CN102264789B

CN102264789B - Composition containing antimicrobials in a hybrid network

Info

Publication number: CN102264789B
Application number: CN2009801533301A
Authority: CN
Inventors: R·玛尼梵南; T·艾斯; M·黄; A·费克特科特尔
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-10-28
Filing date: 2009-10-21
Publication date: 2013-09-04
Anticipated expiration: 2029-10-21
Also published as: CN102264789A; WO2010049316A1; KR20110090967A; EP2350158A1

Abstract

The invention relates to a method of preparing a composition comprising (a) reacting - (A) an isocyanate component with in average at least two isocyanate groups per molecule, - (B) a binder component comprising at least one alkoxysilane (B2), wherein the binder component (B) has in average at least two functional groups reactive to isocyanates per molecule, thus obtaining a prepolymer and subsequently (b) hydrolyzing and polycondensing said prepolymer in the presence of - water and - at least one antimicrobial agent (Z) comprising at least one antimicrobial active (Z1) and optionally a particulate carrier substance (Z2), wherein the at least one antimicrobial agent (Z1) is unreactive during step (b). The present invention furthermore relates to compositions obtainable by said method, to coatings comprising said compositions and to a kit of parts comprising a curable composition containing said components (A), (B), and (Z) for joint application. The present invention furthermore concerns the use of said compositions for preparing antimicrobial coatings.

Description

Mix the cancellated composition that comprises biocide

Technical field

The present invention relates to a kind of preparation method for compositions, it comprises

(a) make following component reaction:

-(A) average per molecule has the isocyanate component of at least two isocyanate group,

-(B) comprising the binder ingredients of at least a organoalkoxysilane (B2), wherein said binder ingredients (B) average per molecule has at least two to the functional group of responding property of isocyanic ester,

So, obtain prepolymer, then,

(b) in the presence of following material, the described prepolymer of hydrolysis and polycondensation:

-water and

-at least a biocide (Z), it comprises at least a anti-microbial active matter (Z1) and optional particulate carrier material (Z2),

Wherein said at least a anti-microbial active matter (Z1) is anergy during step (b).

The invention further relates to by the obtainable composition of described method, relate to the coating that comprises described composition, and relate to and comprise the suit in order to combined utilization (kit) that contains described component (A), (B) and curable compositions (Z).The invention further relates to described composition for the preparation of the purposes of antimicrobial coatings.

Background technology

Aspect performance, safety and environment conformability, the requirement of coatings applications is uprised gradually.Known coating based on isocyanic ester and tackiness agent (namely containing the component to the hydrogen atom of responding property of isocyanic ester)---is called polyurethane coating---hereinafter provides high chemical resistance, flexibility, resistance to abrasion, weathering resistance and shock-resistance.The protection that such coating provides has special importance at automobile, building, boats and ships and chemical field.

Polyurethane coating or film can for example utilize isocyanic ester addition polymerization method, prepare by compound (polyvalent alcohol or polyamines) and polyfunctional isocyanic ester (polyisocyanates) reaction that comprises multifunctional hydroxyl or amino.Reaction between the active hydrogen atom of isocyanate group (NCO) and tackiness agent utilizes catalyzer to accelerate usually.

Usually, can produce difference between single component (1K) and two-pack (2K) coated material.The double-component coat material not long ago could mix up to using, thereby only had limited operable time.The characteristics of this class system are fast setting after component is mixed.On the contrary, single-component system has long working life (that is, being kept the enough low time length of viscosity to be used for processing by the resin system of catalysis).Realized this point by for example end-blocking NCO group so far.But when such coating curing, end-capping reagent is escaped.

Be to comprise polyisocyanates and tackiness agent for the known in the art two component curable mixture of the tackiness agent of polyvalent alcohol or polyamines---particularly based on---provides good performance and can solidify at low temperatures.

The needs that this area exists exploitation to have above-mentioned advantage and have the coating of long-term anti-microbial properties simultaneously.Therefore, several different coatings have been proposed in the prior art.

For example from US patent No.452,410 and 5,556, the 699 known zeolites that in antimicrobial coatings, use silico-aluminate or comprise some metal ion.Yet the coating that comprises zeolite or silico-aluminate is opaque, and their use is limited to the coating that thickness is less than 15 microns usually.

From US-A-6,596,401 known uses comprise the composition of silane copolymer and biocide, and wherein said multipolymer is the reaction product of silane and the polyvalent alcohol of at least a polyisocyanates, functional organic.Yet US-P 6,596,401 unexposed hybrid networks.

US patent No.6,572,926 disclose polymeric matrix, and it is exposed in the polymerisable quaternary ammonium salt that is dissolved in the solvent, such as dimethyl stearyl-[3-(trimethoxysilyl) propyl group] ammonium chloride.Quaternary salt in the solvent is aggregated matrix absorption, thereby polymerization produces the matrix that the surface is soaked into by biocide thus.The biocide of polymerization also penetrates the surface to certain degree of depth, forms interpenetrating(polymer)networks.

This method is limited to polymeric matrix by the infiltration of the mixture of some polymerisable quaternary ammonium salts and solvent or swelling.In another embodiment, disclose polymerisable quaternary ammonium salt is joined in the commercially available obtainable coating, thereby original position forms interpenetrating(polymer)networks.Yet, leach only to avoid by the polymerization biocide from coating.And disclosed coating does not still demonstrate the antimicrobial acivity of enough Chinese People's Anti-Japanese Military and Political College enterobacterias (E.Coli).

Summary of the invention

An object of the present invention is to provide the antimicrobial composition that anti-microbial active matter wherein can not leach described composition.A relevant purpose of the present invention provides wherein that antimicrobial acivity is long-term, particularly in the aging coating that continues 5 year period down.Described antimicrobial coatings should can be used for large-scale biocide.

Another object of the present invention provides antimicrobial composition, coating particularly, and it demonstrates anti-streptococcus aureus (Staphylococcus aureus) and colibacillary high effect.In addition, described antimicrobial coatings should be at room temperature kills these bacteriums effectively being no more than in the time of twenty four hours.

Simultaneously, an object of the present invention is to provide antimicrobial coatings, it has chemical resistant properties and weathering resistance, and demonstrate high optical characteristics, enough flame retardant resistance, to good adhesion and the high-wearing feature of polycarbonate and aluminum matrix.

Embodiment

Method of the present invention and solved the problems referred to above by the obtainable composition of described method and coating.Embodiment preferred be described in hereinafter with claims in.The combination of embodiment preferred does not depart from scope of the present invention.

The present invention comprises as defined above step (a) and (b) for the preparation of method for compositions.Step (a) and (b) be described in greater detail in hereinafter.Preferred composition of the present invention exists as coating.

Step (a)

According to the present invention, step (a) comprises makes the following substances reaction, so obtains prepolymer:

-(B) comprising the binder ingredients of at least a organoalkoxysilane (B2), wherein said binder ingredients (B) average per molecule has at least two to the functional group of responding property of isocyanic ester.

Prepolymer refers to still comprise further polymerization and/or crosslinked reactive group or the polymerization system in site.In situation of the present invention, organoalkoxysilane (B2) comprises hydrolyzable group, and this hydrolyzable group forms inorganic reticulated structure according to step (b) in the presence of water, as the part of the hybrid network that obtains.

Each mean value about functionality refers to weighted number average (number-weighted average).

NCO group in the component (A) can change in relative wide scope with the mol ratio that reactive functional groups in the component (B)---is reactive hydrogen atom---.(A) NCO group in: the mol ratio of reactive hydrogen atom can be 10: 1 to 1: 10 (B).But NCO group in (A) preferably: the mol ratio of reactive hydrogen atom is 2: 1 to 1: 2 (B), is 1.1: 0.9 to 0.9: 1.1 especially.NCO group in preferred especially (A): the mol ratio of reactive hydrogen atom is essentially 1: 1 (B).

Isocyanate component (A)

It is well known by persons skilled in the art being suitable for isocyanic ester of the present invention, perhaps can be synthetic according to method known to those skilled in the art.

The term isocyanic ester refer to per molecule have at least one-molecule of NCO group.Isocyanate component can be made up of the single isocyanic ester that per molecule has two a-NCO group at least, or is made up of the mixture that average per molecule has different isocyanic ester of at least two-NCO group.Therefore, isocyanate component of the present invention (A)-number-average of NCO group is at least 2.The term vulcabond refers to that per molecule has the isocyanate compound of two-NCO group.

Component (A) preferably comprises at least a oligopolymer based at least a vulcabond, and the NCO-functionality of described vulcabond is more than 2, and this oligopolymer is called polyisocyanates hereinafter.This oligopolymer based on vulcabond has the low poly structure that contains the unit that comes from vulcabond, and is well known by persons skilled in the art.Preferably, component (A) is the oligomeric '-diphenylmethane diisocyanate (oligomeric MDI) of the known PMDI of being called of those skilled in the art or thick MDI.

As the parent vulcabond, preferably use the vulcabond with 4 to 20 carbon atoms.In principle, the parent vulcabond can mix use with itself or with oligopolymer.Yet preferably, vulcabond uses with oligomeric form.

The example of common vulcabond is aliphatic diisocyanate, such as tetramethylene diisocyanate, 1, derivative, trimethyl cyclohexane vulcabond or the tetramethyl-hexane diisocyanate of 5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-, two isocyanide acyl group hexanes), eight methylene diisocyanates, decamethylene vulcabond, ten dimethylene diisocyanates, ten tetramethylene diisocyanate, lysinediisocyanate; Alicyclic diisocyanate, such as 1,4-, 1,3-or 1,2-two isocyanide acyl group hexanaphthenes, 4,4 '-or 2,4 '-two (isocyanide acyl group cyclohexyl) methane, 1-isocyanide acyl group-3,3,5-trimethylammonium-5-(isocyanatomethyl) hexanaphthene (isophorone diisocyanate), 1,3-or 1,4-two (isocyanatomethyl) hexanaphthene or 2,4-or 2,6-, two isocyanides acyl group-1-methylcyclohexane and 3 (or 4), 8 (or 9)-two (isocyanatomethyl), three ring [5.2.1.02,6] decane isomer mixtures; And aromatic diisocyanate; such as toluene 2; 4-or 2; 6-vulcabond and isomer mixture thereof; between-or right-xylylene diisocyanate; 2,4 '-or 4,4 '-two isocyanide acyl group ditane and isomer mixtures thereof; phenylene 1; 3-or 1; the 4-vulcabond; 1-chlorine phenylene-2, the 4-vulcabond; naphthylidene 1, the 5-vulcabond; biphenylene 4; 4 '-vulcabond; 4; 4 '-two isocyanide acyl groups-3,3 '-dimethyl diphenyl; 3-methyldiphenyl methane 4,4 '-vulcabond; tetramethylxylylene diisocyanate; 1; 4-two isocyanide acyl group benzene or 4,4 '-two isocyanide acyl group phenyl ether.

Usually, it also is suitable having the average more senior isocyanic ester that surpasses 2 isocyanate group.Suitable example comprises triisocyanate; such as three isocyanide acyl group nonanes, 2; 4; 6-three isocyanide acyl group toluene, triphenylmethane triisocyanate or 2; 4; 4 '-three isocyanide acyl group phenyl ether, the perhaps mixture of vulcabond, triisocyanate and the more senior polyisocyanates that obtains by the corresponding aniline/formaldehyde condenses of phosgenation (phosgenating), it shows as the polyphenyl polyisocyanate that comprises methylene bridge.

Alicyclic and aliphatic diisocyanate is preferred.Particularly preferably be 1-isocyanide acyl group-3; 3; 5-trimethylammonium-5-(isocyanatomethyl)-hexanaphthene (isoflurane chalcone diisocyanate), 1; 6-two isocyanide acyl group hexanes, 4; 4 '-two (isocyanide acyl group cyclohexyl) methane and 3 (or 4); 8 (or 9)-two (isocyanatomethyl), three ring [5.2.1.02,6] decane isomer mixtures.

Component (A) can comprise the polyisocyanates that comprises biuret, carbamate, allophanate and/or isocyanurate group and the mixture that contains polyisocyanates, preferably comprises the polyisocyanates of isocyanurate group and/or comprises the polyisocyanates of allophanate groups.The polyisocyanates that especially preferably mainly comprises isocyanurate group.Very particularly preferably, the mark of isocyanurate group be equivalent to nco value at least 5%, preferably at least 10%, more preferably at least 15 weight % (with the C of molar weight 126g/mol ₃N ₃O ₃Calculate).

Preferably the example as the polyisocyanates of component (A) comprises:

1) polyisocyanates that has isocyanurate group and obtain from aromatic series, aliphatics and/or alicyclic diisocyanate.Particularly preferably be corresponding aliphatics and/or alicyclic isocyanide acyl group isocyanuric acid ester herein, particularly based on those of hexamethylene diisocyanate and isoflurane chalcone diisocyanate.The isocyanuric acid ester that exists is three isocyanide acyl group alkyl or three isocyanide acyl group cycloalkyl isocyanuric acid esters in particular, and it is the cyclic trimer of vulcabond, perhaps for have the mixture of the more higher homologue that surpasses an isocyanurate ring with it.The NCO content that described isocyanide acyl group isocyanuric acid ester has usually is 10 to 30 weight %, is 15 to 25 weight % especially, and average N CO functionality is 2.6 to 8.

2) have the isocyanate group of aromatic series, aliphatics and/or alicyclic bonding urea groups diketone vulcabond (uretdione diisocyanate), be preferably the urea groups diketone vulcabond with aliphatics and/or alicyclic binding groups, particularly derived from those of hexamethylene diisocyanate or isoflurane chalcone diisocyanate.Urea groups diketone vulcabond is that the cyclic dimer of vulcabond closes product.Urea groups diketone vulcabond can be used as independent component or as with the mixture of other polyisocyanates, particularly with 1) in the mixture of those polyisocyanates of mentioning use.

3) has biuret group and have---preferred alicyclic or the aliphatics bonding---polyisocyanates of isocyanate group, particularly three (6-isocyanide acyl group hexyl) biurets of aromatic series, alicyclic or aliphatics bonding or itself and the mixture of higher homologue more.The NCO content that these polyisocyanates with biuret group have usually is 18 to 22 weight %, and average N CO functionality is 2.8 to 6.

4) have carbamate and/or allophanate groups and have aromatic series, aliphatics and/or alicyclic bonding---preferred aliphat and/or alicyclic bonding---polyisocyanates of isocyanate group, obtain as can for example passing through excessive hexamethylene diisocyanate or isoflurane chalcone diisocyanate and monohydroxy-alcohol or polyol reaction, described monohydroxy-alcohol or polyvalent alcohol are such as for example methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonylcarbinol, just-dodecanol (lauryl alcohol), 2-Ethylhexyl Alcohol, Pentyl alcohol, stearyl alcohol, hexadecanol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1, the ammediol monomethyl ether, cyclopentanol, hexalin, the ring octanol, cyclododecanols, TriMethylolPropane(TMP), neopentyl glycol, tetramethylolmethane, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, 1, ammediol, 2-ethyl-1, ammediol, the 2-methyl isophthalic acid, ammediol, ethylene glycol, glycol ether, triglycol, Tetraglycol 99, five glycol, glycerine, 1, the 2-dihydroxypropane, 2,2-dimethyl-1,2-ethylene glycol, 1, the 2-butyleneglycol, 1, the 4-butyleneglycol, 3-methylpentane-1, the 5-glycol, 2-ethyl hexane-1, the 3-glycol, 2,4-diethyl-octane-1, the 3-glycol, the neopentyl glycol hydroxy new pentane acid ester, ditrimethylolpropane, Dipentaerythritol, 2,2-two (4-hydroxy-cyclohexyl) propane, 1,1-, 1,2-, 1,3-, with 1, the 4-cyclohexanedimethanol, 1,2-, 1,3-or 1,4-cyclohexanediol, or its mixture.Has NCO content that these polyisocyanates of carbamate and/or allophanate groups have usually for being 12 to 24 weight % based on those of HDI.18-24 weight % especially, average N CO functionality is 2.5 to 4.5.

The polyisocyanates of 5) Bao Han oxadiazine triketone (oxadiazinetrione) groups is preferably derived from hexamethylene diisocyanate or isoflurane chalcone diisocyanate.The polyisocyanates that this bag contains oxadiazine three ketone groups can be prepared by vulcabond and carbonic acid gas.

6) comprise the polyisocyanates of iminooxadiazinedionegroups groups, preferably derived from hexamethylene diisocyanate or isoflurane chalcone diisocyanate.This polyisocyanates that comprises iminooxadiazinedionegroups groups can utilize special catalyst to be prepared by vulcabond.

7) polyisocyanates of uretonimine (uretonimine)-modification.

8) polyisocyanates of carbodiimide-modification.

9) for example from the hyperbranched polyisocyanates of the known kind of DE-A1 10013186 or DE-A1 10013187.

10) from two-and/or the urethane polyisocyanate prepolymers of many-isocyanic ester and alcohol.

11) polyureas-polyisocyanate prepolymers.

Described polyisocyanates 1) to 11) can be used as the mixture use, if suitable, also can be used as the mixture use with vulcabond.

The polyisocyanates that preferably comprises isocyanuric acid ester and/or biuret group.In addition, these mixtures also can comprise a small amount of urea groups diketone, biuret, carbamate, allophanate, oxadiazine triketone, iminooxadiazinedionepolyisocyanates diketone and/or uretonimine groups, its amount preferably is less than 25 weight % separately, more preferably be less than 20 weight % separately, most preferably be less than 15 weight % separately, be lower than 10 weight % separately especially, and be lower than 5 weight % separately in particular, be lower than 2 weight % separately very especially, all based on corresponding functional group meter.

As the isocyanic ester in the component (A), particularly preferably be the isocyanuric acid ester of following isoflurane chalcone diisocyanate: its NCO content according to DIN EN ISO 11909 is 16.7%-17.6%, and/or average N CO functionality is 3.0 to 4.0, and is preferred 3.0 to 3.7, more preferably 3.1 to 3.5.This compounds that comprises isocyanurate group preferably is no more than 150 according to the HAZEN/APHA chromatic number of DIN EN 1557.

Especially preferably also have following 1 as isocyanic ester in the component (A), the isocyanuric acid ester of 6-hexamethylene diisocyanate: its NCO content according to DIN EN ISO 11909 is 21.5-23.5%, and/or average N CO functionality is 3.0 to 8, and is preferred 3.0 to 3.7, more preferably 3.1 to 3.5.This compounds that comprises isocyanurate group preferably is no more than 60 according to the chromatic number of DIN ISO 6271.Comprise this compounds of isocyanurate group at 1000s ^-1Shearing rate under, under 23 ℃, be 1000 to 20000mPas according to the viscosity of DIN EN ISO 3219, be preferably 1000 to 4000mPas.

In a preferred embodiment, total chlorinity that described isocyanate component (A) has is less than 400mg/kg, and more preferably total chlorinity is less than 80mg/kg, most preferably less than 60, especially less than 40, especially less than 20 with even less than 10mg/kg.

Particularly preferably; isocyanate component (A) comprises at least a following compound that is selected from: 1-isocyanide acyl group-3; 3; 5-trimethylammonium-5-(isocyanatomethyl)-hexanaphthene (isoflurane chalcone diisocyanate), 1; 6-two isocyanide acyl group hexanes (HDI), 4; 4 '-two (isocyanide acyl group cyclohexyl) methane and 3 (or 4), 8 (or 9)-two (isocyanatomethyl)-tristane and isomer mixtures thereof.

1,6-, two isocyanide acyl group hexanes (HDI) are very particularly preferred.

Binder ingredients (B)

According to the present invention, binder ingredients (B) comprises at least a organoalkoxysilane (B2), and wherein said binder ingredients (B) average per molecule has at least two to the functional group of responding property of isocyanic ester.

In a preferred embodiment, binder ingredients (B) comprises (B1) at least a tackiness agent that can not react and (B2) at least a organoalkoxysilane in step (b).

Preferably, the tackiness agent (B1) that can not react in step (b) is the tackiness agent that does not contain alkoxysilane groups.

It is well known by persons skilled in the art being suitable for tackiness agent of the present invention (B1), perhaps can be synthetic according to method known to those skilled in the art.

The tackiness agent (B1) that is used for the object of the invention preferably comprises at least two to the compound of the hydrogen atom of responding property of isocyanic ester.Especially, described tackiness agent comprises hydroxyl (OH group) and/or primary amino and/or secondary amino group.

In one embodiment of the invention, use polyvalent alcohol or polyamines as tackiness agent (B1).Polyvalent alcohol refers to comprise the organic molecule of at least 2 of average per molecules (number average (number-weighted)) OH group.In addition, polyamines refers to comprise the organic molecule of at least 2 of average per molecules (number average) primary amino or secondary amino group (that is reactive amino).

Component (B) preferably is at least 15 according to the OH number of DIN 53240-2, preferably at least 40, more preferably at least 60 and 80mg KOH/g resin solid at least most preferably.Described OH quantity can be at the most 350, preferably at the most 240, more preferably at the most 180 and 140mg KOH/g resin solid at the most most preferably.

Preferred OH number also depends on application.According to Manfred Bock, " Polyurethane f ü r Lacke und Beschichtungen ", p.80, Vincentz-Verlag, 1999, lower OH number is favourable for effective adhesion and corrosion control.For top layer material, for example use to have the OH number and be the polyacrylic ester of about 40 to 100mg KOH/g resin solid; For the weather coated material, use has the OH number and is the polyacrylic ester of about 135mg KOH/g resin solid; For high chemical resistance, use has the OH number and is the polyacrylic ester of about 170mg KOH/g resin solid.In some cases, the polyester for the flyer coating has much higher OH number.

Preferably, binder ingredients (B) comprises at least a polyvalent alcohol or at least a polyamines or both, and at least a polyvalent alcohol or at least a polyamines are as tackiness agent (B1).The binder ingredients (B1) that especially preferably comprises at least a polyvalent alcohol.

The example of preferred adhesive (B1) is polyacrylate polyol, polyester polyol, polyether glycol, polyurethane polyol; Polyurea polylol; The polyester polyacrylate polyol; The polyester-polyurethane polyvalent alcohol; Urethane polyacrylate polyol, polyurethane-modified Synolac; Fatty acid modified polyester-polyurethane polyvalent alcohol, with the multipolymer of allyl ethers, have for example graftomer of the described compound of different glass transition temperature, and the mixture of described tackiness agent.Special optimization polypropylene acid esters polyvalent alcohol, the pure and mild polyether glycol of polyester polyols, at least a polyacrylate polyol particularly, it comprises on average at least two of per molecules, preferably two to ten, more preferably three to ten and three to eight hydroxyls most preferably.

Measure according to DIN 53240-2, the preferred OH number of preferred adhesive (B1) is 40 to 350mg KOH/g resin solid for polyester, preferred 80 to 180mg KOH/g resin solid, for polyacrylate polyol (polyacrylate-ol), be 15 to 250mg KOH/g resin solid, preferred 80 to 160mg KOH/g.

Described tackiness agent (B1) can also have according to DIN EN ISO 3682 and is 200mg KOH/g at the most, and preferably at the most 150, the acid number of 100mg KOH/g at the most more preferably.

The acid number of tackiness agent (B1) should be preferably at least 10, more preferably 80mg KOH/g at least.Perhaps, may be less than 10, therefore described tackiness agent contains acid hardly.

This class polyacrylate polyol preferably molecular weight Mn is at least 1000, more preferably at least 2000, and 5000g/mol at least most preferably.Described molecular weight Mn can be for example at the most 200 000, preferably at the most 100 000, more preferably at the most 80 000, and 50 000g/mol at the most most preferably.

Described polyacrylate polyol is the multipolymer of at least a (methyl) acrylate and at least a following compound: described compound have at least one, preferably with regard to a hydroxyl and at least one, preferably with regard to (methyl) acrylate group.

The latter can be α for example, the monoesters of beta-unsaturated carboxylic acid and glycol or polyvalent alcohol, described α, beta-unsaturated carboxylic acid is such as vinylformic acid, methacrylic acid is (in this manual for simply, be called " (methyl) vinylformic acid "), described glycol or polyvalent alcohol preferably have 2 to 20 C atoms and at least two hydroxyls, such as ethylene glycol, glycol ether, triglycol, 1, the 2-propylene glycol, 1, ammediol, 1,1-dimethyl-1,2-ethylene glycol, dipropylene glycol, triglycol, Tetraglycol 99, five glycol, tripropylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, neopentyl glycol, the neopentyl glycol hydroxy new pentane acid ester, 2-ethyl-1, ammediol, the 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, the 6-hexylene glycol, the 2-methyl isophthalic acid, the 5-pentanediol, 2-ethyl-1, the 4-butyleneglycol, 2-ethyl-1, the 3-hexylene glycol, 2,4-diethyl-octane-1, the 3-glycol, 2,2-two (4-hydroxy-cyclohexyl) propane, 1,1-, 1,2-, 1,3-and 1,4-two (methylol) hexanaphthene, 1,2-, 1,3-or 1, the 4-cyclohexanediol, glycerine, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, tetramethylolmethane, ditrimethylolpropane, Dipentaerythritol, sorbyl alcohol, N.F,USP MANNITOL, Glycerol dimer, threitol, erythritol, adonitol (ribitol), arabitol (arabitol), Xylitol, galactitol (melampyrum), maltose alcohol, Palatinitol, molar weight is 162 to 4500, preferred 250 to 2000 poly-THF, molar weight be 134 to 2000 poly--1, ammediol or polypropylene glycol, or molar weight is 238 to 2000 polyoxyethylene glycol.

Preferred vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-or 3-hydroxypropyl acrylate, 1,4-butyleneglycol one acrylate or vinylformic acid 3-(acryloxy)-2-hydroxy-propyl ester, preferred especially vinylformic acid 2-hydroxyl ethyl ester and/or methacrylic acid 2-hydroxyl ethyl ester.

Described hydroxyl monomer in copolyreaction with the mixture of other polymerisable monomer in use, the monomer of the preferred free redical polymerization of described other polymerisable monomer preferably comprises the C that surpasses 50 weight % ₁-C ₂₀, preferred C ₁-C ₄Alkyl (methyl) acrylate, (methyl) vinylformic acid, the vinyl aromatic compound with 20 C atoms at the most, the vinyl esters of carboxylic acids, the vinyl halides that comprise 20 C atoms at the most, the non-aromatic hydrocarbon with 4 to 8 C atoms and 1 or 2 two key, unsaturated nitrile, and composition thereof those.Especially preferably comprise the C that surpasses 60 weight % ₁-C ₁₀Those polymkeric substance of alkyl (methyl) acrylate, vinylbenzene, vinyl imidazole or its mixture.

In addition, polymkeric substance can comprise the hydroxy functional monomers that meets above-mentioned hydroxy radical content, if suitable, also comprises other monomer, and example is (methyl) vinylformic acid glycidyl epoxy ester, ethylenic unsaturated acid, particularly carboxylic acid, acid anhydrides or acid amides.

Other polymkeric substance is polyesterols for example, as by condensation poly carboxylic acid (particularly dicarboxylic acid) and the obtainable polyesterols of polyvalent alcohol (particularly glycol).In order to ensure the polyester polyol functionality that is suitable for polymerization, also partly use triol, tetrol etc., and triprotic acid etc.

Polyester polyol is known, for example is known in Ullmanns

Der technischen Chemie, the 4th edition, the 19th volume, the 62nd to 65 page.Preferably use the polyester polyol that obtains by dibasic alcohol and di-carboxylic acid reaction.As free polycarboxylic substituting, also can use polycarboxylate or its mixture of corresponding multi-carboxy anhydride or corresponding lower alcohol to prepare polyester polyol.Described poly carboxylic acid can be aliphatics, alicyclic, araliphatic (araliphatic), aromatic series or heterocycle, and if suitable, can be replaced and/or be undersaturated by for example halogen atom.The example that can mention comprises following:

Oxalic acid, toxilic acid, fumaric acid, succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, dodecandioic acid, phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, nonane diacid, 1,4-cyclohexane dicarboxylic acid or tetrahydrophthalic acid, suberic acid, nonane diacid, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, carbic anhydride, Pyroglutaric acid, maleic anhydride, dimer (fatty acid) yl, its isomer and hydrogenated products, but and esterified derivative, such as the dialkyl of acid anhydrides or described acid, C for example ₁-C ₄Alkyl ester, preferable methyl, ethyl or n-butyl.Preferred formula HOOC-(CH ₂) _yThe dicarboxylic acid of-COOH, wherein y is 1 to 20 numeral, preferred 2 to 20 even number is preferably succsinic acid, hexanodioic acid, sebacic acid and dodecane dicarboxylic acid.

Suitable polyvalent alcohol for the preparation of polyesterols comprises 1, the 2-propylene glycol, ethylene glycol, 2,2-dimethyl-1,2-ethylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 3-methylpentane-1, the 5-glycol, 2-ethyl hexane-1, the 3-glycol, 2,4-diethyl octane-1, the 3-glycol, 1, the 6-hexylene glycol, molar weight is 162 to 4500, poly--THF of preferred 250 to 2000, molar weight be 134 to 1178 poly--1, ammediol, molar weight be 134 to 898 poly--1, the 2-propylene glycol, molar weight is 106 to 458 polyoxyethylene glycol, neopentyl glycol, the neopentyl glycol hydroxy new pentane acid ester, 2-ethyl-1, ammediol, the 2-methyl isophthalic acid, ammediol, 2,2-two (4-hydroxy-cyclohexyl) propane, 1,1-, 1,2-, 1,3-and 1, the 4-cyclohexanedimethanol, 1,2-, 1,3-or 1,4-cyclohexanediol, tri hydroxy methyl butane, TriMethylolPropane(TMP), trimethylolethane, neopentyl glycol, tetramethylolmethane, glycerine, ditrimethylolpropane, Dipentaerythritol, sorbyl alcohol, N.F,USP MANNITOL, Glycerol dimer, threitol, erythritol, adonitol (ribitol), arabitol (arabitol), Xylitol, galactitol (melampyrum), maltose alcohol or Palatinitol, if suitable, it is alkoxyization as mentioned above.

Preferred alcohol is general formula HO-(CH ₂) _xThose of-OH, wherein x is 1 to 20 number, preferred 2 to 20 even number.Preferably ethylene glycol, butane-1,4-glycol, hexane-1,6-glycol, octane-1,8-two pure and mild dodecanes-1,12-glycol.Neopentyl glycol preferably in addition.

In addition, also suitable is for example by reacting obtainable polycarbonate diol with phosgene and excessive low-molecular-weight alcohol, described low-molecular-weight alcohol be defined as those of the synthetic component of polyester polyol.

The suitable polyester glycol that is based on lactone also, it is homopolymer or the multipolymer of lactone, the hydroxyl termination adducts of preferred lactone and suitable difunctionality starting molecule.Suitable lactone is preferably the (CH derived from general formula HO- ₂) _zThose of the compound of-COOH, wherein z is 1 to 20 number, wherein MU (methylene unit) H atom also can be by C ₁To C ₄Alkyl replaces.Example is 6-caprolactone, beta-propiolactone, gamma-butyrolactone and/or methyl-6-caprolactone, 4-hydroxy-benzoic acid, 6-hydroxyl-2-naphthoic acid or pivalolactone, and composition thereof.The example of suitable starting ingredient comprises that afore mentioned rules is as the low molecular weight diol of the synthetic component of polyester polyol.The phase emergencing copolymer of 6-caprolactone is particularly preferred.Also can use lower polyester diols or polyether glycol as the initiator for the preparation of lactone polymer.As substituting of lactone polymer, also can use the hydroxycarboxylic acid polycondensate of chemically suitable corresponding lactone.

In addition, also be suitable for as polymkeric substance be Aethoxy Sklerol, its addition reaction by oxyethane, propylene oxide or butylene oxide ring and H-active ingredient prepares.The polycondensate of butyleneglycol also is suitable.In addition, can use the hydroxyl-functional carboxylic acid, such as for example dimethylol propionic acid or dimethylolpropionic acid.

Described polymkeric substance can certainly be the compound that comprises primary amino or secondary amino group.

Preferably, tackiness agent (B1) is polyvalent alcohol and/or polyamines, particularly polypropylene glycol or 1,5-pentanediol.

Organoalkoxysilane (B2)

According to the present invention, step (a) comprises makes isocyanate component (A) and binder ingredients (B) reaction, and wherein binder ingredients (B) comprises at least a organoalkoxysilane, and has average at least two functional groups to responding property of isocyanic ester.

The organoalkoxysilane (B2) that per molecule has two reactive functional groups is preferred.Described functional group is preferably the hydroxyl of responding property of isocyanic ester or primary amino or secondary amino group.Organoalkoxysilane (B2) with two primary aminos and/or secondary amino group is particularly preferred.

In an especially preferred embodiment, organoalkoxysilane (B2) comprises the compound of at least a formula (I)

Wherein

N is 1 to 6 integer;

R ¹Be selected from H and the C that can be straight chain, side chain or ring-type ₁-C ₆Alkyl;

R ²And R ³Be independently selected from OH, OR ¹With can be the C of straight chain, side chain or ring-type ₁-C ₆Alkyl, R ¹Has aforesaid implication;

R ⁴And R ⁵Be independently selected from H, can be the C of straight chain, side chain or ring-type ₁-C ₆Alkyl, C ₁-C ₆Aminoalkyl group and C ₁-C ₆Hydroxyalkyl, described alkyl are straight chain, side chain or ring-type.

R ⁴And R ⁵Be preferably especially-CH ₂CH ₂-NH ₂With-CH ₂CH ₂-OH.

Condition is that described organoalkoxysilane (B2) comprises at least two to the functional group of responding property of isocyanic ester.

Very particularly preferably, organoalkoxysilane (B2) is selected from least a of following substances: N-(3-(trimethoxysilyl) propyl group) quadrol, 1-(3-(trimethoxysilyl) propyl group) diethylenetriamine, two (3-(methylamino-) propyl group) Trimethoxy silane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, the gamma-amino propyl trimethoxy silicane, 3-(N-styryl methyl-2-aminoethylamino) propyl trimethoxy silicane, the combination of N-phenyl amino Union carbide A-162 and two-(γ-trimethoxy-silylpropyl) amine and these organoalkoxysilanes.

More preferably, organoalkoxysilane (B2) is selected from 3-[two (2-hydroxyethyl) amino] propyl-triethoxysilicane] and the 3-[(2-aminoethylamino) propyl group] Trimethoxy silane at least a.

The amount of described alkoxysilane compound containing trialkylsilyl group in molecular structure (B2) is preferably 2 to 60 weight % with respect to component A and B gross weight.Particularly preferably, the amount of described alkoxysilane compound containing trialkylsilyl group in molecular structure (B2) is 6 to 30 weight % with respect to component A and B gross weight, very particularly preferably is 10 to 20 weight %.

The reaction of the compound that carries out according to the present invention can be carried out in many ways.In a preferred embodiment, isocyanate component (A) and the binder ingredients (B1) of total amount and (B2) reaction simultaneously.

In another embodiment, binder ingredients (b1) and excessive di-isocyanate reaction form isocyanate-terminated polyurethane prepolymer.Can promote the formation of this prepolymer by using excessive isocyanate component (A).In other words, the isocyanate functional group's who exists in reaction mixture quantity is greater than the quantity of the alcohol functional group that exists in reaction mixture.Preferably, the isocyanate functional group is 1.1: 1 to 2: 1 with the ratio of alcohol or other isocyanate-reactive functional group.More preferably, the ratio of isocyanate functional group and alcohol functional group is 1.5: 1 to 2: 1, most preferably 1.6 to 1.8.

Then, described isocyanate-terminated polyurethane prepolymer and organoalkoxysilane (B2) reaction form the polyurethane-urea-silicone copolymers with side chain alkoxyl group.

Step (b)

According to step of the present invention (b), in the presence of following substances, prepolymer hydrolysis and the polycondensation that will in step (a), obtain:

-water and

Term " anti-microbial active matter " refers to have the compound of antimicrobial acivity, and wherein said compound can be organic molecule, inorganic or organic ion material or particulate matter.

Step (b) can be undertaken by many diverse ways.The existence of water can obtain by utilizing dissolved constituent (A) and/or water-containing solvent (B), such as preferred acetone as solvent.By this method, be hydrolyzed and cause the needed water of polycondensation and be present in inherently in the described system.Also can add water separately before at step (b).

In whole specification sheets, water-content is by Karl Fischer Titration, preferably measures according to the coulometry Karl Fischer titration of ISO 760:1978.

Preferred water-content is determined with respect to the weight of organoalkoxysilane (B2) in the step (b).With respect to 100 weight part organoalkoxysilanes (B2), the water-content in step (b) is that 5 to 100 weight parts are suitable.Preferably, the organoalkoxysilane with respect to 100 parts (B2), the water amount in step (b) are 8 to 50 weight parts, particularly preferably are 10 to 35 weight parts, very particularly preferably are 10 to 25 weight parts.

Step (b) can be at room temperature or at from 30 to 100 ℃, carries out under the temperature of from 30 to 60 ℃ rising especially.Step (b) can be simultaneously at standard pressure or 0.1 to 300mbar, particularly carry out under 1 to 100mbar the vacuum.Step (b) also can be called drying process, and wherein hydrolysis and polycondensation take place inherently.Preferably, carry out step (b), make to form coating.In other words, the formation of the present composition and the coating on matrix are carried out simultaneously.

The hydrolysis of step (b) and polycondensation can be randomly by catalysts.Appropriate catalyst is well known by persons skilled in the art such as bronsted lowry acids and bases bronsted lowry.

Step (b) obtains comprising the polymer network structure of anti-microbial active matter (Z1).Anti-microbial active matter (Z1) does not covalently bind in the silica network that obtains during the step (b), and in specific embodiment, it discharges in the time of can automatically discharging or be triggered.Step (b) comprises the siloxy groups condensation that makes hydrolysis, thereby forms covalently bound silica network to urethane, and it comprises the anti-microbial active matter (Z1) of embedding form rather than covalently bound form.Preferably, composition of the present invention keeps anti-microbial active matter (Z1), preferably in the presence of water with its release.

Biocide (Z)

Biocide (Z) can by the mixture of single antimicrobially active compounds (Z1), antimicrobially active compounds (Z1) that two or more are different or more than one antimicrobially active compounds (Z1) among the carrier substance (Z2) of particle form or on and form.

According to the present invention, prerequisite is that described at least a anti-microbial active matter (Z1) is anergy during step (b).Term " anergy " refers to that described anti-microbial active matter (Z1) can not react during step (b), that is, during the hydrolysis and polycondensation in the presence of water, can not with the prepolymer coreaction.Term " reactive " and " reaction " refer to chemical reaction, namely form chemical bond, and this interacts different such as embedding with physics.In other words, " in anergy during the step (b) " refers to not form chemical bond basically with anti-microbial active matter (Z1) during step (b).

Step (b) comprises preferably utilizes hydrolysis and polycondensation component (B2) to make the further polymerization of described prepolymer, described component (B2) and prepolymer covalent attachment.

Preferably, described anti-microbial active matter (Z1) do not comprise can with any functional group of Si-OH radical reaction, described Si-OH group preferably exists as intermediate in step (b).In other words, described anti-microbial active matter does not covalently bind in the cancellated inorganic part of mixing that forms during the step (b).

In principle, under the condition of above-mentioned definition, can use any biocide (Z).

In a preferred embodiment, biocide (Z) not only comprises anti-microbial active matter (Z1), and comprises particulate carrier material (Z2).The reactive group that carrier substance (Z2) in a specific embodiments can react during the surface is included in step (b).

According to first embodiment preferred that hereinafter is called " PE-1 ", biocide (Z) comprises as the silver ions of anti-microbial active matter (Z1) with as one of the zeolite of particulate carrier material (Z2) and polyalcohol hydrogel.

According to second embodiment preferred that hereinafter is called " PE-2 ", biocide (Z) comprises the particulate anti-microbial active matter (Z1) with number average bead diameter 1 to 500nm, be selected from: (i) zinc oxide and (II) comprise the titanium dioxide of AgBr and phosphatic rock.

The titanium dioxide of sealing with AgBr and phosphatic rock is well known by persons skilled in the art.Known AgBr strengthens photocatalysis property and/or the antimicrobial efficacy of titanium dioxide.Known phosphatic rock is encapsulated with and helps prevent the degraded of organic polymer on every side.

According to the 3rd embodiment preferred that hereinafter is called " PE-3 ", biocide (Z1) is selected from quaternary ammonium salt and 2-bromo-2-nitropropane-1, at least a in the 3-glycol.

Hereinafter, embodiment preferred PE-1, PE-2 and PE-3 at length are discussed.

According to embodiment preferred PE-1, biocide (Z) comprises as the silver ions of anti-microbial active matter (Z1) with as one of the zeolite of particulate carrier material (Z2) and polyalcohol hydrogel.

In principle, any zeolite that can keep silver ions all is suitable for as particulate carrier material of the present invention (Z2).The zeolite granular that keeps the silver ions with anti-microbial properties is that prior art is known.For example, the silver zeolite that can be used for the object of the invention is described among US-P 4911898, US-P 4911899, US-P 4938955, US-P4906464, US-P4775585 and the WO 03/055314.

The polyalcohol hydrogel that keeps silver ions also is well known in the prior art.In principle, can use can keep silver ions any polyalcohol hydrogel as particulate carrier material of the present invention (Z2).

Term " gel " refer to comprise liquid phase and solid phase, be the material that long chain molecule is formed by the interconnection polymerizable molecular that forms tridimensional network.Polymer network structure is embedded in the liquid medium.Gel preferably has the co-continuous phase.Hydrogel refers to that wherein liquid phase is the gel of water.

The polymer backbone of hydrogel is normally formed by the hydrophilic monomer unit, and it can be neutral or ion.The example of neutral hydrophilic monomeric unit is oxyethane, vinyl alcohol, (methyl) acrylamide, N-alkylation (methyl) acrylamide, N-methylol (methyl) acrylamide, the N-vinyl-amine, the N-vinyl formamide, the N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylformamide, (methyl) acrylic acid hydroxy alkyl ester is such as hydroxyethyl methylacrylate, vinyl pyrrolidone, (methyl) acrylate of polyoxyethylene glycol mono allyl ether, the allyl ethers of polyoxyethylene glycol, sugar unit is such as glucose or semi-lactosi.The example of cationic hydrophilic monomeric unit is ethylene imine (protonated form), diallyldimethylammonium chloride and propyl methyl acid amides trimethyl ammonium chloride.The example of anionic monomer unit is (methyl) vinylformic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, vinyl phosphonate, 2-methacryloxy ethane sulfonic acid, 4-vinylbenzenesulfonic acid, allyl sulphonic acid, vinyl toluene sulfonic acid and vinyl benzene phosphonic acids (each cited compound is the deprotonation form).

Be suitable for also can obtaining by polymerization unsaturated acid in the presence of a small amount of multiple ethylenically unsaturated compounds as the hydrogel of particulate carrier material (Z2), described unsaturated acid is vinylformic acid, methacrylic acid and/or propenyl amido propane sulfonic acid for example.Suitable hydrogel particularly comprises specific organosilicon comonomer, as three (2-acetoxyl group ethyl dimethylsilane oxygen base) silyl propyl group acrylate and/or methacrylic ester, three (2-propyloic dimethylsilane oxygen base) silyl propyl group acrylate and/or methacrylic ester, three (3-hydroxypropyl dimethyl siloxy-) silyl propyl group acrylate and/or methacrylic ester, the acrylate of the alkyl siloxanes that the functionality fluorine replaces and methacrylic ester are such as three (3,3,3-trifluoro propyl dimethylsilane oxygen base) silyl propyl group acrylate and/or methacrylic ester, three [3-seven fluorine isopropoxide propyls)] dimethylsilane oxygen base silyl propyl group acrylate and/or methacrylic ester, and three (pentafluorophenyl group dimethylsilane oxygen base) silyl propyl group acrylate and/or methacrylic ester.Other hydrogel that is called super water absorption polymer also is suitable.Such hydrogel for example is described in US-P 4,057, and 521, among US-P 4,062,817, US-P 4,525,527, US-P 4,286,082, US-P 4,340,706 and the US-P 4,295,987.

By ethylenic unsaturated acid graft copolymerization obtainable hydrogel on different substrates also is suitable for as particulate carrier material (Z2), described matrix is polysaccharide, polyalkylene oxide and derivative thereof for example.Such graft copolymer is known, for example is known in US-P 5,011,892, US-P 4,076,663 and US-P 4,931,497.

After hydrogel is pulverized, use known contact drying or convection drying method to make its drying usually.The example of contact drying device is hot plate, film type, pot type, contact zones, screen cylinder (sieve drum) formula, screw, rolling disk or contact disc moisture eliminator.The example of comvection dryer is that (Kirk-Othmer 7,326-398 for pellet type, chamber formula, channel-type, flat screen type, board-like, rotary drum, free decline shaft type, sieve belt, streaming, atomizing, fluidized-bed, moving-bed, oar formula or ball bed formula moisture eliminator; (3rd) 1,598-624; 8,75-130,311-339; 5,104-112; Ullmann 1,529-609; 11,642 ff.; (4th) 2,698-721; Vt Industrielle Praxis: " Fortschritte auf dem Gebiet der Einbandtrockner, Teil 1:Auslegungsverfahren, E.Tittmann; Research Disclosure 96-38363: " Drying of Pasty Materials using a Continuous Through-Circulation Belt Dryer ").

It is crosslinked slightly that the hydrogel that uses among the present invention is preferably.Vinyl, non-vinyl or double mode (dimodal) linking agent can be used as linking agent separately or as mixture or with different array configurations.Advantageously use this area to become known for the polyvinyl linking agent of super water absorption polymer usually.Preferred compound with at least two polymerizable double bonds comprises: divinyl compound or polyvinyl compound, such as Vinylstyrene, divinyl toluene, divinyl dimethylbenzene, divinyl ether, divinyl ketone and trivinylbenzene; The diester of unsaturated monocarboxylic or poly carboxylic acid and polyvalent alcohol or polyester are such as two of following polyvalent alcohol-or three-(methyl) acrylate: ethylene glycol, glycol ether, triglycol, Tetraglycol 99, propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, TriMethylolPropane(TMP), glycerine, polyoxyethylene glycol and polypropylene glycol; Can react the unsaturated polyester that obtains such as toxilic acid by any above-mentioned polyvalent alcohol and unsaturated acid; The diester of undersaturated monocarboxylic acid or poly carboxylic acid and following polyvalent alcohol or polyester, described polyol derivative is from C ₂-C ₁₀2 to 8 C of polyvalent alcohol and every hydroxyl ₂-C ₄The reaction of alkylene oxide unit is such as TriMethylolPropane(TMP) six oxyethyl group triacrylates; Two-or three-(methyl) acrylate that can obtain by the reaction of polyepoxide and (methyl) vinylformic acid; Two (methyl) acrylamide, such as N, N-methylene radical-diacrylamine; Can pass through polyisocyanates (such as toluenediisocyanate, hexamethylene diisocyanate, 4,4 '-diphenylmethanediisocyanate) and contain the carbamyl ester that the monomer reaction of the prepolymer of NCO and hydroxyl obtains, the described NCO of containing prepolymer obtains by described vulcabond and the compound reaction that contains active hydrogen atom, and described carbamyl ester is such as passing through two (methyl) vinylformic acid carbamyl ester that above-mentioned vulcabond and the reaction of (methyl) Hydroxyethyl acrylate obtain; Two (first generation) allyl ethers of polyvalent alcohol or poly-(first generation) allyl ethers, such as polyoxyethylene glycol diallyl ether, allylation starch and allylation Mierocrystalline cellulose, described polyvalent alcohol is such as alkylene glycol, glycerine, polyalkylene glycol, polyoxyethylene polylol and carbohydrate; Polycarboxylic diallyl ester or polyene propyl diester are such as diallyl phthalate and hexanodioic acid diallyl ester; With the ester of the list of undersaturated monocarboxylic acid or poly carboxylic acid and polyvalent alcohol (first generation) allyl ester, such as allyl methacrylate(AMA) or (methyl) acrylate of polyoxyethylene glycol mono allyl ether.

The linking agent of preferred type comprises, for example two (methyl) acrylamide; Allyl group (methyl) acrylate; The diester of (methyl) vinylformic acid and polyvalent alcohol or polyester are such as diethylene glycol diacrylate, Viscoat 295 and polyethyleneglycol diacrylate; With diester or the polyester of undersaturated monocarboxylic acid or poly carboxylic acid and polyvalent alcohol, described polyol derivative is from C ₁-C ₁₀2 to 8 C of polyvalent alcohol and every hydroxyl ₂-C ₄The reaction of alkylene oxide unit is such as ethoxylated trimethylolpropane triacrylate.

According to embodiment preferred PE-1, biocide (Z) comprises the silver ions as anti-microbial active matter (Z1).Described anti-microbial active matter (Z1) exists preferably as silver salt.

The example of silver salt comprises; silver acetate for example; acetopyruvic acid silver; silver azide; silver carbide; silver arseniate; silver benzoate; the fluorine silver hydride; one silver fluoride; silver fluoride; Argentic fluoride (silver borfluoride); silver bromate; Silver monobromide; silver carbonate; silver chloride; silver chlorate; silver chromate; silver citrate; silver cyanate; silver cyanide; (suitable; suitable-1; the 5-cyclooctadiene)-1; 1; 1; 5; 5; 5-hexafluoro Acetyl Acetone acid silver; silver dichromate four-(pyridine)-complex compound; siliver diethyldithiocarbamate; silver fluoride (l); silver fluoride (II); 7; 7-dimethyl-1; 1; 1; 2; 2; 3; 3-seven fluoro-4,6-suberic acid silver; hexafluoro-antimonic acid silver; the hexafluoro-silver arseniate; phosphofluoric acid silver; silver iodate; Silver iodide; isothiocyanic acid silver; silver potassium cyanide; silver lactate; silver molybdate; Silver Nitrate; silver nitrite; silver suboxide (I); silver suboxide (II); silver oxalate; silver perchlorate; perfluorobutyric acid silver; perfluorinated acid silver; silver permanganate; perrhenic acid silver; Trisilver phosphate; the silver trinitrophenolate monohydrate; silver propionate; silver selenate; silver selenide; silver selenite; Sulfadiazine Silver; Sulfuric acid disilver salt; silver sulfide; silver sulfite; silver telluride; silver tetrafluoroborate; silver tetraiodomecurate; four wolframic acid silver; silver thiocyanide; tosic acid silver; the trifluoromethanesulfonic acid silver salt; trifluoroacetic acid silver salt and vanadic acid silver.Also can use the mixture of various silver salt.Preferred silver salt is silver acetate, silver benzoate, silver bromate, silver chlorate, silver lactate, silver molybdate, Silver Nitrate, silver nitrite, silver suboxide (I), silver perchlorate, silver permanganate, silver selenate, silver selenite, Sulfadiazine Silver and Sulfuric acid disilver salt.Most preferred silver salt is silver acetate and Silver Nitrate.Also can use the mixture of silver salt.

The preferred content of silver in described hydrogel is 0.07 to 0.7 weight % with respect to the hydrogel gross dry weight.

According to embodiment preferred PE-2, biocide (Z) comprises the particulate anti-microbial active matter (Z1) with number average bead diameter 1 to 500nm, is selected from: zinc oxide and comprise AgBr and the titanium dioxide of phosphatic rock.

Number average bead diameter refers to as measure the value of combining image assay determination by TEM.

Number average bead diameter as the particulate anti-microbial active matter of component (Z1) is preferably 5 to 100nm, is 10 to 50nm especially, particularly preferably is 15 to 45nm, very particularly preferably is 20 to 40nm.

Preferably use the stable particle of anti-microbial active matter (Z1).If Z1 is zinc oxide, it is preferred then utilizing acrylic polymers to stablize.

Preferably use the zinc oxide that has mixed as the doping agent of description in US-A 2005/0048010 in addition.

Can doping agent be joined in the zinc oxide fluid dispersion by mode well known by persons skilled in the art.The suitable doping agent that is used for zinc oxide be many electronics or the metal ion of an electronics less on outer electronic shell especially.The main group metal of oxidation state+III and subgroup metal are specially suitable.Boron (III), aluminium (III), gallium (III) and indium (III) are very particularly preferred.These metals can join with the form of soluble salt in the dispersion liquid, and the selection of metal-salt depends on whether it is dissolved in the dispersion agent with the concentration of expecting.Under the situation of aqueous dispersions, many inorganic salt or its mixture all are suitable, such as carbonate, halogenide, with EDTA salt, nitrate, with the salt of EDTA, acetyl-pyruvate etc.Doped precious metal also is fine such as palladium, platinum, gold etc.

Particularly preferably use the Zinc oxide nanoparticle of finishing as anti-microbial active matter (Z1).The finishing of ZnO nano particle is well known by persons skilled in the art, for example is described among the US-A 2006/0210495, includes it in this specification sheets by the mode of quoting as proof.Finishing preferably obtains by coating materials is administered on the ZnO nano particle, is applied to especially in the dispersion liquid that comprises described nano particle.Especially, suitable coating materials be disclosed in US-A 2006/0210495 the 89th section (page 5) in the 183rd section (the 6th page).

Also can use the surface of modifying the ZnO nano particle in US-A 2007/0243145 as the polymkeric substance of describing, the document is included this specification sheets in by the mode of quoting as proof.

The described polymkeric substance that is used for modification ZnO nano grain surface for purpose of the present invention preferably is selected from the multipolymer of describing as at the 18th section (page 2) to the 35th section (page 3).

The suitable titanium dioxide that comprises AgBr and phosphatic rock is known in M.R.Elahifard, S.Rahimnejad, and S.Haghighi, M.R.Gholami, J.Am.Chem.Soc 2007; 129 (31); Among the 9552-9553.

Preferably, be used for TiO of the present invention ₂Be finishing, utilize silane as coating materials especially.

Different suitable silane as coating materials is listed in the document, includes its content in this specification sheets by the mode of quoting as proof, particularly:

-US-P 6,013, and 372, the 13 hurdles (the 54th goes) be (the 54th row) to the 14th hurdle,

-US-P 6,663,851, the 2 hurdles (the 9th row) to the 2nd hurdle (the 54th row) and

-US-A 2006/0159637, the 44 section (page 2) is to the 83rd section (page 3).

Can use the mixture of two or more above-mentioned silane to carry out finishing.

Also preferably use the photocatalyst contain antimicrobial enhancing agent, as at US-P 6,013, describe in 372, include its content in this specification sheets by the mode of quoting as proof, particularly the 15th page.

Also preferably use as at the photocatalyst that contains hotchpotch of the 15th page of 25-30 line description of US-P 6013372.

US patent 6627173,7175911 and 5597515 has been described the titanium dioxide of doping nitrogen, fluorine and carbon, and it also is suitable.

In a preferred embodiment, with applying TiO as the phosphatic rock calcium of in US-A 2007/0154378, describing ₂, include its content in this specification sheets by the mode of quoting as proof, particularly the 15th section and the 16th section (page 2).

According to the 3rd embodiment preferred " PE-3 ", biocide (Z1) is selected from quaternary ammonium salt and 2-bromo-2-nitropropane-1, at least a in the 3-glycol.

Preferred quaternary ammonium salt is benzyl alkyl-dimethyl ammonium chloride, [2-[[2-[(2-propyloic) (2-hydroxyethyl) amino] ethyl] amino]-2-oxygen base-ethyl] cocoa alkyl dimethyl ammonium hydroxide, benzyl-C _12-14-alkyl-dimethyl ammonium chloride, benzyl-C _12-16-alkyl-dimethyl ammonium chloride, benzyl-C _12-18-alkyl-alkyl dimethyl ammonium chloride, C _12-14-alkyl [(ethylphenyl) methyl] alkyl dimethyl ammonium chloride, just-C _10-16-alkyl trimethylene diamines and chloroacetic reaction product, two-C _8-10-alkyl-dimethyl ammonium chloride, dialkyl group (C _8-18) the Dimethyl Ammonium compound, Timbercote 2000, hexadecylpyridinium chloride, xenyl-2-alcohol, bronopol (bronopol), hexadecylpyridinium chloride, parachlorometacresol, chloroxylenol (chloroxylenol), D-glyconic acid and N; N "-two (4-chloro-phenyl-s)-3,12-diimino-2,4,11, the compound of the 13 4 azepine tetradecanes, two amidines (2: 1), ethanol, formaldehyde, formic acid, glutaraldehyde, oneself is-2 years old, the 4-diolefinic acid, 1-phenoxy group propan-2-ol and 2-phenoxypropanol, oligomeric-(2-(2-oxyethyl group) ethoxyethyl group chlorination guanidine), two (permonosulphuric acid salt) two (vitriol), five potassium, the 2-phenoxyethyl alcohol, Phthalyldicarboxaldehyde, 6-(phthalimido) crosses oxy hexanoic acid, poly-(hexamethylene-diamine chlorination guanidine), (E, E)-oneself is-2 years old, 4-diolefinic acid potassium, third-1-alcohol, propan-2-ol, tetrahydroxy Jia Ji phosphonium salt, orthoxenol and orthoxenol salt, 1-(3-chlorallyl)-3,5,7-three azepines-1-nitrogen diamantane salt, (5-chloro-2, the 4-dichlorophenoxy)-phenol, 3,4,4 '-trichloro-symmetrical diphenyl urea (neko), neighbour-benzo-right-chlorophenol, right-hydroxy benzoate, 2-(thiocyanomethylthio) benzothiazole, 3,5-dimethyl-1,3,5-thiadiazine alkane-2-thioketones, 2,4 dichloro benzene methyl alcohol.

2-bromo-2-nitropropane-1, the 3-glycol is particularly preferred as anti-microbial active matter (Z1).

Hereinafter embodiment preferred refers to embodiment preferred PE-1, PE-2 and PE-3 as described above.

Preferably, the amount of described biocide Z is 1 to 10 weight % based on the composition gross dry weight.

Gross dry weight refers to the weight of composition after desolventizing.

In a preferred embodiment, also comprise antimicrobial components (Z ') according to composition of the present invention, it can be with component (A) during step (b) and/or (B) reacts in the presence of water.Therefore, antimicrobial components (Z ') is covalently bond to the cancellated inorganic part of resulting mixing.

Preferred biocide (Z ') comprise the organoalkoxysilane part, and represented by following formula (II):

Wherein

-R ₁Be C ₁-C alkyl, preferred C ₈-C ₃₀Alkyl,

-R ₂And R ₃, R ₄And R ₅Be C independently of one another ₁-C ₃₀Alkyl or hydrogen and

-X is counter ion, such as Cl ^-, Br ^-, I ^-Or CH ₃COO ^-

Being used for organosilicon quaternary ammonium salt examples for compounds of the present invention is 3-(triethoxysilyl)-propyl-dimethyl octadecyl ammonium chloride, 3-(trimethoxysilyl) propyl group methyl dioctyl ammonium chloride, 3-(trimethoxysilyl) propyl-dimethyl decyl (cecyl) ammonium chloride, 3-(trimethoxysilyl)-propyl group methyl didecyl ammonium chloride, 3-(trimethoxysilyl) propyl-dimethyl dodecyl chlorination ammonium, the two dodecyl chlorination ammoniums of 3-(trimethoxysilyl)-propyl group methyl, 3-(trimethoxysilyl) propyl-dimethyl tetradecyl ammonium chloride, 3-(trimethoxysilyl) propyl group methyl double hexadecyl ammonium chloride and 3-(trimethoxysilyl) propyl-dimethyl octadecyl ammonium chloride.

The amount of described biocide (Z ') in composition advantageously is with respect to composition dry weight about 0.1% to about 50%.The preferred amount of this reagent is 1% to 10% of composition based on the composition dry weight.

Catalyzer

Reaction between polyisocyanates A and the binder compound B is preferably by using catalyzer to carry out.

The limiting examples of appropriate catalyst is tertiary amine, such as N, N-dimethylaminoethanol, N, N-dimethyl-hexahydroaniline-two (2-dimethyl aminoethyl) ether, N-ethylmorpholine, N, N, N ', N '; N "-pentamethyl--diethylenetriamine and 1-2 (hydroxypropyl) imidazoles, and metal catalyst is such as stannous octoate, stannous octoate, dibutyl tin dilaurate, two lauric acid, two hot tin or or dibutyl tin dilaurate, mercaptan two fourth tin, acetopyruvic acid iron, lead octoate 36 and two ricinolic acids, two fourth tin.Preferably, catalyzer is tinbase.Most preferred catalyzer is two lauric acid, two hot tin or dibutyl tin dilaurates.

Other component

Preferably, composition of the present invention also comprises solvent (D).

The example of solvent (D) be alcohol, ester, ester alcohol, ether, ether alcohol, aromatic series and/or fat (alicyclic ring) family hydrocarbon, and composition thereof and halohydrocarbon.Via aminoresin, also alcohol can be introduced in this mixture.

Preferred chain acid alkyl ester, chain acid alkyl ester alcohol, alkoxylate chain acid alkyl ester and composition thereof.

The example of ester comprises n-butyl acetate, ethyl acetate, acetic acid 1-methoxy propyl-2-base ester, acetic acid 2-methoxyl group ethyl ester; and the monoacylphosphine ester of ethylene glycol, glycol ether, triglycol, propylene glycol, dipropylene glycol or tripropylene glycol and diacetyl ester, such as acetic acid butyl glycol ester.Other example is carbonic ether, such as preferred 1, and 2-NSC 11801,1,2-propylene carbonate or 1,3-propylene carbonate.

Ether is for example tetrahydrofuran (THF) (THF), diox, and dimethyl, diethyl or the di-n-butyl ether of ethylene glycol, glycol ether, triglycol, propylene glycol, dipropylene glycol or tripropylene glycol.

Alcohol is for example methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonylcarbinol, n-dodecane alcohol (lauryl alcohol), 2-Ethylhexyl Alcohol, cyclopentanol or hexalin.

Alkanoates alcohol is for example poly-(C ₂To C ₃) alkylene glycol (C ₁To C ₄) the monoalky lether acetic ester.Ether alcohol is for example poly-(C ₂To C ₃) alkylene glycol two (C ₁To C ₄) alkyl oxide, dipropylene glycol dme, preferred butyl glycol.

Aromatic hydrocarbon mixture is mainly to comprise C ₇To C ₁₄Aromatic hydrocarbon and can comprise those of 110 to 300 ℃ of boiling ranges, preferred especially toluene, neighbour-,-or various isomer, ethylbenzene, cumene, the tetraline of the various isomer of right-dimethylbenzene, trimethylbenzene, durene and comprise their mixture.

The example is the Solvesso from ExxonMobil Chemical

Series, particularly Solvesso for example

100 (CAS no.64742-95-6 mainly is C9 and C10 aromatic hydrocarbon, the about 154-178 of boiling range ℃), 150 (the about 182-207 of boiling range ℃) and 200 (CAS no.64742-94-5), and from the Shellsol of Shell

Series, from the Caromax of Petrochem Carless Series, for example Caromax 18, perhaps from the product of DHC Hydrosol for example

A/170.The hydrocarbon mixture that comprises paraffinic hydrocarbons, naphthenic hydrocarbon and aromatic hydrocarbon also is commercially available obtainable, name is called Kristalloel, and (for example Kristalloel 30, the about 158-198 of boiling range ℃, or Kristalloel 60:CAS no.64742-82-1), petroleum solvent (similarly, CAS no.64742-82-1 for example) or solvent naphtha (lightweight: the about 155-180 of boiling range ℃, heavy: the about 225-300 of boiling range ℃).The aromatic hydrocarbon content of this hydrocarbon mixture surpasses 90 weight % usually, preferably surpasses 95 weight %, more preferably surpasses 98 weight %, most preferably surpasses 99 weight %.Suggestion is used has the hydrocarbon mixture that lacks naphthalene content especially.

The density according to DIN 51757 can be less than 1g/cm under 20 ℃ for described hydrocarbon ³, preferably less than 0.95, more preferably less than 0.9g/cm ³

The content of described aliphatic hydrocarbon is usually less than 5 weight %, preferably less than 2.5 weight %, more preferably less than 1 weight %.

Halohydrocarbon is for example chlorobenzene and dichlorobenzene or its isomer mixture.

Fat (alicyclic ring) family hydrocarbon is the isomer mixture of naphthane, alkylation naphthane and straight or branched alkane and/or naphthenic hydrocarbon for example.

Preferred n-butyl acetate, ethyl acetate, acetic acid 1-methoxy propyl-2-base ester, acetic acid 2-methoxyl group ethyl ester and composition thereof.

The mixture of this kind can be with volume ratio 10: 1 to 1: 10 preparation, preferably with volume ratio 5: 1 to 1: 5, more preferably with volume ratio preparation in 1: 1.

Preferred examples is butylacetate/dimethylbenzene, 1: 1 methoxyacetic acid propyl ester/dimethylbenzene, 1: 1 butylacetate/solvent naphtha 100,1: 2 butylacetate/Solvesso

100 and 3: 1 Kristalloel 30/Shellsol

A.

Alcohols is for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, amylalcohol isomer mixture, hexanol isomer mixture, 2-Ethylhexyl Alcohol or octanol.

The example of operable other common coating additive (E) comprises oxidation inhibitor, stablizer, activator (promotor), weighting agent, pigment, dyestuff, static inhibitor, fire retardant, thickening material, thixotropic agent, tensio-active agent, viscosity modifier, softening agent or sequestrant.

Suitable thickening also comprises common organic and inorganic thickening agent, such as Walocel MT 20.000PV or wilkinite except (being total to) polymkeric substance of free radical (being total to) polymerization.

The example of operable sequestrant comprises ethylenediaminetetraacetic acid and salt and beta-diketon.

Suitable weighting agent comprises silicate, and example is can be by the silicate of silicon tetrachloride hydrolysis acquisition, such as the Aerosil from Degussa

Diatomite, talcum powder, pure aluminium silicate, Magnesium Silicate q-agent, calcium carbonate etc.

Suitable stabilizers comprises common UV absorption agent, such as oxanilide, triazine and benzotriazole (latter be can from

The Tinuvin that obtains

Serial) and benzophenone.They can use separately, perhaps use with suitable free-radical scavengers, and example is sterically hindered amines, such as 2,2,6,6-tetramethyl piperidine, 2,6-di-t-butyl piperidines or derivatives thereof, two (2,2,6,6-tetramethyl--4-piperidyl) sebate for example.The usage quantity of stablizer is generally based on the solid ingredient that is included in the preparation and counts 0.1 to 5.0 weight %.

Also can comprise pigment.According to CD

Chemie Lexikon-Version 1.0, Stuttgart/New York:Georg Thieme Verlag 1995 is the colored or achromatic tinting material of particulate, organic or inorganic with reference to the pigment of DIN 55943, it is dissolved in the applicating medium hardly.

Almost insoluble finger is lower than the applicating medium of 1g/1000g 25 ℃ solubleness herein, is preferably lower than 0.5, more preferably is lower than 0.25, most preferably is lower than 0.1, is lower than the applicating medium of 0.05g/1000g especially.

The example of pigment comprises the system of any desired absorptivity pigment and/or effect pigment (effect pigment), preferred absorptivity pigment.About the quantity of pigment component with select without any restriction.They can optionally adjust to meet specific requirement, such as the color impression (color impression) of expectation.

Effect pigment refers to all pigment of demonstrating small pieces type structure and giving top coat specific decoration color effect.Described effect pigment comprises all pigment that tell on that for example can be applied in usually in vehicles japanning and the industrial coating.The example of this class effect pigment is pure metal pigment, such as aluminium, iron or copper pigment; Interference capability pigment (for example, is used titanium dioxide and Fe such as the mica of coating of titanium dioxide, the mica of iron oxide coatings, the mica of mixed oxide coatings ₂O ₃Or titanium dioxide and Cr ₂O ₃Coating), the aluminium of coating of metal oxides or liquid crystal pigment.

The common organic or inorganic absorptivity pigment of described colorific absorptivity pigment for for example can in coatings industry, using.The example of organic absorptivity pigment is the blue or green pigment of azo pigment, phthalein, quinacridone pigment and pyrrolopyrrole pigment.The example of inorganic absorptivity pigment is iron oxide pigment, titanium dioxide and carbon black.

For the purpose of this specification sheets, the solids content of coating composition of the present invention is defined as component (A) and (B) sum and component (A), (B) and (D) ratio of sum.According to the present invention, described solids content is for example 25% to 90 weight %, preferably 40% to 80 weight %.

Component (A) and (B) normally used ratio be 0.2: 1 to 5: 1 (based on NCO group in (A) with (B) in the ratio of OH group), preferably, the ratio of using is 0.4: 1 to 3: 1, more preferably, the ratio of using is 0.5: 1 to 2: 1, and most preferably the ratio of Shi Yonging is 0.8: 1 to 1.2: 1.

Use

Composition of the present invention can be advantageously used in the preparation antimicrobial coatings.Composition of the present invention can be used as coating, and it can be used as varnish and/or colored paint in priming paint, finish paint or varnish (clearcoat)/colored paint (basecoat) composition especially.They also are used for spray applications.

Said composition can provide rapid reaction, lasting coating, and it has long working life and good curing.Curable compositions of the present invention provides has the clear coat that improves resistance to marring.Composition of the present invention also can be used as tackiness agent, elastomerics and plastics in principle.

Coated material of the present invention is applicable to the multiple matrix of coating, comprise woodwork, paper, yarn fabric, leather, non-woven fabric, frosting, glass, pottery, mineral building materials such as cement moulded work and fiber-cement plate, coating or the metal of coating not.Preferred described curable compositions is used for particularly the plastics of sheet-form or the purposes of metallic coating, the coating on the surface that more preferably is made of metal.

Described antimicrobial composition and the coating that comprises described antimicrobial composition are applicable to other field of hospital environment, medical facilities, water treatment plant, catering service and packaging field, drug test chamber, child health care equipment and the extra antimicrobial protection of needs especially.Described antimicrobial composition can be advantageously used in the food utensil with the coating that comprises described antimicrobial composition, such as mixing tank, the service dish, the salad rod, tank, walkin, water cooler, display stands and Counter service, home appliances is such as refrigerator, washing machine, drying machine, garbage grinder and rubbish compressor, food-processing machine such as mincer, dish, conveyer, storage tank, slicing machine and food processing plant, medical facilities are such as fascia panel, frame, sterilization equipment, bedpan, table top, the procuratorial work table, walkie fork lift truck, bed, and lighting installation, hospital and both privately and publicly owned's interior arrangement is such as push pedal (pushplate), kickplate, the towel divider, door, escalator, elevator, with the rest room device, and as the part of transportation means such as automobile inner part and surface, aircraft interior components and surface and train internal part and surface.

According to ordinary method known to the skilled, adopt coated material of the present invention to be coated with described matrix, described ordinary method comprises at least a coated material of the present invention or coating agent is administered to target matrix with the thickness of expectation, and, remove the volatile constituent (drying) of coated material---if heating when suitable---.If expectation repeats this operation one or many.Being applied to matrix can carry out in known manner, for example by spraying, shovel be coated with, blade coating, brushing, roll-in, cylinder coating or topple over.Coat-thickness is generally about 3 to 1000g/m ², preferred 10 to 200g/m ²Then, can be cured.

Solidify and pass through dry coating---after coated material is applied to matrix---usually and make the coating of using accept thermal treatment (curing) to finish, if wherein said drying is suitably under the temperature that is lower than 80 ℃, preferably under room temperature to 60 ℃, more preferably under room temperature to 40 ℃, carry out, 72 hours at the most time of drying, preferably at the most 48 hours, more preferably at the most 24 hours, most preferably at the most 12 hours and at the most 6 hours especially, described thermal treatment (preferred air) or under rare gas element under oxygen-containing atmosphere, under 80 to 270 ℃ temperature, preferably under 100 to 240 ℃, more preferably under 120 to 180 ℃, carry out.The generation that coated material solidifies is along with the amount of the coated material of using and the crosslinked energy variation of introducing via the heat passage of high-energy radiation, hot surface or gaseous medium convection current, it carries out the several seconds, for example, under the situation that coil coating (coil coating) and NIR drying are united, be 5 hours at the most, for example, thick film on thermo-sensitive material (high-build) system is no less than 10 minutes usually, preferably is no less than 15 minutes, more preferably is no less than 30 minutes and most preferably is no less than 45 minutes.Dry comprise the solvent of removing existence in fact, in addition, even in this period, also can with adhesive reaction, and solidify the reaction that comprises in fact with tackiness agent.

Except thermofixation, perhaps replace thermofixation, solidify and also can utilize IR and NIR radiation to carry out, adopt the NIR radiometer to be shown in wavelength region 760nm to 2.5 μ m, preferred 900 to 1500nm electromagnetic radiation herein.

Be solidificated in 1 second to 60 minutes, preferred 1 minute to 45 minutes time and carry out.

The example that is used for the suitable matrix of coated material of the present invention comprises thermoplastic polymer, especially polymethylmethacrylate, poly-n-butyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, poly(vinylidene fluoride), polyvinyl chloride, polyester, polyolefine, vinyl cyanide-ethylene, propylene-diene-styrene copolymer (A-EPDM), polyetherimide, polyetherketone, polyphenylene sulfide, polyphenylene oxide or its mixture.

Can also mention the multipolymer of polyethylene, polypropylene, polystyrene, polyhutadiene, polyester, polymeric amide, polyethers, polycarbonate, polyvinyl acetal, polyacrylonitrile, polyacetal, polyvinyl alcohol, polyvinyl acetate, resol, urea resin, melamine resin, Synolac, Resins, epoxy or urethane, its block or grafting and the adulterant of these materials.

Preferably can mention ABS, AES, AMMA, ASA, EP, EPS, EVA, EVAL, HDPE, LDPE, MABS, MBS, MF, PA, PA6, PA66, PAN, PB, PBT, PBTP, PC, PE, PEC, PEEK, PEI, PEK, PEP, PES, PET, PETP, PF, PI, PIB, PMMA, POM, PP, PPS, PS, PSU, PUR, PVAC, PVAL, PVC, PVDC, PVP, SAN, SB, SMS, UF, UP plastics (according to the abbreviated name of DIN 7728) and aliphatic polyketone.

Particularly preferred matrix has: polyolefine, and such as PP (polypropylene), it randomly can be isotactic, syndyotactic or atactic, and randomly can be non-oriented, perhaps can have single shaft or biaxial stretch-formed orientation; SAN (styrene acrylonitrile copolymer), PC (polycarbonate), PVC (polyvinyl chloride), PMMA (polymethylmethacrylate), PBT (poly-(butylene terephthalate)), PA (polymeric amide), ASA (acrylonitrile-styrene-acrylic ester copolymer) and ABS (acrylonitrile-butadiene-styrene copolymer), with and physical mixture (adulterant).The adulterant of preferred especially PP, SAN, ABS, ASA and ABS or ASA and PA or PBT or PC.Particularly preferably be polyolefine, PMMA and PVC.

Especially preferred is the ASA that meets DE 196 51 350 especially, and the ASA/PC adulterant.The PMMA of same preferred polymethylmethacrylate (PMMA) or impact modification.

Another kind of preferred matrix with coated material coating of the present invention is metal.Described metal has especially had those that another kind films, such as having electropaining layer, two road undercoats, priming paint or colored paint.These are filmed can be solvent based, water base or the powder coating base, can be crosslinked, partial cross-linked or thermoplastic, can be in its volume integrally curing, perhaps can wet pressing wet (wet-on-wet) use.

As for the metal types that relates to, suitable metal can be any desired metal in principle.Yet especially, it is the metal or alloy that is typically used as the structural metal material and needs corrosion prevention.

Described surface is the surface of iron, steel, Zn, Zn alloy, Al or Al alloy in particular.These can be the body structure surfaces of being made up of described metal or alloy fully.Perhaps, described structure can only be used these washings, and himself can be made by the material of other kind, such as comprising other metal, alloy, polymkeric substance or matrix material.They can be the surfaces of the foundry goods made by galvanized iron or steel.In an embodiment preferred of the present invention, described surface is the steel surface.

Zn alloy or Al alloy are known to the skilled.The technician selects the property quality and quantity of alloy compositions according to the final use of expectation.The general component of zinc alloy comprises Al, Pb, Si, Mg, Sn, Cu or Cd especially.The general component of aluminium alloy comprises Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti especially.Described alloy also can be the approximately equalised Al/Zn alloy of amount of Al and Zn wherein.Steel with the alloy coat of these kinds is commercially available obtainable.Steel can comprise general alloy compositions known to the skilled.

Coating composition of the present invention also can be used for handling tinplate/steel (tin plate).

Can demonstrate good anti-microbial properties by the coating that curable compositions of the present invention obtains.

It is known to those skilled in the art that under appropriate condition particularly in the presence of appropriate catalyst and water, the polymkeric substance based on urethane that obtains according to the present invention is polyurethane-polyurea-silica polymer.

Another object of the present invention provides a kind of suit that comprises curable compositions, and described composition comprises as unitary part:

A) at least a polyisocyanates as defined above (A),

B) at least a have at least two binder ingredientss to the functional group of responding property of isocyanic ester (B) as defined above,

C) the organoalkoxysilane C of at least a isocyanate-reactive as defined above and

D) at least a biocide as defined above (Z).

Embodiment

In the following embodiments, use following abbreviation:

The preparation of polyurethane prepolymer (HPP-A50):

Under 50 ℃, vacuum, in the Schlenck flask, make dry 2 hours of the dibutyl tin dilaurate of the hexamethylene diisocyanate (HDI) of 1g and 0.17g.In another flask, add poly-(propylene glycol) (PPG, 2.7g) and 3-[two (2-hydroxyethyl) amino of 0.84g] propyl-triethoxysilicane] (AMSI), and dry in a vacuum under 50 ℃.After 2 hours, the acetone of 15ml is joined in the flask that comprises PPG and AMSI.Inclusion is transferred in another flask, then 50 ℃ of following restir 2 hours.

TiO ₂The preparation of/AgBr/ phosphatic rock:

TiO with 1 gram ₂The hydroxyapatite of [Degussa P-25] and 0.05g joins in the distilled water of 100mL, and stirs this suspension.Then, the hexadecyl methyl brometo de amonio (CTAB) with 1.2g joins in the suspension continuation stirring.Afterwards, to the NH that wherein is added in 2.3mL fast ₄OH (the NH of 25 weight % ₃) in the AgNO of 0.21g ₃At room temperature, stirring the suspension that obtains spends the night.Afterwards, filtration product is used distilled water wash, and dry down at 80-110 ℃.At last, in air, the photocatalyst of 500 ℃ of following calcination preparations 3 hours.

The preparation of hydrogel:

Under supersound process, NIPAM (0.80g) and MBA (20mg) are dissolved in the H of 8.0ml ₂Among the O.Then, under agitation, add APS solution (the 10mg/1ml H of 1ml in the solution of as above preparation ₂O) and TEMED solution (the 0.128ml/1ml H of 1ml ₂O).In several minutes, obtain transparent hydrogel.This hydrogel is cut into small pieces, then, uses H ₂O washing three times.Then, hydrogel is immersed AgNO ₃Solution (100mg/20ml H ₂O) in 8 hours.Using H ₂After the O washing 3 times, under vacuum, dry load has Ag under being higher than 45 ℃ ⁺Hydrogel 24 hours.

Synthesizing of antimicrobial coatings:

Embodiment 1: to the AJ-100 of 5g according to adding 0.05g in the acetone soln of the polyurethane prepolymer HPP-A50 of described method acquisition, a kind of as Agion The biocide of selling (contains Ag ⁺Zeolite), add the acetone of 50mL again, and stirred 1 hour.The water-content of this mixture is 13 weight parts with respect to 100 weight part AMSI.Then, the solution that obtains is transferred on the POLYCARBONATE SHEET with coating form, and in 100 ℃ baking oven dry 2 hours.

Embodiment 2: identical with embodiment 1, difference is to use the AJ-100 of 0.25g.

Embodiment 3: identical with embodiment 1, difference is to use the Zinc oxide nanoparticle of 0.05g to replace AJ-100.

Embodiment 4: identical with embodiment 3, difference is to use the Zinc oxide nanoparticle of 0.5g to replace AJ-100.

Embodiment 5: identical with embodiment 1, difference is to use the polyalcohol hydrogel biocide that contains silver ions of 0.05g to replace AJ-100.

Embodiment 6: identical with embodiment 5, difference is to use the polyalcohol hydrogel biocide that contains silver ions of 0.5g to replace AJ-100.

Embodiment 7: identical with embodiment 1, difference is to use the biocide TiO of 0.05g ₂/ AgBr/ phosphatic rock replaces AJ-100.

Embodiment 8: identical with embodiment 7, difference is to use the biocide TiO of 0.5g ₂/ AgBr/ phosphatic rock replaces AJ-100.

Embodiment 9: identical with embodiment 1, difference is to use the bronopol (BNP) of 0.05g to replace AJ-100.

Embodiment 10: identical with embodiment 10, difference is to use the BNP of 0.5g to replace AJ-100.

The measurement of antimicrobial acivity

According to Nippon Standard JIS Z 2801:2000-antimicrobial acivity and effect test---measure antimicrobial acivity.Table 1 has compared the antimicrobial acivity of the urethane of the biocide that contains different amounts.The viable cell mean number calculating that the viable cell mean number of measuring immediately after the antimicrobial acivity that provides in the table 1 is based on and is seeded on the coating that does not contain biocide, the viable cell mean number of measuring last 24 hour after in the coating that does not contain biocide and the coatingsurface with antimicrobial coatings were measured after last 24 hour as according to shown in the formula of JIS Z 2801:2000.

Table 1: the antimicrobial acivity of antimicrobial coatings

Claims

1. one kind prepares method for compositions, and it comprises:

(a) make following component reaction:

So, obtain prepolymer, then,

-water and

-at least a biocide (Z), it comprises at least a anti-microbial active matter (Z1) and randomly, particulate carrier material (Z2),

Wherein said at least a anti-microbial active matter (Z1) during step (b) be anergy and

Wherein in step (b), the amount of water is with respect to 100 parts of prepolymer gross dry weights, 10 to 50 weight parts.

2. according to the process of claim 1 wherein that described biocide (Z) comprises as the silver ions of anti-microbial active matter (Z1) with as a kind of in zeolite and the polyalcohol hydrogel of being selected from of particulate carrier material (Z2).

3. be 1 to 500nm particulate anti-microbial active matter (Z1) according to the process of claim 1 wherein that described biocide (Z) comprises at least a number average bead diameter, be selected from (i) zinc oxide and (ii) comprise the particle of titanium dioxide, AgBr and phosphatic rock.

4. be selected from quaternary ammonium salt and 2-bromo-2-nitro the third-1, at least a anti-microbial active matter (Z1) in the 3-glycol according to the process of claim 1 wherein that described biocide (Z) comprises.

5. according to each method of claim 1 to 4; wherein said isocyanate component (A) comprises at least a in the following material: 1-isocyanide acyl group-3; 3; 5-trimethylammonium-5-(isocyanatomethyl)-hexanaphthene, 1; 6-two isocyanide acyl group hexanes, 4; 4 '-two (isocyanide acyl group cyclohexyl) methane and 3 (or 4), 8 (or 9)-two (isocyanatomethyl) tristane and isomer mixtures thereof.

6. according to each method of claim 1 to 5, wherein said isocyanate component (A) comprises 1,6-, two isocyanide acyl group hexanes.

7. according to each method of claim 1 to 6, wherein said binder ingredients (B) comprises at least a tackiness agent (B1) that is selected from polyvalent alcohol and polyamines.

8. according to each method of claim 1 to 7, wherein said binder ingredients (B) comprises at least a tackiness agent (B1) that is selected from polypropylene glycol and 1,5-pentanediol.

9. according to each method of claim 1 to 8, wherein organoalkoxysilane (B2) comprises the compound of at least a formula (I):

Wherein

N is 1 to 6 integer;

R ¹Be H or C ₁-C ₆Alkyl;

R ²And R ³Wei – OH, OR independently ¹Or C ₁-C ₆Alkyl;

R ⁴And R ⁵Be H, C independently ₁-C ₆Alkyl, C ₁-C ₆Hydroxyalkyl or C ₁-C ₆Aminoalkyl group;

10. according to each method of claim 1 to 9, wherein said organoalkoxysilane (B2) comprises at least a in the following material: N-(3-(trimethoxysilyl) propyl group) quadrol, 1-(3-(trimethoxysilyl) propyl group) diethylenetriamine, two (3-(methylamino-) propyl group) Trimethoxy silane, N-β-(aminoethyl)-gamma-amino propyl trimethoxy silicane, N-(2-aminoethyl)-3-aminopropyl-methyl dimethoxysilane, the gamma-amino propyl trimethoxy silicane, 3-(N-styryl methyl-2-aminoethylamino) propyl trimethoxy silicane, N-phenyl amino Union carbide A-162 and two-(γ-trimethoxy-silylpropyl) amine and aforesaid combination.

11. according to each method of claim 1 to 10, the amount of wherein said biocide (Z) is 1 to 10 weight % based on the composition gross dry weight that obtains.

12. a composition is according to each acquisition of claim 1 to 11.

13. a coating, it comprises the composition of claim 12.

14. a suit that comprises curable compositions, described curable compositions comprise the following component that is used for combined utilization as unitary part,

A) isocyanate component (A), its average per molecule has at least two isocyanate group,

B) binder ingredients (B), it has average at least two functional groups to responding property of isocyanic ester,

C) at least a to responding property of isocyanic ester organoalkoxysilane and

D) at least a biocide (Z),

Each defines in each in claim 1 to 11 freely.

15. according to the composition of claim 12 purposes for the preparation of antimicrobial coatings.