DD273846A1 - PHOSPHORUS-BASED ADHESIVE - Google Patents

Abstract

The invention relates to a phosphorus-containing adhesion promoter for increasing the bond strength in methacrylate-bonded or -coated or polyvinyl chloride-bonded or -coated composites. Composite materials include metals, organic polymers, ceramics and glasses as well as fillers as well as hard, living tissues such as bones and teeth in combination with each other and with each other. The adhesion promoter according to the invention contains 0.01 to 10% by mass of N-acylaminomethanebisphosphonic acid or its salts of the general formula mentioned in the description in an aqueous solution. For methacrylate-bonded composites with hard human tissue, the adhesion promoter contains 0.01 to 10% by weight, preferably 0.1 to 2% by mass, of N-acylaminomethanebisphosphonic acid or its physiologically acceptable salts (water-soluble alkali or alkaline earth salts) in an aqueous one Solution.

Description

Field of application of the invention

The invention relates to a phosphorus-containing adhesion promoter for increasing the bond strength in methacrylatverklebten or -coated cdor polyvinylchloridverklebten or -coated composites. The materials of the composites are both metals and organic polymers, ceramics and glasses and fillers as well as hard, living Gewsbe such as bones and teeth in conjunction with each other and among themselves.

Characteristic of the known state of the art

To improve adhesion between composite materials, a number of adhesion promoters and adhesive coatings have been developed and described.

For use in stomatology in particular esters of phosphoric acid, which contain in the organic Re M vinyl, acryloyl or other unsaturated groups have been boschrieben in recent years, such. In Euro-PS 0058483, Euro-PS 0074708 and Euro-PS 0088527 A2. The application of phosphorous or phosphonic acid esters with C-C multiple bonds in the organic part of the molecule as a bonding agent between composite resin and dental material (dentin and / or enamel) takes place for. U.S. Patent 4,255,075 and U.S. Patent 4,368,043. For the same purpose, U.S. Patent No. 4,525,493 discloses diphosphonic acids having the moiety

Ü O

Λ Il "O

FT-P-O-P-FT OH OH

wherein -R 'and R ² - are organic radicals having at least one CC multiple bond used.

However, most products of this type are not sufficiently hydrolysis-resistant, especially not under the conditions prevailing in the oral cavity, i. H. Starch contact with salivary fluid with changing temperature (fluctuations by about 40K) and pH conditions Improved hydrolysis resistance show phosphinic acid derivatives which are described as being used as adhesion promoters in the bonding of hard human tissues in DE-OS 2818068 and in adhesions of Ivory with methacrylates average tensile strength values of 7.3 MPa were achieved.

The same applies to the application of the 1-methacryloxy-ethane-1,1-bisphosphonic acid described in DE-OS 3150285 A1, wherein

Here, too, the bond strengths left something to be desired.

Object of the invention

The aim of the invention is to provide a novel phosphorus-containing adhesion promoter with increased bond strength, even under physiological conditions, which consists of relatively easily accessible starting materials and can be processed without organic solvents.

Explanation of the essence of the invention

The invention has for its object to develop from derivatives of Aminomethanbisphosphonsäure a the invention objective corresponding adhesion promoter for methacrylatverklebte or -coated or polyvinylchloridverklebte or -coated composites.

The phosphorus-containing adhesion promoter according to the invention contains 0.01 to 10 parts by mass in% of N-acylaminomethane bisphosphonic acid of the general formula

PO (OH) _{2 R} 2

C- (CH ₂ ) -rf PO (OH) _O

in which R ^{1 is} -H, -OH or an alkyl radical having 1 to 5C atoms, R ^{2 is} -H or an alkyl radical having 1 to 5C atoms and η is an integer between 0 and 5, or their salts, in one aqueous solution.

For methacrylate-bonded composites with hard human tissue according to the invention the coupling agent contains 0.01 to 10% by weight, preferably 0.1 to 2% by mass, of N-Acylaminomethanbisphosphonsäure or their physiologically acceptable salts in an aqueous solution. Physiologically acceptable salts are water-soluble alkalis or alkaline earth salts.

The application of phosphorophosphoric adhesion promoter according to the invention follows in such a way that on pretreated and pretending surfaces of the hard human Gevv os and the other composite material before Methacrylatverklebung either from 0.01 to 10 mass%, preferably 0, From 1 to 2 by weight in%, which applies N-Acylamiriomethanbisphoäphonsäure or their physiologically ungekonkolllichen salts in an aqueous solution existing adhesion promoter, or a dried and crushed mixture of the bonding agent and a filler mixed with the Klebr.toffpolymer applied. The mixture of adhesion promoter and filler material according to the invention in a mass-Verhältris adhesion promoter to filler of 0.1 to 100 to 10 to 100, preferably from 2 to 100 prepared. The phosphorus-containing adhesion promoter according to the invention is characterized by the following advantages:

1. Superior bond strength of 16MPa on average, which is maintained even in the biological environment (temperature change, hydrolysis, mechanical stress, etc.) for a long time.

2. Very good biocompatibility.

3. Easy processing, since the compounds of the invention are incorporated into the adhesive polymer.

4. The good water solubility of the compounds of the invention requires no organic solvents.

5. Simple preparation of the starting materials and the novel N-acyl-aminomethanbisphosphonsäuren.

The preparation of the N-acyl-aminoalkanbisphosphonsäuren takes place in a conventional manner by reacting corresponding acyl chlorides with Aminoalkanbisphosphonsäuron in alkaline solution.

The invention will be further described by the following embodiments without being limited thereto.

embodiments

example 1

Preparation of N-acyl-aminomethane bisphosphonic acids

1 mol of aminomethane bisphosphonic acid is dissolved in 500 ml of water in a solution of 3.2 mol of K ₂ CO ₃ , 1 mol of the acyl chloride (for example, acrylic acid chloride) is added dropwise with ice cooling, the temperature not exceeding 283K. After acidification with hydrochloric acid, the free bisphosphonic acid from the solution by ion exchange or as a potassium salt by crystallization

be won.

Example 2

By dissolution of N-acryloyl-amiMomethanbisphosphonsäure in Aaua dist. in a concentration of 1% by weight in% prepares a Grurdierungszubereitung. A bovine melt sample and a cuboid of a nickel-chromium alloy are polished to a grit size of 600 using a wet grinder.

The polished surface of the cattle tooth is treated with a 37% orthophosphoric acid solution for 30 seconds, sprayed for 20 seconds and dried with oil-free compressed air. The nickel-chromium alloy is blasted with Al ₂ O ₃ core (400 μm grain size, 20 seconds at 0.5 MPa jet pressure and 5 cm distance from the jet nozzle).

Then apply the prepared primer to the dried surfaces, let them act for at least 30s, spray them and dry. Thereafter, the solids are contacted using an adhesive polymer of the following composition. The whole 1 day and 30 days are stored in artificial saliva at a temperature of 37 ° C or in a temperature change load device over 1440 cycles (1 cycle = 30s 18 ⁰ C bath and 30s 60 ° bath). After storage, the pressure-shear load capacity is measured with a pressure tester at a crosshead speed of 0.5 mm / min.

The results obtained are summarized in Table 1.

Composition of the adhesive polymer

A parts by weight

Bisphenol A diglycidyl methacrylate (Bis-GMA) 16.7

Triethylene glycol dimethacrylate (TEGMA) 7.1

N, N-di (.beta.-hydroxyethyl) -p-toluidine

02

The components (A) and (B) are mixed immediately before their use in a weight ratio of 24:76 and processed immediately the adhesive polymer.

Tabeile 1

Bond strength in MPa 1 day 30 days 1440 cycles

16.0 14.0 14.3

Example 3

100 parts by weight Hydroxylatpatit ähnlhhe or fillers are mixed with 200Gew. parts of the primer composition of Ex.2 dried under constant agitation at 12O ⁰ C. The resulting filler is ground with a ball mill and mixed with an adhesive polymer of the following composition. The buffed and Ni-Cr alloy surfaces polished and conditioned according to Example 2 are contacted using this opaque adhesive composition. After storage as in Beispie! 2, the compressive shear capacity was measured. The results obtained are shown in Table 2.

B Parts by weight silangekoppelteranorgan. filling body 69.6 Until r.ViA 4.3 TEGMA 1.9 Benzoyl peroxide (silane: methane) aryloxypropyltrimethoxysilan) Filler: pyrogenic SiO ₂ 0.2

Composition of the adhesive mass

A parts by weight B parts by weight

Bis-GMA 16.7 well-connected anory m. 43.3 7.1 packing 2.7 TEGMA 0.2 Bis-GMA 1.9 N, N-D- (ß-hydroxyethyl) -p-toluidine TEGMA 0.2 B (nzoyl peroxide 27.9 ΟΙίΑρ + primer preparation

The components (A) and (B) are mixed immediately before use in a weight ratio of 24:76 and processed immediately the adhesive composition.

Table 2

Bond strength in MPa 1 day 30 days 1440 cycles

16.0 15.6 16.0

As can be seen from Table 2, the cured compound of the present invention maintains its superior bond strength over a long time.

Example 4

Two planar Ni-Cr specimens blasted according to Example 2 are brought into contact using the adhesive preparation according to Example 3. After storage according to Example 2, the compressive shear capacity was measured, the results are shown in Table 3.

Table 3

Bond strength in MPa 1 day 30 days 1440 cycles

19.0 18.8 19.0

Claims (7)

1. A phosphorus-containing adhesion promoter for increasing the bond strength in Methacrylatverklebten or -coated or solyvinylchloridverklebten or-coated composites, characterized in that the adhesion promoter 0.01 to 10 parts by weight in% N-Acylaminomethanbisphosphonsäure the general formula PO (OH) ₂ R ² R ¹ -C (CH ₂ ) _n -NHCO-C _x PO (OH) ₂ "→ CH ₂ in which R ^{1 is} -H, -OH or an alkyl radical having 1 to 5 C atoms, R ^{2 is} -H or an alkyl radical having 1 to 5 C atoms and η is an integer between 0 and 5 or their salts, in an aqueous solution. 2. A phosphorus-containing adhesion promoter for increasing the bond strength in methacrylatverklebten bonds according to claim 1 with hard human tissue, characterized in that the adhesion promoter contains 0.01 to 1C mass fractions in% of N-Acylaminomethanbisphosphonsäure or their physiologically acceptable salts in an aqueous solution. 3. Phosphorhaltig Haftvermittl tr according to claim 2, characterized in that it contains 0.1 to 2 parts by mass in% of N-Acyuminomethanbisphosphonsäure or their physiologically acceptable salts in an aqueous solution. 4. A phosphorus-containing adhesion promoter according to claim 2 and 3, didurch characterized in that the physiologically acceptable salts are water-soluble alkali or Eialalkalisalze. 5. A method for increasing the bond strength in methacrylate-bonded bonds with hard human tissue, characterized in that the pretreated and adhered surfaces of the hard human tissue and the other composite material before the Methacrylatverklebung - One from 0.01 to 10 parts by mass in% N-acyl-amino-methane-bisphosphonic the general formol PO (OH) _{2 o} R ³ -C (CH ₉ ) - NHCO - ι PO (OH) ₂ ^{X> CH} 2 in which R ^{1 is} -H, -OH or an alkyl radical having 1 to 5 C atoms, R ^{2 is} -H or an alkyl radical having 1 to 5 C atoms and η is an integer between 0 and 5, or their physiologically acceptable radicals Apply salts in an aqueous solution existing adhesion promoter, or - applying a dried and comminuted mixture of the primer and a filler mixed with the adhesive polymer. 6. The method according to claim 5, characterized in that one - Applies a consisting of 0.1 to 2 parts by mass in% of N-acyl-aminomethanbisphosphonsäure or their physiologically acceptable salts in an aqueous solution of adhesion promoter, or - applying a dried and comminuted mixture of this coupling agent and a filler mixed with the adhesive polymer. 7. The method according to claim 5 and 6, characterized in that preparing the mixture on bonding agent and filler in a mass ratio bonding agent to filler of 0.1 to 100 to 10 to 100, preferably from 2 to 100 prepared. δ. A method according to claim 5 to 7, characterized in that the physiologically acceptable salts are water-soluble alkali or alkaline earth metal salts.