DE102009014685A1 - Antimicrobial coating material based on an amino- or hydroxyl-functional reactant for isocyanates - Google Patents

Abstract

The object of the invention to develop a process for the preparation of a solvent-free coating material and a solvent-free coating material based on an isocyanate-crosslinkable polymerization product from which emanates an antimicrobial effect, was achieved by presenting amino / hydroxy groups-functional binder in a batch container, Following this approach, the pigments, fillers and additives are added and mixed, then this approach for the installation of miniaturized water deposits an additive in the form of alkali or alkaline earth aluminosilicates with the general formula M / O-AlO.xSiO.yHO be incorporated, the be homogenized in this system by means of energy input without changing the crystal structure and thus as a complex anion formed in this system ion donors, consisting of energy input generated nanoparticles of semimetals and / or their organis chen and inorganic compounds, act.

Description

The The present invention relates to a solvent-free lightfast, with the coating object shrinkage compliant and material, form and non-positive coating material the base of an isocyanate-crosslinkable amino- or hydroxy-functional and / or from its derivative derivable reactant as Binders and / or other reaction resins containing primary particles in the sense of nanotechnology for the establishment of a biocide depot in the Matrix are equipped.

• – mindestens einen Polyester und/oder
• – mindestens ein Polyether, welche beiden Ausgangsstoffe mindestens zwei gegenüber Isocyanaten reaktionsfähige funktionelle Gruppen aufweisen;
• – mindestens ein Polyol und/oder
• – mindestens ein Polyamin und/oder
• – mindestens ein Alkanolamin
• – mindestens eine Verbindung mit mindestens einer zur Anionenbildung befähigten funktionellen Gruppe und mindestens einer, insbesondere zwei, mit Isocyanaten reaktionsfähigen Gruppen;
• – mindestens ein Polyisocyanat und/oder
• – mindestens ein Polyisocyantaddukt;
• – mindestens ein Blockierungsmittel für Isocyanatgruppen, welche bei einer bestimmten Reaktionstemperatur von den von ihnen blockierten Isocyanatgruppen wieder abgespaltet oder in Gegenwart der Vernetzungsmittel über eine Austauschreaktion wieder freigesetzt werden; sowie
• – mindestens ein Neutralisationsmittel für die anionische Stabilisierung im wäßrigen Medium, welche anorganische und/oder organische Basen enthalten oder hieraus bestehen;

miteinander umgesetzt werden.After DE 19 910 492 A1 are a solvent-free coating material based on a reactive polyurethane and a new polyurethane dispersion, and a method for the production of multi-layer coatings on optionally primed substrates known. Thereafter, a newly found polyurethane was disclosed which can be produced by

• - At least one polyester and / or
• - At least one polyether, which two starting materials have at least two isocyanate-reactive functional groups;
• At least one polyol and / or
• At least one polyamine and / or
• - At least one alkanolamine
• At least one compound having at least one functional group capable of forming anions and at least one, in particular two, isocyanate-reactive groups;
• At least one polyisocyanate and / or
• - At least one Polyisocyantaddukt;
• - At least one blocking agent for isocyanate groups, which are cleaved again at a certain reaction temperature of the blocked isocyanate groups or released again in the presence of crosslinking agents via an exchange reaction; such as
• - At least one neutralizing agent for the anionic stabilization in an aqueous medium, which contain inorganic or / and organic bases or consist thereof;

be implemented together.

adversely affects in this proposed coating material that he is described as solvent-containing and for the drying 50 to 155 ° C are required (drying time 20 minutes at 155 ° C and 42 μm layer thickness). The solids content is specified with a maximum of 55 wt .-%. Therefore is this coating material for the (IMC) in-mold coating process not suitable.

After US 2003/0004265 A1 and based on that US 2003/0105220 A1 is a polyurea-based coating material containing a polyester product for surface-coating (top-coat) for use on a substrate. This polyurea-based paint contains two reactive constituents, namely, an isocyanate as the first component and a low-viscosity amino-functional resin as the second component.

This known surface-sealing paints on the basis of polyurea is descriptive exclusively as a surface coatable coating system (topcoat) used. The reason for this is the intended, the surface adhesion based composition of this Coating system on freely accessible surfaces of already shaped moldings after their shaping. Furthermore, this coating system is not solvent-free. The disadvantage is that one coated with this system Surface not because of the material composition can be painted over without pretreatment.

• a) Herstellen einer Lösung aus Polyvinylacetat, einem Konservierungsmittel und einem Lösungsmittel,
• b) Aufbringen der Lösung auf die technische Oberfläche, und
• c) Trocknen der auf die technische Oberfläche aufgebrachten Lösung unter Ausbildung der Schicht.

In the WO 002006133754 A1 For example, a process for preparing an antimicrobial-release layer on a technical surface is described. The process disclosed therein comprises three process steps:

• a) preparing a solution of polyvinyl acetate, a preservative and a solvent,
• b) applying the solution to the technical surface, and
• c) drying the applied to the technical surface solution to form the layer.

The Method is further characterized by the fact that preferably as a preservative benzoic acid, sorbic acid, Natamycin, bacteriocins, plant extracts or mixtures thereof and as Solvent an ethanol-water mixture, ethyl acetate or Acetone can be used.

Also to this, the prior art determining method is to be noted that the substances used on a solvent-containing system based. The active ingredients are organic in nature and are on one existing surface of a shaped body applied, there to have the appropriate effect from the coated surface achieve.

Furthermore, after the DE 10 2007 008 670 A1 the use of the viscosity-controlling carbon nanotubes in binder systems and solvent-free coating systems with carbon nanotubes based on functional reactants for in-mold coating (IMC) and top coating, and a process for the preparation thereof known. According to this teaching, it is possible to produce at the boundary layers between the coating material and the molding a cross-sectional surfaces cross-compound. An antibacterial effect is not provided.

all Previously known systems have in common that the antimicrobial Effect either basically only on the surface is generated and not from the coating material out permanently the surface of the coating body emitted is or, although a good adhesion of the coating material on the surface of the coating body because interfacial layer compound, no antibacterial effect is provided.

aim This invention is a solvent-free and Light-resistant coating material based on a curable polymerization product for industrial Processing on metallic and non-metallic base substrates for use in highly polluted by bacterial germs Range as a germ-reducing coating material for both To provide topcoat as well as for in-mold-coat, the during processing no volatile organic Releases substances in the form of solvents.

Of the Invention is based on the object, a solvent-free and light-resistant coating material based on a curable polymerization product based on amine or hydroxyl, the is crosslinkable with an isocyanate and to control the viscosity in binders consisting of artificial resins hydroxyls and / or amino-functional reactants for isocyanates and incorporated in the binder Carbonnanotubes, the simultaneously having an antimicrobial effect and a process for the production, to develop.

These The object has been disclosed in the independent claim Teaching solved.

The Invention is intended below to an embodiment be explained in more detail.

In The accompanying drawing shows the operating principle:

Preparation example

in the Batch containers are up to 35% amino and / or hydoxylgruppenfunktionelles Binder submitted. This approach is the pigments, fillers and additives added and mixed. Then be miniaturized water depots installed in this system. In one Masterbatch, consisting of binder with semi-metal shares parallel the metallic ion donors, in the form of semi-metal parts or organic or inorganic compounds of the semimetals introduced. By An appropriate energy input into this system will be in the top-down process (eg agitator mill, roller mill, ultrasonic generator) generates the corresponding primary particles.

Subsequently the system is using a percentage of the masterbatch mixed. Thereafter, the remaining binder components to 100% - added to the base and homogenized. Dependent on from the physical and chemical properties of the used Pigments, fillers and existing additives are the necessary ones Observe temperature parameters.

Under same specification can be made by adding other ion donors further antimicrobial properties are generated.

On the basis of the amino-functional isocyanate reaction partners, a coating material has been developed which has a strong antimicrobial effect. The mechanism of action is based on ions being generated within a polymer matrix. The generation of ions requires charge carriers that can move freely in the molecular lattice. Through the use of zeolites, a large amount of water is stored in the polymer composite. For example, zeolite A has a framework structure of AlO ₄ and SiO ₄ tetrahedra. They form a covalent lattice with cavities, which usually contain water. This grid is a huge anion. Therefore, the cavities contain a corresponding number of cations dissolved in the inner water or coordinated on the inner walls.

The framework structure consists of AlO ₄ and SiO ₄ tetrahedra in the ratio 1: 1. In this case aluminum and silicon atoms are alternately connected to one another by oxygen atoms. Since the tetrahedra share an oxygen atom at each knot site, each oxygen and silicon atom has 2 oxygen atoms. From an assessment of the oxidation states, it follows that each Al atom of the covalent framework generates a negative charge. This charge is due to ionic bonds with cations such. B. Ag ⁺ balanced. The combination of the Al and Si tetrahedra leads to a spatially three-dimensional structure.

Out Tetrahedra can be a variety of structures form what the large number of different zeolites explained.

in the Example zeolite A, the so-called sodalite cage is formed.

Each oxygen atom is in the Near the lines drawn between the atoms. This illustration shows only three bonding directions of the Al and Si tetrahedra. The fourth direction allows linking with other sodalite cages. At this junction of sodalite cages, a new cage is formed in the center, called an alpha cage, with eight linked unit cells. When many unit cells line up, a microscopic cube-shaped crystal forms. Each crystal is a single giant multi-anion.

The charge of the multi-anion is balanced by an ionic bond to cations. In an anhydrous zeolite, the cations occupy fairly tight coordination sites near the Si _n Al _n O _2n rings.

contains Zeolite water, the cations are very mobile. You are in the water (almost) solved and thus exchangeable with other cations. This property is crucial for the antimicrobial effect.

Selectivity in ion exchange:
Ag ⁺ > Na ⁺ > K ⁺ > NH ₄ ⁺ > Li ⁺ > Ba ²⁺ > Ca ²⁺ > Cd ²⁺ > Mg ²⁺

An ion exchange with Ag ⁺ makes it easy to store silver ions in the zeolite. Silver is very preferred. When used as an additive in surface coatings, silver is released in low dosage. Silver ions have biocidal properties.

The Water z. B. in zeolite A is in the sodalite and alpha-cages. They are almost freely movable, interacting but strong with the cations and the anionic zeolite lattice. Therefore, the vapor pressure of the water in the zeolite is much lower, as the vapor pressure of free water. The water can be heated be removed from the zeolite without changing the lattice structure or to destroy. Upon heating the zeolite, it appears as if the solid would cook. It flows gaseous water from the solid and whirls the crystals on.

Of the Alpha Cage and the sodalite cage are enough free interior volume and sufficiently large ring openings (also called pores or channels) around water molecules to take or leave.

Ion exchange with Ag ⁺ makes it easy to store silver ions in the zeolite. Silver is very preferred. When used as an additive in surface coatings, silver is released in low dosage.

at an addition of metals or their compounds go into this Solution, the charge carriers can become exchange and become ions, which are around the respective Move atomic nucleus. These ions in turn attack the biological cell structures at.

metal ions unfold the antibacterial effect on the release of electrically positively charged (+) particles is based, the so-called Ions. In a very natural way, bacteria and germs, Mushrooms and microorganisms by blocking energy production killed.

In the antimicrobial coating material based on an amino- or hydroxyl-functional reactant for Isocyanates (PANADUR system) are metals and / or their active ingredients inorganic or organic compounds, such as. Silver, silver complexes, Hydroxylapatite, encapsulated nanosilver particles, copper and their Used complexes. They can be organic and inorganic Be connections.

silver ions z. B. have a bactericidal from a concentration of 0.1 ppm and fungicidal action. If silver ions enter the cell interior of microorganisms, block the enzymes of the respiratory chain there, destabilize the cell membrane and interfere with cell division. Thanks to this Mechanism of action, bacteria can not resist To train silver. As with almost all chemical or biochemical Reactions apply here: the smaller the silver particles, the larger the reactive surface, the bigger the bactericidal effect.

By the firmly anchored in the polymer matrix water is a long-term effect the charge carrier secured.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 19910492 A [0002]
• US 2003/0004265 A1 [0004]
• US 2003/0105220 A1 [0004]
• WO 002006133754 A1 [0006]
• - DE 102007008670 A1 [0009]

Claims (9)

A process for the preparation and processing of a solvent-free, antimicrobial coating material based on an amino and / or hydoxyl functional reactant for isocyanates, characterized in that are presented in a batch container amino / hydoxyl group-functional binder, then added to this approach pigments, fillers and additives and mixed Subsequently, this approach for the installation of miniaturized water depots, an addition in the form of alkali or alkaline earth metal aluminosilicates with the general formula M ₂ / O ₂ -Al ₂ O ₃ xSiO ₂ yH ₂ O incorporated, in this system by means of Energy input are homogenized without changing the crystal structure and thus as a complex anion of trained in this system ion donors, consisting of energy input generated nanoparticles of semimetals and / or their organic and inorganic compounds, acts. Method according to claim 1, characterized that as a miniaturized water deposit inorganic and organic water-adsorbing substances, such as zeolites, CaSO4 (calcium sulfate), superabsorbers be used. Method according to claim 1, characterized that by the energy input an ion exchange of cations in the crystal lattice of the water depot is effected and thus creates a biocide depot. Process according to Claims 1 to 3, characterized that the energy input into this system in the top-down process (eg. B. agitator mill, roller mill, ultrasonic generator) takes place and the corresponding primary particles with antibacterial Effect generated thereby. Solvent-free coating material with antimicrobial action on the basis of an amino- and / or hydroxyl-functional reactant for isocyanates, characterized in that the solvent-free coating material is formed from two reactive components, wherein the component A of an aliphatic isocyanate and / or its mixtures and the component B consist of a proportion of 50 to 90% crosslinkable with the component A binder based on an amino- and / or hydroxyl-functional reactants and / or mixtures thereof, wherein the component B is a proportion of 10 ^-3 to 40% of nanoparticles of semimetals and / or their organic and inorganic compounds containing fillers in the form of primary particles in the size of 1 to 100 nm, 0 to 7% stabilizers and 0 to 3% auxiliaries and the energy input by means of ultrasonic and / or roller mill in the power range from 500 W / s to 4000 W / s. Solvent-free coating material according to claim 5, characterized in that the coating material in the Interaction with the nanoparticles of metals and / or their enhancing the effect of organic or inorganic compounds as baits for microorganisms appearing Aggregate of nanoparticles from hydroxyapatite (bone ash) contains. Solvent-free coating material according to claim 5 and 6, characterized in that in the coating material for Achieving an antimicrobial effect metals and / or their organic or inorganic compounds are used. Solvent-free coating material according to claim 5 to 7, characterized in that in the coating material for Purpose of ion formation within the material matrix as so-called Water trap or dryer called miniaturized Water depots are used in the approach. Solvent-free coating material according to claim 5, characterized in that the coating material is a mixed, to assist the processability of the coating material and as an excipient for deaeration and defoaming known chemical additive with an affinity to gases and / or adhesion to a mold wall reducing internal or external release agent and / or with a thixotropic influence and / or with a the moisture content reducing additive in the reactive Component B is provided.