WO2001012725A1

WO2001012725A1 - Curable antimicrobial hyperbranched polymer compositions

Info

Publication number: WO2001012725A1
Application number: PCT/FI2000/000679
Authority: WO
Inventors: Mikael Skrifvars; Karri Airola; Matti Kaarnakari
Original assignee: Neste Chemicals Oy
Current assignee: Neste Chemicals Oy
Priority date: 1999-08-11
Filing date: 2000-08-10
Publication date: 2001-02-22
Anticipated expiration: 2002-02-11
Also published as: AU6446500A; FI19991705L; FI19991705A7

Abstract

The invention relates to curable antimicrobial hyperbranched polymer compositions, to a method for the manufacture thereof and to their use in applications wherein antimicrobial effect is desired. The antimicrobial hyperbranched polymer composition comprises a hyperbranched polymer or a combination of hyperbranched polymers, an antimicrobial compound or a mixture of antimicrobial compounds, and optionally a polyester resin.

Description

Curable antimicrobial hyperbranched polymer compositions

The present invention relates to curable antimicrobial hyperbranched polymer compositions, to a method for the manufacture thereof and to their use in applications wherein antimicrobial effect is desired.

Plastic materials, such as fiber reinforced plastics comprising polyester resins, are widely used in several consumer products, such as bath tubs, sinks, wash basins, in panels used in automobiles and recreational vehicles, marine vessels and boats.

Oligomers with a highly branched structure and with a spherical shape constitute a family of polymers, which has been increasingly studied during recent years. These oligomers are referred to as hyperbranched polymers having three-dimensional molecular architecture and possessing starburst topology. These polymers are also named as dendritic polymers or dendrimers. Hyperbranched polymers differ signifi- cantly from conventional linear oligomers, because the linear oligomer of sufficient molecular weight for polymer resins often contains an entanglement of flexible molecular chains, usually with only two terminal functional groups on each molecule, while the hyperbranched polymer is a compact spherical molecule with many branches which carry a high number of terminal functional groups on each molecule. These unique features of the hyperbranched polymers yield interesting and special properties which make these compounds very attractive and useful in several applications. The spherical shape yields the compounds favourable and different rheological properties, such as lower viscosity, when compared with the conventional linear oligomers. The high number of terminal, functional groups, which can be mod- ified, results in a variety of physical and chemical properties. Oligomers with a strongly branched structure can be used in applications, such as catalysts, as carriers for drug substances in pharmaceutical industry, as pharmaceuticals, cosmetics, adhesives, coatings, composites, agricultural chemicals and as multifunctional crosslinking agents.

Patent US 5 418 301 discloses a dendritic macromolecule of polyester type comprising a central initiator molecule or initiator polymer having one or more reactive hydroxyl groups (A). The groups (A) are under formation of an initial tree structure bonded to reactive carboxyl groups (B) of a monomeric chain extender having the two reactive groups (A) and (B). The tree structure is optionally extended and further branched from the initiator molecule or initiator polymer by addition of further molecules of a monomeric chain extender by means of bonding between the reactive groups (A) and (B) thereof and it is thereafter optionally further extended by a reaction with a chain stopper.

A series of hyperbranched (meth)acrylated polyesters with different number of terminal double bonds per molecule and methods for the manufacture thereof have been disclosed in patent application WO 96/07688. This publication discloses a hyperbranched polyester of a polyol with 3 to 10 reactive hydroxyl groups and an aromatic polycarboxylic anhydride with 2 to 4 carboxyl groups, each hydroxyl group of the polyol forming an ester linkage with one anhydride group of the polycarboxylic anhydride, and further glycidyl (meth)acrylate or allyl glycidyl ether forming ester linkages with the remaining carboxyl groups of the anhydride and free hydroxyl groups. Further, in the hyperbranched polyester, (meth)acrylic anhydride and/or an aliphatic carboxylic anhydride form ester linkages with free hydroxyl groups.

Deodorant compositions are disclosed in EP 858 797. These compositions comprise dendrimers, the terminal groupings of which consist of a primary amine function.

WO 93/18079 relates to a hyperbranched polymer comprising a nucleus and polyol and polycarboxy residues, the hyperbranched polymer having at least 6 terminal hydroxyl or carboxyl groups and a Carothers gel point lower than 1. The hyperbranched polymer having at least 6 terminal hydroxyl- or carboxyl groups, is obtainable by starting with a nucleus compound containing at least one hydroxyl group as the nucleus and reacting it with a compound containing at least one anhydride group, after which the resulting first generation acid-terminated addition product is reacted with a compound containing at least one epoxy group; the resulting first generation hydroxyl-terminated addition product thereafter is reacted, in the second generation, with a compound containing at least one anhydride group, after which the resulting second generation acid-terminated addition product, is reacted with a compound containing at least one epoxy group, resulting in a second generation hydroxyl-terminated addition product, and in at least one generation monomers are used that have at least one functional group besides the anhydride group or epoxy group.

WO 95/02008 discloses an invention relating to a process for the preparation of a dendritic macromolecule, wherein an amount of a core molecule comprising at least one functional group is dissolved in a solvent, after which alternatingly an addition reaction and a hydrogenation reaction are carried out, during the addition reaction vinyl cyanide units being added to the solution which react with the functional groups in such a manner that a dendritic macromolecule with terminal cyanide groups is formed, and during the hydrogenation reaction the cyanide groups being reduced in solution by means of hydrogen and a suitable catalyst in such a manner that functional amine groups are formed, wherein the solvent in which the hydrgenation reaction takes place is an alcohol which contains an amount of ammonia, the molar ratio between the amount of ammonia and the number of cyanide groups being higher than 0.8.

The surface of products based on dendritic macromolecules or hyperbranched polyesters are under constant exposure to bacteria, fungi and microbes that exist in the respective environments. Especially products which are used in hospitals, in kitchens, in bathrooms and in other environments, which are particularly associated with pathogen development, are easily contaminated with microbes, and the presence of humidity or moisture in this environment enhances the growth of pathogens. Bacteria, fungi and other pathogens can grow and multiply on the surfaces of the products and significant levels of microbe contamination can build up. Thus it can be seen that there exists a need for hyperbranched polymers with antimicrobial effect, and which can be used in applications where antimicrobial effect is required.

An object of the invention is to provide curable antimicrobial hyperbranched polymer compositions.

A further object of the invention is to provide a method for the manufacture of curable antimicrobial hyperbranched polymer compositions.

A still further object of the invention is the use of said curable antimicrobial hyperbranched polymer compositions in applications wherein antimicrobial effect, a high curing rate and an acceptable degree of curing and good mechanical properties in the final product are desired.

Characteristics of the curable antimicrobial hyperbranched polymer compositions, of the method for the manufacture thereof and of their use are stated in the claims.

The objects of the invention are achieved by a curable antimicrobial hyperbranched polymer composition and by the method for the manufacture thereof according to the invention. It has been found that hyperbranched polymer compositions with an antimicrobial agent or a combination thereof according to the invention can be manufactured and that further, the cured hyperbranched polymer product exhibits a significant antimicrobial effect. Thus, according to the invention, an antimicrobial agent, which exhibits an effect against bacteria, fungi, viruses, yeasts, molds etc., or a combination of antimicrobial agents is incorporated into a curable hyperbranched polymer resin or into a mixture thereof or into a conventional polymer resin comprising additionally a hyperbranched polymer or a mixture thereof. The amount of the antimicrobial agent depends on the application field and on the antimicrobial compounds are phenolic compounds such as triclosan (2,4,4' -trichloro- 2'-hydroxydiphenylether) which can be used in an amount of 0.1-10 wt% and preferably 0.2-5 wt%, polyhexamethylene biguanide derivatives, a base or a salt in an amount of 0.1-10 wt%, or chlorhexidine derivatives, a base or a salt in an amount 0.1-10 wt% or quaternary ammonium compounds such as benzalkonium chloride in an amount of 0.1-10 wt%. The antimicrobial agent is preferably incorporated into the hyperbranched polymer by using a carrier, suitably an organic solvent, such as styrene, toluene, acetone, tetrahydrofurane, ethylacetate or combinations thereof or an aqueous solvent like water, or combinations of solvents. The antimicrobial agent may also be incorporated into the hyperbranched polymer without any added carrier, and the hyperbranched polymer itself acts as a matrix or carrier for the antimicrobial agent.

Hyperbranched polymers are dendritic macromolecules with the following structure:

B-Z A-Z

/ /

X-AB-M X-BA-M

\ \

B-Z A-Z

(la) or (lb)

wherein

X = initial core molecule, polymer or their derivative, having one or more reactive groups A or B

A = reactive hydroxyl group

B = reactive carboxyl group

M = core of a chain extender

Z = a further extender having carbonyl or hydroxyl functionality and being able to add branches to a tree-like structure or optionally a terminator stopping the chain growth Suitable hyperbranched polymers are

1) Dendritic hydric or carbocyclic cored macromolecules wherein: (i) a central initiator molecule or initiator polymer is a molecule having at least one reactive hydroxyl group (A), which is bonded to a reactive carboxyl group (B) in a monomer chain extender having two other reactive groups (A) or (B) to be reacted further introducing thus a tree-like branching with ester linkages

B

B B

AB,

B B B

B or

(i) a central initiator molecule or initiator polymer is a molecule having at least one reactive carboxyl group (B), which is bonded to a reactive hydroxyl group (A) in a monomer chain extender having two other reactive groups (A) or (B) to be reacted further introducing thus a tree-like branching with ester linkages

(ii) ester linkages are formed through know-in-art synthetic methods, which are a) esterification of alcohol and carboxylic acid removing condensate water; b) esterification of alcohol and carboxylic acid removing condensate water; b) esterification of carboxylic acid by treating it with alcohols in the presence of dehydrating agents; c) esterification of carboxylic acid by treating with tert-butyl ethers and catalysts; d) reaction of carboxylic anhydride with alcohol; e) reaction of carboxylic acid chloride with alcohol; f) reaction of carboxylic acid with a reactive epoxy group in a reactant; g) esterification through transesterification

(iii) an extender which is a reactive molecule or polymer being able to create an ester linkage by means presented above through methods a) to g), adds branching to the initial molecule or to its derivative

and/or

(iv) optionally an extender molecule or polymer terminates a chain.

The central initiator molecule or initiator polymer is selected from the group consisting of a) an aliphatic, a cycloaliphatic or an aromatic diol, b) a triol, c) a tetrol, d) anhydroennea-heptitol or dipentaerythritol, e) a monofuntional alcohol, f) an alkoxylated polymer having a molecular weight of not more than 8000 and being produced by a reaction between an alkylene oxide and one or more hydroxyl groups originating from compounds a) through f); and preferably the initiator molecule is selected from the group consisting of ditrimethylolpropane, ditrimethylolethane, dipentaerythritol, pentaerythritol, alkoxylated pentaerythritol, triethylolethane, trimethylolpropane, alkoxylated trirnethylolpropane, glycerol, neopentyl glycol, dimethylolpropane, and l,3-dioxane-5,5-dimethanol.

The monomeric chain extender is selected from the following groups: a) mono- functional carboxylic acid having at least two hydroxyl groups, b) monofuntional carboxylic acid having at least two hydroxyl groups wherein one or more of the hydroxyl groups are hydroxyalkyl substituted; and preferably said chain extender is selected from the group consisting of dimethylolpropionic acid, α,α,- dihydroxybenzoic acid.

The chain stopper is selected from the group consisting of a) a saturated monofunctional carboxylic acid or a saturated fatty acid or an anhydride thereof, b) an unsaturated fatty acid, c) an unsaturated monofunctional carboxylic acid, d) a difunctional or a polyfunctional carboxylic acid or an anhydride thereof, e) an adduct or a reaction product of a difunctional or a polyfunctional carboxylic acid or an anhydride thereof, f) an aromatic monofunctional carboxylic acid, g) an epihalohydrin, h) a glycidyl ester of a monofunctional acid or of a fatty acid which acid has 1-24 carbon atoms, i) an epoxide of an unsaturated fatty acid with 3-24 carbon atoms, and preferably said chain stopper is selected from the groups consisting of lauric acid, linseed fatty acid, soybean fatty acid, tall oil fatty acid, dehydrated castor fatty acid, capric acid, caprylic acid, trimethylolpropane diallyl ether maleate, acetic acid, metacrylic acid, acrylic acid, benzoic acid, para-tert.bu- tylbenzoic acid, l-chloro-2,3-epoxy propane, l,4-dichloro-2,3-epoxy butane and epoxidized soybean fatty acid.

2) Hyperbranched polyesters of a polyol with 3 to 10 reactive hydroxyl groups and an aromatic polycarboxylic anhydride with 2 to 4 carboxyl groups, each hydroxyl group of the polyol forming an ester linkage with one anhydride group of the polycarboxylic anhydride, and further glycidyl methacrylate, glycidyl acrylate or allyl glycidyl ether forming ester linkages with the remaining carboxyl groups of the anhydride and free hydroxyl groups. Further, in the hyperbranched polyester, methacrylic anhydride and/or acrylic anhydride and/or an aliphatic carboxylic anhydride form ester linkages with free hydroxyl groups formed from the previous reaction.

3) Hyperbranched polyesters based on a polyol core molecule, a polycarboxylic anhydride as a branching extender and an epoxyacrylate as an end groups, and more specifically hyperbranched polyesters of a polyol with 2 to 10 reactive hydroxyl groups, preferably of equivalent reactivity, and a polycarboxylic anhydride with 2 to 4 carboxyl groups, preferably with 3 carboxyl groups, each hydroxyl group of the polyol forming an ester linkage with one anhydride group of the polycarboxylic anhydride, and further glycidyl methacrylate, glycidyl acrylate or allyl glycidyl ether forming ester linkage with the remaining carboxyl groups of the anhydride and free hydroxyl groups, and further unsaturated, aromatic or aliphatic anhydride forming ester linkages with free hydroxyl groups.

4) Multifunctional macromers of polycarboxylic acids comprising 2 to 4 reactive carboxylic groups and glycidyl methacrylate, glycidyl acrylate or allyl glycidyl ether forming esterlinkages with the carboxylic groups of the acid, and further unsaturated, aromatic or aliphatic anhydride forming ester linkages with the free hydroxyl groups.

5) Hyperbranched polymers comprising a nucleus and polyol and polycarboxy residues, the hyperbranched polymer having at least 6 terminal hydroxyl or carboxyl groups and a Carothers gelpoint lower than 1, and said hyperbranched polymer having at least 6 terminal hydroxyl or carboxyl groups is obtainable by starting with a nucleus compound containing at lest one hydroxyl group as the nucleus and reacting it with a compound containing at least one anhydride group, after which the resulting first generation acid-terminated addition product is reacted with a compound containing at least one epoxy group; the resulting first generation hydroxyl-terminated addition product thereafter is reacted, in the second generation, with a compound containing in the second generation, with a compound containing at least one anhydride group, after which the resulting second generation acid- terminated addition product, is reacted with a compound containing at least one epoxy group, resulting in a second generation hydroxyl-terminated addition product, and in at least one generation monomers are used that have at least one functional group besides the anhydride group or epoxy group.

6) Dendritic macromolecules obtainable by a process via the Michael addition comprising the following steps: a) virtually all functional groups of the core molecule are reacted with one or more vinyl cyanide units; b) virtually all incorporated vinyl cyanide units are hydrogenated to amine groups; c) virtually all amine groups thus formed are reacted with vinyl cyanide units;

steps b) and c) being carried out alternatingly (N-l) times in order to obtain a macromolecule of the desired generation N. The value of N mostly varies from 1 to 10; N preferably has a value of 2 or higher, in particular 3 or higher.

7) Dendrimers obtainable by a process wherein an amount of a core molecule, preferably 1 ,4-diaminobutane, is dissolved in methanol, and reacted with an excess of a vinyl cyanide, preferably acrylonitrile, in a Michael addition reaction whereby a nitrile-terminated reaction product is obtained. In a next reaction step, the nitrile groups of the resulting reaction product are hydrogenated in the precence of hydrogen whereby an amine terminated reaction product is obtained whereby water is used as a solvent. Thereafter, the amine terminated reaction product is again reacted with an excess of acrylonitrile. The Michael addition reaction and the hydrogenation reaction are repeated until a dendrimer of the desired generation is obtained.

Hyperbranched polyesters are suitable for antimicrobial compositions according to the invention.

The antimicrobial hyperbranched polymer compositions according to the invention can be used in styrene free or low styrene content unsaturated polyester resins to give the resins additionally improved mechanical properties. The mechanical properties of these cured unsaturated polyester resins are significantly improved when up to 95 wt% and preferably 5-30 wt% of the hyperbranched polymer or a combination thereof is added into a high solids unsaturated polyester. The mechanical properties of the cured unsaturated antimicrobial polyester resins thus mechanical properties of the cured unsaturated antimicrobial polyester resins thus obtained can be widely modified and adjusted according to the final use of the resin.

The antimicrobial hyperbranched polymer compositions according to the invention can be used as resins which can be cured by conventional curing systems, such as thermally initiated curing using intitators like aliphatic azo compounds or organic peroxides, such as benzoyl peroxide, by a redox reaction initiated curing using organic peroxides, such as methyl ethyl ketone peroxide and metal salts, by photochemically initiated curing using UV-light or by radiation initiated curing by EB-radiation.

The antimicrobial hyperbranched polymer resins have a lower viscosity than conventional oligomer resins and they can be used with or without diluting comonomers. The antimicorbial hyperbranched polymers may however also comprise monofunctional or multifunctional comonomers or mixtures thereof, and a suitable amount of a comonomer is 5-20 wt%. As multifunctional comonomers, compounds with reactive double bonds, preferably with 1-6 (meth)acrylate or acrylate groups can be used, and such as trimethylol propanetri(meth)acrylate, hexanediol diacrylate, trimethylolpropane triallylether, pentaerythritol tri/tetraallylether, triallyl cyanurate, trimethylolpropane triacrylether and pentaerythritol tetraacrylether are suitable. As monofunctional comonomers vinyl aromatic monomers, such as styrene, p-methylstyrene or vinyl toluene are suitable and also alkyl (meth)acrylate, such as methyl (meth)acrylate may be used. The antimicrobial hyperbranched polymers comprising any of the previously mentioned hyperbranched polymers and antimicrobial compounds can be used in many different fields, where antimicrobial effect is desired, such as coating, adehesives, laminates, foils, thin-films, composites, synthetic lubricants, fiber reinforced plastics, medical materials and dental material.

The invention is illustrated in more detail in the following Examples which Examples 1-4

Properties of cured antimicrobial hyperbranched polymer compositions

Resins were made of 3 different dendrimers Dl, PGL and TMGL, which all contained 1.3 wt% of a 40 wt% solution of triclosan. Resins were cured using a conventional peroxide system. As a reference was used a resin based on dendrimer PGL-3 without the antimicrobial agent. The results for gel time and antimicrobial effect are presented in the following Table 1. The antimicrobial effect was determined by an inhibition zone test. The manufacture of the resins is performed in any manner suitable for polyester resins and any additives used in polyester resins can be used.

Table 1

Structures of used dendrimers

PGL

D1

TMGL In Examples 5-9 are presented the principles for the manufacture of suitable hyperbranched structures (dendrimers A-H), wherein 1) A central mono- or polyhydric initiator molecule or polymer is reacted with monocarboxylic acid having at least two hydroxyl groups 5 2) The sufficiently extended structure is terminated with a chain stopper.

Example 5. Preparation of dendrimer A

₍0 ini_tia_tor (n) chain extension and branching (in) termination with methacryhc acid anhydride

15

1) A central mono- or polyhydric initiator molecule or polymer is reacted with trimellitic anhydride

2) The available carboxylic groups are further reacted with the extender molecules having reactivity towards carboxylic groups

20 3) The sufficiently extended structure is terminated with a chain stopper

Example 6. Preparation of dendrimer B (=D1)

(l) reaction of pentaerythπtol with tπmellitic anhydπde (n) chain extension with ghcidvl methacrylate

AcOAc

(m) termination with acetic acid anhydπde

1) Reaction of a central mono- or polycarboxylic initiator molecule or polymer with epoxy containing reactant

2) The available hydroxylic groups are further reacted with the extender molecules having reactivity towards hydroxylic groups

3) The sufficiently extended structure is terminated with a chain stopper

Example 7. Preparation of dendrimer C (= TMGL)

(l) reacting carboxylic initiator with glycidyl methacrylate (π) termination with acetic acid anhydπde

1) Reaction of a chain extender with itself. The chain extender is a monofunctional carboxylic acid having at least two hydroxyl groups.

2) Termination with chain stopper Example 8. Preparation of dendrimer D

Example 9. Examples of other curable hyperbranched structures E, F, G and H (= PGL)

Claims

1. A curable antimicrobial hyperbranched polymer composition, characterized in that the composition comprises a hyperbranched polymer or a combination of hyperbranched polymers, an antimicrobial compound or a mixture of antimicrobial compounds and optionally a polyester resin.

2. A curable antimicrobial hyperbranched polymer composition according to claim 1, characterized in that the composition comprises 0.1-10 wt%, preferably 0.2-5 wt% of the antimicrobial compound.

3. A curable antimicrobial hyperbranched polymer composition according to claim 1 or 2, characterized in that the antimicrobial compound is a polyhexamethylene biguanide derivative, a chlorhexidine derivative, a quaternary ammonium salt, a phenolic compound and preferably 2,4,4'-trichloro-2'-hydroxy-diphenylether.

4. A curable antimicrobial hyperbranched polymer composition according to any one of claims 1-3, characterized in that the hyperbranched polymer is a dendritic hydric or carboxylic cored macromolecule wherein:

(i) a central initiator molecule or initiator polymer is a molecule having at least one reactive hydroxyl group (A), which is bonded to a reactive carboxyl group (B) in a monomer chain extender having two other reactive groups (A) or (B) to be reacted further introducing thus a tree-like branching with ester linkages

or

(i) a central initiator molecule or initiator polymer is a molecule having at least one reactive carboxyl group (B), which is bonded to a reactive hydroxyl group (A) in a monomer chain extender having two other reactive groups (A) or (B) to be reacted further introducing thus a tree-like branching with ester linkages (ii) ester linkages are formed through know-in-art synthetic methods, which are a) esterification of alcohol and carboxylic acid removing condensate water; b) esterification of carboxylic acid by treating it with alcohols in the presence of dehydrating agents; c) esterification of carboxylic acid by treating with tert-butyl ethers and catalysts; d) reaction of carboxylic anhydride with alcohol; e) reaction of carboxylic acid chloride with alcohol; f) reaction of carboxylic acid with a reactive epoxy group in a reactant; g) esterification through transesterification

and/or

(iv) optionally an extender molecule or polymer terminates a chain.

5. A curable antimicrobial hyperbranched polymer composition according to any one of claims 1-4, characterized in that

the central initiator molecule or initiator polymer is selected from the group consisting of a) an aliphatic, a cycloaliphatic or an aromatic diol, b) a triol, c) a tetrol,d) anhydroennea-heptitol or dipentaerythritol,e) a monofuntional alcohol, f) an alkoxylate polymer having a molecular weight of not more than 8000 and being produced by a reaction between an alkylene oxide and one or more hydroxyl groups originating from compounds a) through f); and preferably the initiator molecule is selected from the group consisting of ditrimethylolpropane, ditrimethylolethane, dipentaerythritol, pentaerythritol, alkoxylated pentaerythritol, trimethylolethane, trimethylolpropane, alkoxylated trimethylolpropane, glycerol, neopentylglycol, dimethylolpropane, and l,3-dioxane-5,5-dimethanol; and the monomeric chain extender is selected from the groups: a) monofunctional carboxylic acid having at least two hydroxyl groups b) monofuntional carboxylic acid having at least two hydroxyl groups wherein one or more of the hydroxyl groups are hydroxyalkyl substituted; and preferably said chain extender is selected from the group consisting of dimethylolpropionic acid, α,α,-bis(hydroxymethyl)butyric acid, acid, α,α-bis(hydroxy)propionic acid and 3,5-dihydroxybenzoic acid;

and the chain stopper is selected from the group consisting of a) a saturated monofunctional carboxylic acid or a saturated fatty acid or an anhydride thereof, b) an unsaturated fatty acid, c) an unsaturated monofunctional carboxylic acid,d) a difunctional or a polyfunctional carboxylic acid or an anhydride thereof, e) an adduct or a reaction product of difunctional or a polyfunctional carboxylic acid or an anhydride thereof, f) an aromatic monofunctional carboxylic acid, g) an epihalohydrin, h) a glycidyl ester of a monofunctional acid or of a fatty acid which acid has 1-24 carbon atoms, i) an epoxide of an unsaturated fatty acid with 3-24 carbon atoms, and preferably said chain stopper is selected from the groups consisting of lauric acid, linseed fatty acid, soybean fatty acid, tall oil fatty acid, dehydrated castor fatty acid, capric acid, caprylic acid, trimethylolpropane diallyl ether maleate, acetic acid, metacrylic acid, acrylic acid, benzoic acid, para-tert.bu- tylbenzoic acid, l-chloro-2,3-epoxy propane, l,4-dichloro-2,3-epoxy butane and epoxidized soybean fatty acid.

6. An antimicrobial hyperbranched polymer composition according to any one of claims 1-3, characterized in that the hyperbranched polymer is a hyperbranched polyester of a polyol with 3 to 10 reactive hydroxyl groups and an aromatic polycarboxylic anhydride with 2 to 4 carboxyl groups, each hydroxyl group of the polyol forming an ester linkage with one anhydride group of the polycarboxylic anhydride, and further glycidyl methacrylate, glycidyl acrylate or allyl glycidyl ether forming ester linkages with the remaining carboxyl groups of the anhydride and free hydroxyl groups; and further, in the hyperbranched polyester, methacrylic anhydride and/or acrylic anhydride and/or an aliphatic carboxylic anhydride form ester linkages with free hydroxyl groups formed from the previous reaction.

7. An antimicrobial hyperbranched polymer composition according to any one of claims 1-3, characterized in that the hyperbranched polymer is a hyperbranched polyester based on a polyol core molecule, a polycarboxylic anhydride as a branching extender and an epoxyacrylate as an end groups, and preferably hyperbranched polyesters of a polyol with 2 to 10 reactive hydroxyl groups, preferably of equivalent reactivity, and a polycarboxylic anhydride with 2 to 4 carboxyl groups, preferably with 3 carboxyl groups, each hydroxyl group of the polyol forming an ester linkage with one anhydride group of the polycarboxylic anhydride, and further glycidyl methacrylate, glycidyl acrylate or allyl glycidyl ether forming ester linkage with the remaining carboxyl groups of the anhydride and free hydroxyl groups, and further unsaturated, aromatic or aliphatic anhydride forming ester linkages with free hydroxyl groups.

8. An antimicrobial hyperbranched polymer composition according to any one of claims 1-3, characterized in that the hyperbranched polymer is a multifunctional macromer of a polycarboxylic acid comprising 2 to 4 reactive carboxylic groups and glycidyl methacrylate, glycidyl acrylate or allyl glycidyl ether forming esterlinkages with the carboxylic groups of the acid, and further unsaturated, aromatic or aliphatic anhydride forming ester linkages with the free hydroxyl groups.

9. An antimicrobial hyperbranched polymer composition according to any one of claims 1-3, characterized in that the hyperbranched polymer is a hyperbranched polymer comprising a nucleus and polyol and polycarboxy residues, the hyperbranched polymer having at least 6 terminal hydroxyl- or carboxyl groups and a Carothers gelpoint lower than 1, and the said hyperbranched polymer having at least 6 terminal hydroxyl- or carboxylgroups is obtainable by starting with a nucleus compound containing at lest one hydroxyl group as the nucleus and reacting it with a compound containing at least one anhydride group, after which the resulting first generation acid-terminated addition product is reacted with a compound containing at least one epoxy group; the resulting first generation hydroxyl-terminated addition product thereafter is reacted, in the second generation, with a compound containing in the second generation, with a compound containing at least one anhydride group, after which the resulting second generation acid- terminated addition product, is reacted with a compound containing at least one epoxy group, resulting in a second generation hydroxyl-terminated addition product, and in at least one generation monomers are used that have at least one functional group besides the anhydride group or epoxy group.

10. An antimicrobial hyperbranched polymer composition according to any one of claims 1-3, characterized in that the hyperbranched polymer is a hyperbranched polyester.

11. Use of an antimicrobial hyperbranched polymer composition according to any one of claims 1-10 in coatings, adhesives, laminates, foils, thin-films, composites, synthetic lubricants, fiber reinforced plastics, medical materials and dental materials.

12. A method for the manufacture of an antimicrobial hyperbranched polymer composition, characterized in that 0.1-10 wt%, preferably 0.2-5 wt% of an antimicrobial compound or a mixture of antimicrobial compounds is incorporated into a hyperbranched polymer, or a combination of hyperbranched polymers.

13. A method according to claim 12, characterized in that a polyester resin is incorporated to the hyperbranched polymer.