adjusting the pH on a Fourdrinier paper machine Processed surface weight of 9 kg, and the resulting web was then passed through a bath, containing a formaldehyde-based crosslinking agent. The paper was then dried and cured. The product worked well as an insert for

55

6 "

6 « Tissue and similar uses where high Keiflfesugkeiten are desired.

Application example 12

A wet, non-fibrous cellulose film was ^eme v ^ & e, 1% water-insoluble, micro-coagensalt containing dispersion. ^ ⁰ * "Tanadi to form a self-adhesive on the substrate KoUagenuberzugs The dried uispersKm the microcrystalline Kollaeensalzes 22L ^ ¹¹¹ A ¹ Application Examples 2 to 9 forth ni α JiT ^Kolla gensalzmenge fluctuated between 0.1 and 0.3 · /. the weight of the substrate. W? Η °° ^ ΐϊ? "* Fflm prepared from the microcrystalline collagen salt was then

Liches, waterproofing nitrocellulose lacquer bath passed and dried. The nitrocellulose layer adhered better to the collagen coated film than did the uncoated film was.

Microcrystalline colloidal collagen is superior to gelatin as an adhesive for non-fibrous cellulose films, because it has a higher molecular weight, it is used in amounts which are only 20% that to be used Gelatin, and in the heat has a greater resistance to flow; Consequently it leads to a stronger, more continuous coating and better adhesion as well a more flexible film than gelatin.

Application example 13

A coating of a 10% dispersion of microcrystalline Collagen salt according to Application Examples 2 to 9 was applied to the using a doctor blade Surface of a non-dried web or a wet gel film made of regenerated cellulose. Another non-dried web or a wet gel film made of regenerated cellulose was applied the layer applied to form a laminate which dried between smooth, heated printing plates would. This structure was clear and transparent; the two webs or films adhered firmly to each other.

A similar, clear and transparent laminate made of regenerated cellulose was created by substitution Made from two sheets of uncoated, dried, regenerated cellulose.

Example 2

An 8 ° gel of microcrystalline collagen salt was prepared by treating ground, freely dried technical skin collagen with a mixture consisting of 25% isopropanol and 75% dilute hydrochloric acid, and the total mixture was mixed for 15 minutes at 25 ° C high shear mixed. The gel was then ^{heated to 80 °} C., and the ends of a row of bottles, closed with screw caps, were dipped into the gel.

The bottles that had received the coating then passed through a forced air oven. Upon drying, the microcrystalline colloidal collagen formed a thin, transparent layer that adhered to the bottles and sealed them hermetically. The coatings could be broken open by cutting open the lower edge of the screw cap, after which the caps could be twisted off.

Application example 14

A gel of the type described in Example 2 was sprayed onto eggs, apples, carrots, tomatoes and cucumbers. As it dried, a thin coating of microcrystalline colloidal collagen formed a protective film on the food. This film could be removed by soaking the food in warm water and brushing it off before the food was consumed. However, microcrystalline colloidal collagen is edible and does not need to be removed. In the case of the Moors, the coating sealed against oxygen and the natural carotene color was retained even after long periods of storage. The microcrystalline colloidal collagen additive added strength to eggs, which reduced shipping and handling breakdowns. The coatings also reduced the amount of moisture lost on storage.

Application example 15

ίο A silver-plated teaspoon was turned into a l ° / oig < Dispersion of the microcrystalline collagen salt immersed and air-dried. The covered " Spoons and an uncoated spoon were placed in a hydrogen sulfide atmosphere. Dei uncoated spoons began to tarnish after about 5 minutes; the coated spoon showed 20 minutes long no trace of a run-up.

Application example 16
ao

20 g of finely chopped cow skin, freed from water by freeze-drying, was placed in 1980 ml of hydrochloric acid solution placed with a pH of 2 and be; 25 to 30 ° C in a grinder for 15 minutes:

as 5400 rpm, comminuted with a 10 cm blade.After completion of the comminution, the 10% gel of the microcrystalline collagen salt was spread on a freeze-drying dish on which it formed a 3 mm thick layer, and freeze-dried overnight (-40 up to - 50 ^c C, 5 micron vacuum heating cycle not above 30 ° C with condensation of the sublimed water at 60 ° C). The product obtained was a 3 mm thick mat which absorbed 65 times its own weight in water. The tensile strength of a dry test strip 25 mm wide was 1.6 kg; the tensile strength in the wet state was quite low for the same test strip, but was still measurable. The product did not disintegrate when soaked in water.

«O A dried, crushed collagen hydrochloride or amine salt, such as B. a crushed, freeze-dried mat of the type described was crushed in water to form a gel containing 1 "o microcrystalline collagen salt. One side of a 12 mm thick mat was coated with the gel and a second mat with the coated side After this layered structure had dried, the mats could only be separated from one another by tearing the mats Crosslinking agent in the coating gel

be decreased.

For the production of photographic films, plates or paper, the light-sensitive The material was dispersed in gelatin and the gelatin was applied to the desired support

In another embodiment of the invention, the microcrystalline collagen salt in these photographic emulsions can completely or partially replace the gelatin. It was found to be about 1 part microcrystalline Koflaeensalr 10 parts ohntoW- phical gelatin. It follows that significantly thinner coatings can be produced, which results in an improved resolution of the photographic image. Unlike gelatin that

is a breakdown product of tropocollagen, tropocollagen is insoluble in neutral water and dissolves but in certain salt solutions and in dilute acid at a pH of about 3. The layers from microcrystalline colloidal collagen according to the invention are more dilute in water and in solutions Acids with a pH value of 3 are insoluble, but absorb water and form highly viscous gels, which can be combined with the conventional components of photographic emulsions and permit the manufacture of photographic films and papers superior to those made from gelatin are.

It is not absolutely necessary to prepare the microcrystalline collagen salt beforehand. It can in situ in the course of the photographic emulsion preparation process.

Photographic emulsions generally contain small amounts of substances such as alum, the is a crosslinking agent for gelatin. These substances can also be used in the production of emulsions using microcrystalline collagen salt to partially or completely replace Gelatin can be used. The crosslinked product is slightly less responsive to water than the non-crosslinked one Product. As with all forms of collagen, all common crosslinking agents can be used be used. The silver halide acts as a crosslinking agent to some extent. Besides that represent substances such as aldehydes, melamine-formaldehyde condensates, water soluble diisocyanates and long chain fatty acids, also satisfactory crosslinking agents represent.

Representative examples of photographic emulsion coatings made in accordance with the present invention will be given described below.

Application example 17

20 g of potassium bromide and 20 g of citric acid were dissolved in 90 g of water, and 7.5 g of photographic gelatin was admixed with the salt solution. The mixture was then heated to 50 ° C to dissolve the gelatin, and then cooled to 30 C ^c.

25 grams of photographic grade silver nitrate (free of copper, mercury and organic impurities) was dissolved in 175 grams of water at 30 ° C and just enough ammonium hydroxide (20 ml) was added to redissolve the silver oxide.

The silver nitrate solution was added to the potassium bromide solution at 30 ° C; the mixture was digested with vigorous stirring for 10 minutes and then poured into a solution of 7.5 g of gelatin in 30 g of water. The temperature of the mixture was raised to 50 ° C and digested for 10 minutes. It was then poured into a porcelain bowl surrounded by ice to solidify the emulsion. The gel was crushed, placed in a clean cloth bag and hung in cold running water (temperature 15 ° C) for at least 1 hour. The washed gel was melted at 40 ° C, and at this temperature 100 ml of a microcrystalline collagen salt dispersion were added , followed by 26 ml of ethanol and 1 ml of a lOf'oigen chromium alum solution. The microcrystalline collagen salt was made from ground, pre-dried cowhide that had been leached with ether to remove the lipoids. The colloidal salt dispersion was prepared by comminuting the collagen in a citric acid solution in a Waring mixer for 15 minutes.

A conventional gelatin photographic mix was prepared in the same manner as however, it differed from the above mixture in that instead of adding the dispersion ίο of the microcrystalline colloid a solution of 23 g Gelatin in 80 g of water was added to the washed gel.

The analysis of the emulsions was as follows:

Inventive hereditary conventions borrowed
Mix mix

Gelatine (photographic quality) ... 15 g 38 g

Microcrystalline collagen salt .. 1.5g -

Water 395 g 375 g

Potassium bromide 20 g 20 g

Silver nitrate 25 g 25 g

Citric acid 20 g 20 g

Ethanol 28 ml 28 ml

Chrome alum (10 ⁿ / o solution in
Water) 1 _m il ml

Conc. Ammonia 20 ml 20 ml

It should be noted that 1.5 g of microcrystalline

lines collagen salt and 20 g of water as equivalent to 23 g of photographic gelatin in the above Mixture were used.

The finished emulsions were applied to heavy weight paper and dried to make paper for

to make pholographic prints. A comparison between the papers produced with the coating composition according to the invention and the papers produced by conventional processes showed that the emulsion layer with microcrystalline collagen salt was significantly thinner than that of the comparison sample. The film was stronger, more flexible and more abrasion resistant. A comparison between the proofs produced by projection printing of the same negative and those produced by conventional processing

showed better resolution and more faithful reproduction of the negative treated according to the invention than standard paper.

In those cases where all of the photographic gelatin is replaced by microcrystalline collagen

salt has been replaced, it has been shown that the collagen salt, which is used in the potassium bromide-citric acid mixture! is added, must have a noticeably higher collagen salt concentration, e.g. 8 to 10 "/ 0 an excretion or precipitation of the collagen

to prevent salt.

An alternative method is the production of the microcrystalline collagen salt in situ, which is carried out by the following example is explained.

Application example 18

Ground, pre-dried cowhide was extracted with ether for 1 hour to remove the lipoids.

15 16

leached and then dried at 35 ° C in a die photographic mixtures of the application vacuum oven to remove the ether. Application examples 17 and 18 are only used as an application of 150 ml of water, 3 g of citric acid, 15 g of the application examples for the usefulness of the application of ground, treated cowhide and 24 g of potassium - the mixture of the inventive coating composition for herbromide was prepared, 5 position of Coatings mentioned, and it is clear, by first adding the citric acid, the ground that these mixtures can be varied as desired, cowhide and the water in a mixer 15 Mi-. Although the application examples were comminuted for a long time, the caustic was only added using the lium bromide applied to paper, and the mixture was explained in the case of photographic emulsions, which were mixed at high speed for 15 minutes, _{10 of} the coating composition according to the invention hergcum the ground skin to be changed in such a way that a set of coatings was used in the same way for a conventional substantial part of it to microcrystalline colloidal cellulose film base and glass plates. The mixture was through a bar. The sensitivity to light against different double filter cloth layers filtered and in the mixer colors can normally be returned by adding. ₁₅ applied light-sensitive colors to regu-

By diluting 30 g of silver nitrate in 50 ml of water. The one with the Bewurde according to the invention Coatings produced slowly to the coating mass of the co-agent bromide dispersion are suitable given and in the mixer for 5 minutes at less also for the production of color films where Mixed speed. There were 20 g of ethanol coupler in the photographic emulsion or added and the mixer was set to thorough so dispersion is included. You can also use it as a Mix for 15 minutes with high speed protective coating or protective cover used operated. The mixture was in one of the die (s) after developing and the bell Using a water aspirator to process the film negatives, slides and prints Removal of air evacuated. Some sheet of paper is applied.

were coated with the dispersion. The remaining 95 In the preparation of a coating mixture for

The rest of the dispersion was put into a porcelain for a specific purpose, this is how it is used

bowl filled, gelled by cooling with ice, chopped up so that it meets the conditions of use

nert, filled into a bag and at 18 ° C corresponds to the finished product. So z. B.

Water washed out to add the potassium bromide and a large number of crosslinking agents

Remove potassium nitrate. After washing 30, e.g. potassium alum, melamine-formaldehyde

the gel was heated to about 60 ° C, precondensate, basic aluminum acetate, cadmium

20 ml of ethanol were added, then mixed, acetate, chrome alum, copper nitrate and barium

and the resulting mixture was evacuated. hydroxide. These crosslinking agents increase the

Paper was coated with this dispersion and the strength and toughness of the films and improve

then air-dried. 35 also the heat resistance of the coatings

The dispersion showed about the same leveling in terms of dimensional stability and properties as the photographic emulsions in terms of discoloration resistance. 17 of the dispersions or of the application example, this cross-linking agents mentioned mediated Kaliumist surprising in view of the fact that the alum to the coatings, the best resistance to dispersion only about lOGew.- ^e / o of an 40 filmbil- discoloration.

the agent, namely microcrystalline collagen- During the acid treatment of collagen

salt, if one reacts this amount with the amount, the acid only reacts with the free or accessible

of the film-forming material in the emulsion of the borrowed amino groups and forms a water-insoluble

Application example 17 compares. Though the salt of collagen. Some of the amino groups

Coating was much thinner than that which the 45 are located within the crystallites and are in

Emulsions of Application Example 17 resulted and collagen bound; as a result, the treated

although the mixture does not have a crosslinking agent or acid, no access to them. The here

Containing hardening agents, the coatings had the nickname "water-insoluble salt des."

sufficient strength and abrasion resistance, collagen ”stands for this reaction product. the

to prevent scratches during processing. How so water-insoluble collagen salts are in this respect

in application example 17, samples also became unique in that they had the property of being aqueous

peeled off and developed. The finished prints form gels that contain 0.5% / q dispersed salt

exhibited the same, sharp resolution, contrasts, which has a pH value of about 3.0 to 3.4,

sharpness and brilliance as in Example 19, with the gels for at least 100 hours made deductions. 55 5 ° C have an essentially stable viscosity.

Claims (3)

have less than 1 μ - dispersed in water, the pH of which is between 2.6 and 3.8, and claims: optionally a crosslinking agent and / or a photosensitizing agent. 1. Collagen-containing coating composition for the 5 in the case of the one used according to the invention, in water Manufacture of self-adhesive coatings based on insoluble, microcrystalline collagen salt any substrate, which means that it is an intermediate stage between the known, that it consists of a viscous collagen fiber and its basic building blocks, the stable gel from about 1 wt .- * / o one in water tropocollagen units, which the advantageous This insoluble, microcrystalline collagen salt has such a property that it swells in water - Made possible by treating collagen, the viscosity achieved thereby at with an aqueous acid solution with a pH standing for weeks, unchanged upright value from 1.7 to 2.6 and grinding the can thereby be obtained, and in particular for hydrolyzed material obtained, to at least the production of advantageous coatings with verstens 10% of the particles of a size less than 15 have improved properties. than 1 μ - dispersed in water, which one obtains this particular intermediate one pH value is between 2.6 and 3.8, and possibly microcrystalline, water-insoluble collagen a crosslinking agent and / or a salt that has practically no tropocoil layers and no photosensitizing agents. It contains forms of degradation and by its 2. Coating composition according to claim 1, da- ao water insolubility in marked contrast characterized in that the microcrystalline is related to the tropocollagen and its degradation stages, Water-insoluble collagen salt at least by being denatured collagens or them 10% by weight from tufts of tropocollagen-containing substances, such as pieces of skin, cartilage units, each with a particle size and fascia, with an aqueous acid solution, in particular no more than 1 μ and a minimum diameter of a hydrochloric acid solution, at a pH value have a knife of 25 A. treated from 1.7 to 2.6 and the resultant 3. Coating compound according to claim 1 and / or hydrolyzed material ground so finely that min or 2, characterized in that the Verstens 10 ⁰ Zo of the particles have a size of less than wetting agent formaldehyde or a derivative 1 μ. When fine-tuning it is expedient. 30 a temperature not exceeding 25 ° C is applied. In order to obtain stable aqueous dispersions of this collagen salt, the pH of the water in which it is dispersed must be kept between 2.6 and 3.8, preferably at 3.2. One obtains 35 a viscosity-stable gel, which is about 1% by weight » ₀ consists of the water-insoluble, microcrystalline collagen salt that is dispersed in water. A particularly advantageous gel is obtained in that the microcrystalline, water-insoluble 40 collagen salt of at least 10% by weight from tufts The invention relates to a collagen-containing bed of tropocollagen units, each one • sealant for the manufacture of self-particle size not exceeding 1 μ and one adhesive coatings on any substrate. Have a minimum diameter of 25 A. Coating and coating compositions, in particular the collagen-containing coating according to the invention iolche made of gelatin, have been used for a long time and in 45 processing mass, which may also be a crosslinking large Used extensively, for example for medium and / or light-sensitizing Glazing and finishing of foodstuffs, which may contain agents, preferably contain molding coatings of packaging of such foodstuffs, aldehyde or a derivative thereof as a crosslinking stage Papers and other carriers. The so far mediated. However, known coating compositions have the 50. The water-insoluble disadvantage used according to the invention, that they lead to coatings that are a microcrystalline colloidal form of collagen have insufficient wet strength. in the form of a collagen salt results when applied It has now been found that these disadvantages affect the surface of the substrate to be coated can be eliminated by that one as loading and after removal of the liquid sealant contained therein a collagen-containing coating means a continental mass adhering firmly to the substrate used, which is a water-insoluble, fine coating with excellent properties, Contains microcrystalline collagen salt. especially excellent wet strength. There Accordingly, the subject matter of the invention is such a coating, even at a pH value, that is collagen-like Coating compound for the types 3 and 4 is insoluble in water, is obtained on Positioning of self-adhesive coatings in any way Substrates, which is characterized, tensile, this wet strength by the addition of that it consists of a viscosity-stable gel made of crosslinking agents can be further improved about 1% by weight of a micro-can which is insoluble in water.