DK173588B1 - Coating agent for collagen-containing materials, its preparation and use - Google Patents

Abstract

Collagenous material coatings containing aldehyde, unsaturated monomers with active hydrogen and unsaturated monomers without active hydrogen, solubilisers and/or dispersants, activators and additives customary per se.

Description

in DK 173588 B1

The present invention relates to materials which can be used as coating material, e.g. as primer (primer or liner) or varnish to improve bonding between collagen-containing materials and curing, polymeric materials.

Collagenous materials are skeletal proteins and major constituents of the human and animal intercellular supports, such as cartilage and bone tissue, skin and tooth (dentin). Within the scope of the present invention, the coating agents are preferably used to treat dentin in the context of dental repair.

Especially in the dental field, curing polymeric materials are used as fillers for dental repairs. As curing polymeric materials, 15 acrylic-based fillings are generally preferred. However, these polymeric fillings have the disadvantage of being poorly adhered to the dentin. To solve this problem, partial cuts on the tooth bone have been made so far and, in addition to the affected area, it has been necessary to remove significant 20 quantities of fresh tooth bone.

In another method, the tooth bone and enamel surfaces are etched with acids, e.g. phosphoric acid, after which the filling is made. Apart from the irritating effect of the mouth area, the acids also readily penetrate the dentin ducts 25 into the tooth and damage the nerve (pulp). In addition, in this method, the binding of the filling to the dentin is poor.

EP Publication No. 141,324 discloses coating agents for collagen-containing materials which contain an aldehyde, an olefinically unsaturated monomer 30 with active hydrogen, optionally also in admixture with an unsaturated monomer without active hydrogen, water, solvents such as acetone or ethanol, and common additions (page 7, lines 24-29, page 10, lines 1-4, and page 14, lines 20-22).

An essential object of the invention, which is the basis of the present application, is a simplification of the process of an adhesive filling treatment, without the loss of strength of the adhesive. The coating material according to the invention can, inter alia, applied to tooth bones (dentin) and tooth enamel. As treatment of most cavities requires treatment of both dental materials, it is desirable and advantageous to have an application solution for both purposes available with the present coating for reasons of application safety and time saving. For this purpose, the known adhesives are less well suited. In order to apply a composite material 10 to dentine alone, according to known methods, an additional working step is required in comparison with the present invention. This additional work step comprises finishing an intermediate layer of a binder / closure material (EP-A 141,324, page 21, lines 10-12; "Enamel Binder").

15 It has proven to be beneficial when, for example,

when filling with dental cavities, first conditioning the fresh dentin surface. Conditioning fluids generally have a pH of 0.1 to 3.5 and may contain an acid having a pKs value of less than 5 and optionally a 20 amphoteric amino compound having a pKs value ranging from 9.0 to 10.6 and a pKg value in the range of 11.5 to 12.5.

The coating agents must form a firmly bonded bond between the conditioned dentin surface and the filler material.

A coating agent for collagen-containing materials has now been found which comprises a) 1-10 wt.% Aldehyde, b) 10-40 wt.% Water-soluble active hydrogen monomer, c) 1-50 wt.% Water-insoluble monomer with two or more. d) 0.01-2.5% by weight photoinitiator, e) 15-70% by weight water, f) 0.2-10% by weight solubility intermediates and / or 35 dispersants, and g) 0-5% by weight of additives known per se. .

3 DK 173588 B1

The present coating agent provides a firm bond between the conditioned dentine surface and the filler material, and the tooth repair thus lasts for years.

The aldehydes (a) may be aliphatic, aromatic or heterocyclic aldehydes.

In aliphatic mono- and dialdehydes, the aldehyde function is bound to a straight-chain or branched aliphatic hydrocarbon group having 1-20, preferably 2-10, especially 2-6, 10 carbon atoms. As aliphatic groups, e.g. are mentioned, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl and hydroxyethyl. Aliphatic aldehydes are e.g. formaldehyde, acetaldehyde, butyraldehyde, glutardialdehyde and glyoxal.

15 In aromatic aldehydes, the aldehyde function is bound to an aromatic group. As aromatic groups are mentioned aromatic hydrocarbons having 6-12 carbon atoms, preferably phenyl, naphthyl and biphenyl. The aromatic groups may be substituted by e.g. C 1-6 alkyl, C 1-6 alkoxy, hydroxyl or carboxyl.

As aromatic aldehydes, e.g. are mentioned benzaldehyde, salicylaldehyde, vanillin and o-phthalaldehyde.

In heterocyclic aldehydes, the aldehyde function is bound to the heterocyclic group. As an example may be mentioned furfuryl aldehyde.

The aldehydes of the coating compositions herein may be mono- or dialdehydes.

For the coating compositions herein, aliphatic mono- and dialdehydes are preferred.

30 Water-soluble monomers are understood to be unsaturated monomers having at 20 ° C a water solubility of more than 5% by weight, preferably 10-100% by weight, based on the mixture of monomer and water.

Preferred are acrylic acid and methacrylic acid and their derivatives such as the acid amides and hydroxyalkyl esters of 2-6 carbon atoms.

4 DK 173588 B1

For example, (meth) acrylic acid, methacrylic acid amide, hydroxy (C2-5 alkyl) methacrylates such as hydroxyethyl methacrylate and hydroxypropyl methacrylate, as well as ethylene, diethylene and triethylene glycol monomethacrylate.

5 The water-insoluble, unsaturated monomers have at 20 ° C

a water solubility of less than 5% by weight, preferably 0.01-3% by weight. They contain two or more polymerizable double bonds in the molecule, especially methacrylic and acrylic acid esters of from divalent to pentavalent alcohols 10 having from 2 to 30 carbon atoms are considered. Particularly preferred are alkoxy (meth) aerylates and urethane group-containing (meth) acrylates.

For example, mention may be made of (meth) acrylic acid esters of formula 15 o

II

A - (- 0-C-C = CH 2) n

X

Wherein A is an n-valent, straight-chain, branched, cyclic, aliphatic, aromatic or mixed aliphatic-aroroatic group having 2 to 25 carbon atoms which may be interrupted by -o or 25 -NH bridges and which may be be substituted by hydroxy, oxy, carboxy, amino or halogen, X means H or methyl, and n represents an integer from 2-8, preferably 2-4.

Preferably, compounds of the following formulas may be mentioned: B1

R 0-CH2-CH-CH2-0 - <^ 3 - <^ 3V ~ ° ~ CH2 ~ CH2 ~ ^ 0R

5 OH CH3 OH

CH3

R 0-CH2-CH-CH2-0Hf3 - (3 ° ~ 'CH2 ~ CH2- H ^ o R

OR CH-, OR

10 d CHg

RO-CH2-CH-CH2 - (> - ^^ - ^^ y-0-CH2-CH-CH2-0R

O-CO-NH-3 ^ 3 O-CO-NH - ^^ ch3

R-Q-CH2-CH2-O-CH2-CH-CH2-O - ^^ y • ^^ - Q-CHg-CH-CHg-O-CHg-CHg-O-R

OH CH3 OH

CH3

R0- (CH2) n-O- ^ 3) - (Z) ~ ° '(CH 2) n'0R

ch3 30 35 6 DK 173588 B1

R0-CCH2) n-O- ^ ~ 3 ~~ S02 '^ ZV ~ O ~ (CH2) n "0R

5 ch3 ch3

RO-CH2-CH-CH2 - ^^ y-O-CH2-CH-CH2 - ^^^ - O-CH2-CH-CH2-0R OH CH3 OH CH3 OH

OH OH

OH-CH2-CH-CH2-OH

A 2, 2

OH

J M -CH2-CH-CH2-0R

OH OH

20

OR

0-CH2-CH-CH2-0R

((J) -CH2 - fQ} -CH2 - ff ^) o-ch2-ch-ch2-or o-ch2-ch ~ ch2-or

OH OH

30 ch3 ch3

R-0-O - CZ / ^ ° ~ R R0 ~~ C »~ /> - ^ H ^ —OR

ch3 ch3 35 _ CH3

RQ — Hy - ^ H ^ —OH

HO CH3 OR

7 DK 173588 B1 0Π

R 0-CH2-CH-CH2-0 - <^ TV ~ ° ~ CH2 ~ CH ~ CH2 ~ 0R

5 OH o-ch2-ch-ch2-or

OH

R0- (CH2) n-O - ^^> - ^^^ - O- (CH2) n-OR ro-ch2-ch-ch2-o-ch2-ch2-ch2-ch2-o-ch2-ch-ch2 -or

OH OH

15 RO \ x ^ y ^ COO-0Η2γ ^ γΌΗ ro ^ sC ^ -ch3 h3c- ^ nC ^ Js-op

Η0Ύ ^ γΌΗ2- OOC - (CH2) 4 - COO- CH2'Nj ^ YOH

20 RO ^ N ^ H CH3

RO-N ^ N ^ CHp-CH-OR ROX- ^ v ^ C-CHp-OR

Th J 2 I ho. hJI 2

25 HO - '^ V ^ OH H3C- ^ n ^ OH

OR

30

R0-CH2-CH2-0ss-XAV ^ j / XjXOH

HCk ^ C ^^ - CH2 - CH2 - O ^ v ^ ND - CH2 - CH2 - OR

35 8 DK 173588 B1 RO-CH2 - ^^^ - CH2-OR RO-CH2 - (^ y ~ ch2-or 5 ch3

RQ-CH --- CV ^ H-OH

ch3 ch3 ch3 10

R0-CH2- <f3TV ~ ° ~ H ^ _ ^ - CH 2 -OR

15

COOCH? CH? -OR

<T ^

x = ^ COOCH2 - CH2 - OR

20 in ortho, meta or para form, ro-ch2-ch2-o-co-nh ^ <<, \ ^ nh-co-o-ch2-ch2-or 25 kAcH3 CHo CH3 I 3 (3 ro- ch2-ch-o-co-nh-ch2-c-ch2-ch-ch2-ch2-nh-co-o-ch-ch2-or 30 CH3 CH3 CH3 9 DK 173588 B1

r-o-ch2-ch2-o-co-nh - ^^^ - ch3 ° "9H

5 NH-CO- \ I

L - * 3 \ o -CH2

R-O- (CH 2) n-O-R 10 R-O- (CH 2 CH 2 O) m-R

CHo I 3 r-o-ch2-c-ch2-o-r CHo

15 J

wherein 0 0

II II

R is CH 2 = C-C or CH 2 = CH-C-20 CH 3 n is a number from 1-4 and m is a number from 0-5.

Also mentioned are derivatives of tricyclodecane (EP-25 Publication No. 0.023,686) and turnover products of polyols, diisocyanates and hydroxyalkylmethacrylates (DE Publication Nos. 37.03.120, 37.03.080 and 37.03.130).

Especially preferred as a monomer is the so-called bis-GMA 30 of the formula γη. CHo i t - v i 3

(CH2 = C-COO-CH2-CH-CH2-O-ζ / - ') 2C

OH CH3 10 DK 173588 B1

Of course, it is possible to use mixtures of the various (meth) acrylic acid esters which can form cross-links. For example, mixtures of 20-70 parts by weight of bis-GMA and 30-80 parts by weight of triethylene glycol dimethacrylate should be mentioned.

5 Photoinitiators (d) are known (Houben-Weyl, The Method of Organic Chemistry, Vol. E20, page 80 et seq., Georg Thieme Verlag Stuttgart, 1987). Preferably, these are carbonyl compounds such as benzoin and derivatives thereof, in particular benzoin methyl ether, benzil and benzyl derivatives, e.g.

4,4-oxydibenzil, and other dicarbonyl compounds such as diacetyl, 2,3-pentanedione and α-diketo derivatives of norbornane and substituted norbornanes such as campherquinone, metal carbonyl compounds such as pentacarbonylmangan, quinones such as 9,10-phenanthrenoquinone

Preferably, the coating materials herein also contain coactivators which, in the presence of photo-polymerization initiators, accelerate the polymerization reaction. Known accelerators are e.g. aromatic amines such as p-toluidine and dimethyl-p-toluidine, trialkylamines such as trihexylamine, polyamines such as Ν, Ν, Ν ', Ν'-tetraalkylalkylenediamines, barbituric acid and dialkylbarbituric acid.

The accelerators are generally present in the coating material in an amount of from 0.01 to ca. 5% by weight.

Also mentioned as coactivators are alkylaminoarylsul phonamides of the formula R4 / R6 R3 R5 wherein R1 and R2 are the same or different and represent hydrogen, methyl, vinyl or phenyl, R3 is hydrogen, methyl or ethyl, R4 and R5 are the same or different and means hydrogen, halo or methyl, or the groups R4 and R5 may, in ortho position, form an annulated, aromatic, six-membered ring, R6 and R7 are the same or different and represent hydrogen, methyl, allyl, methallyl , cyclohexyl, phenyl, benzyl, hydroxyethyl, hydroxypropyl, acryloyloxyalkyl, methacryloyloxyalkyl, 2,3-epoxypropyl or 1,2-dihydroxypropyl-1- (meth) acrylate, or R6 and R7 may be linked to a morpholine or piperidine group .

As alkylaminoarylsulfonamides, e.g. mention is made of: 10 N, N-dimethyl-p-dimethylaminobenzenesulfonic acid amide and N, N-hydroxyethyl-p-dimethylaminobenzenesulfonic acid amide.

The water (s) may e.g. be demineralized water.

Solubility intermediates within the scope of the present invention are volatile solvents (vapor pressure at 25 ° C over 1000 Pa) from the ketones, alcohols and ethers group. Preferred are aliphatic ketones of 3-6 carbon atoms, aliphatic alcohols of 1-5 carbon atoms, glycol mono- (1-4-alkyl) ethers and cyclic ethers of 4-6 carbon atoms. For example, acetone, butanone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol monomethyl ether, tetrahydrofuran and 1,4-dioxane.

Dispersants (f) which can be used according to the invention can be ionic and nonionic surfactants.

Preferred anionic surfactants are e.g. phosphates such as di- (2-ethylhexyl) phosphate Na salt, alcohol sulphates such as oleyl alcohol sulphate, (C 6 O 6 alkyl) benzenesulfonates and (C 1-4 alkyl) sulphonates, especially sulphuric acid dioctyl ester Na salt.

Preferred cationic surfactants may e.g. be quaternary ammonium salts, e.g. methyltrioctylammonium chloride and methyltricaprylylammonium chloride.

According to the invention, nonionic surfactants can also be used in the form of fatty acid derivatives of polyols or of ethylene oxide, ethoxylated fatty alcohols and phenols as well as amphoteric surfactants such as alkylaminoethanesulfonic acid. Preferred are surfactant, high molecular weight compounds. Mention should be made here of water-soluble polyvinyl compounds such as polyvinyl acetate, polymethacrylic acid and polyacrylic acid as well as their alkali metal salts, copolymerisates of sodium methacrylate and methacrylic acid alkyl esters. Also suitable are cellulose derivatives such as methyl cellulose and carboxymethyl cellulose.

Particularly suitable are poly-N-vinylpyrrolidone (2).

Known per se known additives may be stabilizers, inhibitors, light preservatives, dyes, pigments and fluorescents.

Preferred are coating agents for collagen-containing materials consisting of a) 2-8 wt.% Aldehyde, b) 15-40 wt.% Water-soluble active hydrogen monomer, c) 2-40 wt.% Water-insoluble monomer with two or more polymerizable double bonds, d) 0. E) 25-60% by weight of water, 20 f) 0.5-10% by weight of solubility agents and / or dispersants and g) 0-5% by weight of additives known per se, the sum of the constituents yielding 100 weight percent.

Prior to coating a collagen-containing material with the coating material of this invention, this is usually treated with a conditioning liquid. The composition of the conditioner depends on the nature of the material to be coated. Particularly suitable for tooth enamel are 15-60% aqueous solutions of orthophosphoric acid. As conditioning solutions for dentine (dentin), e.g. aqueous solutions of EDTA (eg 0.5 M, adjusted to pH 7.4 with NaOH) or aqueous solutions containing 10% citric acid and 3% iron (III) chloride are used.

Conditioning fluids for a wide range of applications, particularly useful for tooth enamel and tooth bones, contain acids having a pKs value of less than 5 and optionally an amphoteric compound having a pKs value ranging from 9.0 to 10.6 and a pKB value in the range of 11.5 to 12.5. The following acids may be present in the conditioning fluids: phosphoric acid, nitric acid, pyruvic acid, citric acid, oxalic acid, ethylenediaminetetraacetic acid, acetic acid, tartaric acid, malic acid and maleic acid.

Preferably, as amphoteric amino compounds are compounds of the formula

H

10 is -C-R1 wherein r3nh R1 represents a carboxyl group, R2 represents hydrogen or a lower alkyl group optionally substituted with hydroxy, thio, methylthio, carboxy, amino, phenyl, hydroxyphenyl or the groups ίX 20 in R3 means hydrogen or phenyl, or the groups R1 and R3 may be linked to a propyl group or where R1 represents hydrogen, R2 represents a group -A-NH3X where A represents a divalent alkylene group of 1-6 carbon atoms, and X is halogen and R3 is hydrogen.

For example, the following amphoteric amino compounds may be mentioned: glycine, serine, threonine, cysteine, tyrosine, as-paragin, glutamine, alanine, valine, leucine, isoleucine, proline, methionine, phenylalanine, tryptophan, lysine, arginine, histidine, N-phenylglycine, ethylenediamine hydrochloride, propylenediamine hydrobromide, butylenediamine hydrochloride, butylene diamine hydrobromide, leucine hydrochloride and histidine hydrochloride.

14 DK 173588 B1

Furthermore, the conditioning fluid may contain substances from the group of polyethylene glycols and metal hydroxides. In particular, the above-mentioned multi-base acids can also be used as partial metal salts as long as free acid functions 5 remain.

Conditioning fluids containing at least one of the acids from the group pyruvic acid, ethylenediaminetetraacetic acid and citric acid, and optionally an amphoteric amino compound from the group glycine, N-phenylglycine and proline, are especially preferred.

The coating materials of this invention are generally prepared by mixing the components.

The materials of the present invention can be used as coatings, preferably as primers (primers 15 or interlayer) or varnish (varnish) to improve the bond between collagenous materials and hardening polymeric materials.

Collagenous materials occur in many places in the human and animal body. The use of the invention relates, of course, to living and non-living materials. As collagen-containing materials should be mentioned teeth, bones, skin and leather. Preferably, the materials of the present invention are used for coating teeth for preparing tooth fillings for dental repairs.

The hardening polymeric materials are first and foremost determined by the field of application. Thus, e.g. in the dental field for polymerization, only monomers which are physiologically harmless and which can polymerize in the oral region are used, e.g. bis-GMA (bisphenol-A-diglycidyldimethacrylate).

In use, e.g. in a dental repair, the collagen-containing dental material, after mechanical cleaning, is first applied to the described conditioner with a little cotton wool, allowed to act for 60 seconds, the dental material is rinsed with water and dried in an air stream. Then, the present coating material is applied with a small brush in a thin layer, and excess material is distributed in the air stream.

The toothpaste is now applied to the coating material and the two are cured together.

Examples 1-5

Invention materials according to the invention

Using a fast-moving stirrer (2000 rpm), mixtures of the compositions listed below are prepared.

Example 1

5 g of glutardialdehyde 33 g of 2-hydroxyethyl methacrylate 2 g of bis-GMA

0.1 g campherquinone (photoinitiator) 55 g water 5 g acetone

Example 2 5 g of glutardialdehyde 33 g of 2-hydroxyethyl methacrylate 2 g of bis-GMA 0.1 g of campherquinone 59.2 g of water 0.7 g of poly-N-vinyl-2-pyrrolidone 25

Example 3 3.3 g of glutardialdehyde 23.4 g of 2-hydroxyethyl methacrylate 12.6 g of triethylene glycol dimethacrylate

20.5 g bis-GMA

67 mg campherquinone 167 mg N, N-dimethylaminobenzenesulfonic acid diallylamide (coactivator) 38.5 g water 35 g g Poly-N-vinyl-2-pyrrolidone 33 mg 2,6-di-tert-butyl-4-methylphenol (stabilizer) 16 DK 173588 B1

Example 4 3.3 g of glutardialdehyde 23.4 g of 2-hydroxyethyl methacrylate

20.8 g bis GMA

12.7 g triethylene glycol dimethacrylate 70 mg campherquinone 39.3 g water 0.5 g methyltricaprylammonium chloride Example 5 2.5 g glutardialdehyde 18 g 2-hydroxyethyl methacrylate

30 g to GMA

17.5 g triethylene glycol dimethacrylate 15 100 mg campherquinone 29.5 g water 2.5 g poly-N-vinyl-2-pyrrolidone Example 6 20 Application test

The suitability of the coating materials of Examples 1-5 is tested by determining the bond strength of a plastics material containing bis-GMA and triethylene glycol dimethacrylate as monomers and campherquinone as a photoinitiator on dentine and enamel which is pretreated with a conditioning liquid (60). second impact time, water rinse, air drying) and coating material (60 second impact time, air drying).

Extracted and moistened human teeth are used for the test. Teeth are embedded in epoxy resin upon impact. For the dentine measurement, a smooth dentirio surface is produced by wet grinding. The final grinding is done with carbon paper 1000.

For the manufacture of a test body for measuring the bond strength, a cylindrical, two-piece teflon shape is tensioned on the dentino surface treated as described above (Scand.

17 DK 173588 B1 J. Dent. Res. J38, 348-351 (1980)). As a filler, the photo-curing plastic filler material is filled in. A round drill # 18, which is clamped in a hole in a drill holder, is attached to the teflon mold and pressed into the material layer which is still in the curing process. The assembled device is left undisturbed for 10 minutes at room temperature (23 ± 2 ° C), after which the drill holder and teflon mold are removed and the sample is left under water at a temperature of 23 ± 1 ° C.

After 24 hours, the sample is mounted with the drill in an Instron tensile test apparatus (Scand. J. Dent. Res. 88. »348-351 (1980)) and at a rate of 1 mm / minute a tensile strength measurement is performed. The tensile strength is calculated by dividing the load imposed on the filling by the cross-sectional area of the fracture surface of the test body. In each of 15 cases, 5 measurements are taken on test bodies. The following solutions are used as conditioning liquids:

K: 9.1% pyruvic acid 9.1% glycine 20 81.8% water K 2: 17% ethylene diamine tetraacetic acid disodium salt dihydrate 1.7% sodium hydroxide 81.3% water K 3: 35% orthophosphoric acid 65% water .

30 The results of the bond strength measurements are summarized in the table below.

DK 173588 B1 18 0) 10 C— CM H 10 V * k v s x k U o η n n m> 1 P +1 +1 +1 +1 +1

CO

thaw CO CM CO O CM

i — i *. «» S s

Cm <· co cm r · »n

• Η β HH Η Η H

Ό § C \

Ή Z

c) «> - · * r>

H

kj

In O 'c

• H

u 0) c o • H HH PI Π Cl H <U XX X x x

Ό X

C CO

0 (ti X> 0)

-X

J 5-1 xrMH ^ fon W> i CO P + 1 + 1 +1 +1 +1 +1

<CO

Η co h co in h 0% r-i s v% C CM Ifl 51 N rt Cl Ί1

• H S HHHHHH

Ό § C \ C · Η 55 • H CO> ->

P

C

0)

Q

CO

O 'c

• H

0) c o

• Η Η H CM CM CM CM

• H 0) XXXXXX

Ό X

C CO

0 ft X>

CO H CM CM Η M · CO

θ '0)

CH HHHHHH

• H (0 (1) 0) (1) 0) (1) (1) C-H &&&&&&& O 'g g g g g g g $ 0) 0) 0) 0) 0) 0) 0)

HP COCOCOCOCOCO

0) (β X X Μ X X Μ mg w η w w w w 19 DK 173588 B1

Example 7 (Comparative Experiment)

A coating material of the following composition is prepared: 2.5 g of glutardialdehyde 5 18 g of 2-hydroxyethyl methacrylate

30 g to GMA

17.5 g triethylene glycol dimethacrylate 100 mg campherquinone 7.5 g water 10 24.5 g acetone

In the method described in Example 6, the bond strengths are measured on dentine and enamel.

15 Dentin Enamel

Conditioning-Bonding Conditioning-Bonding ring liquid strength Ringing liquid strength [N / mm ^ J [N / mm ^] 20 K 2 1.0 K 3 7.2

Claims (5)

1. Coating agent for collagen-containing materials, characterized in that it consists of a) 1-10 wt.% Aldehyde, 5 b) 10-40 wt.% Water-soluble active hydrogen monomer, c) 1-50 wt.% Water-insoluble monomer with two or more polymerizable double bonds, d) 0.01-2.5% by weight photoinitiator, 10 e) 15-70% by weight water, f) 0.2-10% by weight solubility agents and / or dispersants, and g) 0-5% by weight of additives known per se. Coating agent according to claim 1, characterized in that it consists of a) 2-8 wt.% Aldehyde, b) 15-40 wt.% Water-soluble monomer with active hydrogen, c) 2-40 wt.% Water-insoluble monomer with two or 20%. several polymerizable double bonds, d) 0.01-2.5% by weight photoinitiator, e) 25-60% by weight water, f) 0.5-10% by weight solubility intermediates and / or dispersants, and 25 g) 0-5% by weight known per se. additives. Coating material according to claims 1-2, characterized in that as a component f) a dispersant is used. Coating material according to claims 1-3, characterized in that poly-N-vinyl-2-pyrrolidone is used as a dispersant. Process for preparing coating materials for collagen-containing material, characterized by mixing 35 a) 1-10 wt% aldehyde, b) 10-40 wt% water soluble monomer with active DK 173588 B1 hydrogen, c) 1-50 wt% water insoluble monomer with two or more polymerizable double bonds, d) 0.01-2.5% by weight photoinitiator, 5 e) 15-70% by weight water, f) 0.2-10% by weight solubility precursors and / or dispersants, and g) 0-5% by weight and known additives.