CA2234246C - Water dispersible blocked isocyanates - Google Patents
Water dispersible blocked isocyanates Download PDFInfo
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- CA2234246C CA2234246C CA002234246A CA2234246A CA2234246C CA 2234246 C CA2234246 C CA 2234246C CA 002234246 A CA002234246 A CA 002234246A CA 2234246 A CA2234246 A CA 2234246A CA 2234246 C CA2234246 C CA 2234246C
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- polyisocyanate
- water dispersible
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
Abstract
A water dispersible blocked polyisocyanate of formula (I) R-Y m, where R is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and comprising at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid, and each group Y, which may be the same or different, is a group of formula (II), where each R1 is the same or different when n is more than 1 and each R1 is an alkyl, alkenyl, aralkyl, N-substituted carbamyl, phenyl, NO2, halogen or a group -C(O)-O-R2, where R2 is hydrogen or an alkyl group; n is 0, 1, 2 or 3; and m is an integer of 2 or more.
Description
WATER DISPERSIBLE BLOCKED ISOCYANATES
The present invention relates to water dispersible blocked polyisocyanates, methods for making them, water-based storage stable materials, and coatings containing them.
Blocked polyisocyanates are commonly used in coatings, such as paints, which also contain active hydrogen containing compounds e.g. amines and alcohols. These coatings are'deposited onto the article to be coated and tr.en subsequently hardened by heating, often referred to as stoving. During stowing the blocked polyisocyanates dissociate so that the isocyanate groups become available to react with the active hydrogen containing compounds.
This leads to crosslinking and hardening of the coating.
A blocked polyisocyanate coating composition ideally has two properties: (a) a dissociation temperature low enough to allow hardening without heating to temperatures which degrade the coated item and (b) water dispersibility so that the use of organic solvents can be kept to a minimum or eliminated. However, generally a blocked polyisocyanate having a low dissociation temperature will be highly reactive and thus will be inherently unstable in water so that the two properties are incompatible.
' Various means for increasing water dispersibility have been described.
US 4,522,851 describes a water-dispersible blocked isocyanate in which a hydrophilic group such as an anionic group is chemically incorporated into the polyisocyanate component to make the blocked polyisocyanate water-dispersible. US-A-4,507,427 describes aqueous blocked polyisocyanate solutions or dispersions produced by mixing °
the blocked polyisocyanate with water in the presence of enough base to guarantee the solubility or dispersibility of the polyisocyanates. US 4,098,933 describes water-dispersible blocked polyisocyanates in which the blocking groups contain a hydrophilic group such as a carboxylic acid salt or polyethylene oxide units.
Most conventional blocked polyisocyanates dissociate at temperatures of around 160°C. EP-A-0159117 discloses pyrazole blocked polyisocyanates which dissociate at a temperature significantly lower than this. Since the pyrazole blocked polyisocyanates are more reactive than conventional blocked isocyanates, they are inherently less stable.
The present inventors have now established that, despite their high reactivity, certain pyrazole blocked polyisocyanates can be used in aqueous dispersion coating compositions and that the compositions have good storage stability. Accordingly the present invention provides a water dispersible blocked polyisocyanate of the formula {I) R-~'m { I ) where R is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and comprising at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid, and each group Y, which may be the same or different, is a group of formula ( II ) N--NH-CO-N (R')n (li) where R1 a.s an alkyl, alkenyl, aralkyl, N-substituted carbamyl, phenyl, NOa, halogen or a group -C(O)-O-R2 where R2 is hydrogen or an alkyl group;
n is 1, 2 or 3; and m is an integer of 2 or more.
Preferably m is an integer from 2 to 6, for example 2, 3, 4, 5 or 6. When n is 2 or 3, the groups Rl may be the same or different. When R-Ym contains more than one group -C (O) OR2, the groups Ra may be the same or different.
In addition the present invention provides a water dispersible mixture of blocked polyisocyanates each of the formula R-Ym where the groups R are the same or different and each is an m valent group comprising an aliphatic, cycloaliphatic ' heterocyclic or aromatic group and wherein from 5 to 100 eq.wt~ (preferably from 10 to 100 eq.wt~) of groups R
comprise at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid, and each group Y, which may be the same or different, is a group of formula (II) as defined above.
According to a further embodiment, the invention provides a water dispersible product obtainable by (a) contacting a polyisocyanate of formula (III) R$(NCO)Q (III) wherein Ra is a q valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and q is an'integer greater than 2, with an active hydrogen-containing compound bearing a hydrophilic group which is -(CHZCH20)~,- where p is 3 or more or with a polyhydroxy carboxylic acid group or derivative thereof to form a water dispersible polyisocyanate of formula R(NCO)m where R is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group comprising at least three consecutive ethylene oxide groups or a residue of a polyhydroxycarboxylic acid; and (b) blocking the water dispersible polyisocyanate produced in step (a) with a pyrazole of formula (IV) N-HN (R~)n wherein R1 and n are as defined in relation to formula (I) above. ' A substance is considered to be water dispersible for the purposes of the present invention if it forms a dispersion in water which is uniform on a macroscopic scale but consists of particles or droplets of the substance in water. Preferably the dispersion is a colloid, in which, for example, the particles or droplets of the dispersed ~ substance have a diameter which is about the wavelength of light, for example about 500 nm. In general the particle or droplet is an aggregate of numerous molecules, but is too small to be seen with an optical microscope. The particles or droplets generally pass through most filter papers but can usually be detected by light-scattering, sedimentation and osmosis. Preferably the dispersion is an emulsion or sol of blocked polyisocyanate in water. An emulsion is generally a dispersion of liquid in liquid. A
sol is generally a dispersion of a solid in a liquid.
An alkyl, alkenyl or aralkyl group may be a branched or straight chain group and may be substituted, for example with a halogen, such as fluorine, chlorine or bromine, or -OH. An alkyl group is preferably a C1 to C6 alkyl group, more preferably a C1 to C4 alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl. Most preferably it is methyl. An alkenyl group is preferably a C2 to C6 alkenyl group, for example C2, C3, C4, CS or C6 alkenyl. An aralkyl group preferably has substituted or unsubstituted phenyl as the aryl portion.
' The alkyl portion is generally an alkyl group as defined above.
A polyhydroxy carboxylic acid is a compound having 2 or more hydroxyl groups and one or more carboxylic acid groups, such as dimethylolpropionic acid.
Preferably n is 2 or 3.
Preferably m is an integer from 2 to 6. More preferably m is 2 or 3.
A halogen is, for example chlorine, bromine or fluorine. Preferably it is chlorine or bromine.
An N-substituted carbamyl group is generally of formula -C (O) NR3R4, where R3 and R4 may be the same or different and each is hydrogen or an alkyl or alkenyl group, provided that R3 and R4 are not both hydrogen.
According to one embodiment the group R in the blocked isocyanate of formula (I) comprises at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid. According to a second embodiment, from 5 to 100 by equivalent weight of groups R
comprise at least three consecutive ethylene oxide groups or at least one residue of a.polyhydroxycarboxylic acid.
Consecutive ethylene oxide groups are groups bonded directly together. Three consecutive ethylene oxide groups can be represented as - (CH2CH20) 3-. When R comprises consecutive ethylene oxide groups, it preferably comprises at least five, for example at least 7, 9 or 12 consecutive ethylene oxide groups. Preferably R comprises 0.01 to 25~
by~weight, based on the weight of the unblocked ' polyisocyanate, of ethylene oxide units, more preferably 0.5 to 25~ by weight. R may comprise further ethylene oxide groups which are not consecutive with or bonded _ 7 _ directly to the three consecutive ethylene oxide groups.
When R comprises residues of polyhydroxy carboxylic acid, it preferably comprises at least 2 residues, ' preferably at least 3, for example 5, 8, 12 or more residues of polyhydroxy carboxylic acid. Preferably R
comprises 0.01 to 25~ by weight, based on the weight of the unblocked polyisocyanate of polyhydroxy carboxylic acid residues, more preferably o.5 to 25~ by weight.
R may comprise residues of polyhydroxy carboxylic acid as well as at least three consecutive ethylene oxide groups. When less than 100 wt~ of groups R comprise at least one residue of polyhydroxy carboxylic acid or at least three consecutive ethylene oxide groups, preferably at least 15 wt~, for example, at least 20, 30, 40, 50 or 60 wt~ of groups R comprise at least one residue of polyhydroxy carboxylic acid or at least three consecutive ethylene oxide groups. When the polyhydroxy carboxylic acid is dimethylol propionic acid (DMPA) the ratio of isocyanate/hydroxyl groups is generally 0.05 to 0.7, preferably 0.2 to 0.3 on an equivalent weight basis, so isocyanate is in excess.
Preferably at least one group Y is _ g _ N N
-NH-CO-N -NH-CO -N
N N
-NH-CO -N -NH-CO -N
~3 'N02 CH3 \Hr More preferably at least one group Y is ~3 N
i NH CO N
The present invention provides a process for producing a water dispersible blocked polyisocyanate which process comprises contacting a polyisocyanate of formula R(NCO)m with a blocking agent, where R and m are defined as for the blocked isocyanate of formula (I). Preferably the resulting blocked polyisocyanate contains no free isocyanate groups.
The present invention further provides a process which comprises (a) contacting a conventional polyisocyanate of formula (III) as defined above with an active hydrogen-containing compound bearing a hydrophilic group which is -(CH2CH20)p- where p is 3 or more - g _ or a carboxylic acid group or derivative thereof to form a water dispersible polyisocyanate of formula R(NCO)m; and (b) blocking the water dispersible polyisocyanate produced in step (a) with a pyrazole of formula (IV) as defined above.
The blocking agents used in the present invention are pyrazoles of the formula (IV) as defined above.
Examples of suitable pyrazoles include 3,5-dimethylpyrazole, 3-methylpyrazole, 4-nitro-3,5-dimethylpyrazole and 4-bromo-3,5-dimethyl-pyrazole. The preferred blocking agent is 3,5-dimethylpyrazole.
The polyisocyanate of formula R(NCO)m which is to be blocked is a water dispersible organic polyisocyanate suitable for crosslinking compounds containing active hydrogen. Suitable polyisocyanates comprise, for example, aliphatic groups including cycloaliphatic, aromatic, heterocyclic, and mixed aliphatic aromatic groups. The polyisocyanates contain 2, 3 or more isocyanate groups.
The polyisocyanate of formula R(NCO)m may be, for example, selected from those described in US 4,522,851 or may be a polyisocyanate prepolymer obtained by reacting a conventional polyisocyanate, such as a diisocyanate, with a compound comprising at least three consecutive ethylene oxide units or at least one polyhydroxy carboxylic acid residue.
The conventional polyisocyanates are generally C1 to Cl2 alkylene diisocyanates, or dimers or trimers thereof, aryl diisocyanates or cycloalkyl diisocyanates. The conventional polyisocyanates include, for example toluene diisocyanate, such as 2,4- and 2,6-toluene diisocyanate ethylene diisocyanate and mixtures thereof, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate,~ 2,4,4-trimethylhexamethylene-1,6 diisocyanate, phenylene diisocyanate, tolylene or naphthylene diisocyanate, 4,4'-methylene-bis(phenyl isocyanate), 4,4'-ethylene-bis(phenyl isocyanate), w,w'-diisocyanato-1,3-dimethyl benzene, w,w'-diisocyanato-1,4-dimethylcyclohexane, w,w'-diisocyanato-1,4-dimethyl benzene, w,w'-diisocyanato-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatocyclohexane, 4,4'-methylene-bis(cyclohexyl isocyanate), 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, dimer acid-diisocyanate, w,w'-diisocyanatodiethyl benzene, w,w'-diisocyanatodimethyl toluene, w,w'-diisocyanatodiethyl toluene, fumaric acid bis(2-isocyanato ethyl) ester, triphenylmethane triisocyanate, 1,4-bis(2-isocyanato-prop-2-yl) benzene and 1,3-bis(2-isocyanato prop-2-yl) benzene.
Particularly preferred conventional polyisocyanates ' are the biuret, uretdione or isocyanurate of a C1 to Cla alkylene diisocyanate, such as 1,6-hexamethylene diisocyanate (HMDI). The isocyanurate of HINDI is the isocyanate "trimer" and has the structure , (CH2)~NCO
O
N
N N
OCN(CH2)G/ ~ \(~2~C0 O
The uretdione of HMDI is the "dimer" and has the structure O
/C~
O~ (~~6 ~ j (~2)6 NCO
C
O
The polyisocyanate prepolymers may be obtained by reaction of an excess amount of the conventional polyisocyanate with an active hydrogen containing compound, for example, a polyol or a polyamine, such as a lower molecular weight polyol or polyamine, for example having a molecular weight of 300 or less, or a medium molecular weight polyol or polyamine, for example a polyol or polyamine having a molecular weight of 300 to 8000.
In addition to the at least one residue of polyhydroxy WO 97/12924 PCT/GB96/02440 - ' carboxylic acid or at least three consecutive ethylene oxide groups, the polyol or polyamine preferably comprises, for example, dimers, trimers or polymers of one or more of ethylene glycol, propylene glycol, 1,3-butylene glycol neopentyl glycol, 2,2,4-trimethyl-1,3-pentane diol, hexamethylene glycol, cyclohexane diethanol, hydrogenated bisphenol-A, trimethylol propane, trimethylol ethane, 1,2,6-hexane triol, glycerine, sorbitol or pentaerythritol.
Preferably the polyol or polyamine comprises residues of at least one of diethylene glycol, triethylene glycol or polyethylene glycol, preferably in an amount that the resulting unblocked polyisocyanate comprises 0.01 to 25% by weight of ethylene oxide units. Preferably the active hydrogen containing compound is a polyoxyalkylene amine such as Jeffamine* M-1000.
The di- or polyisocyanate obtained by the above reaction may comprise a biuret group having the structure CONH
CONH
or an allophanate group having the structure NCOO
CONH - -The polyisocyanate may be cyclic, for example a derivative, * trade mark such as an ester, of isocyanuric acid.
Preferably the isocyanate group of the polyisocyanate is not bonded directly to an aromatic nucleus in the group R.
The reaction between the polyisocyanate R(NCO)m and the blocking group is exothermic. Since the reaction product will dissociate if the temperature is raised sufficiently, cooling may be required to keep the temperature of the reaction mixture down, preferably to 80°C or less. The resulting blocked polyisocyanate is then recovered and may be isolated or purified.
The present invention further provides an aqueous dispersion of at least one blocked isocyanate as defined herein. Surprisingly the aqueous dispersions are storage stable for at least four months at room temperature whilst providing blocked polyisocyanates which dissociate at relatively low temperatures.
At 40°C these dispersions have been found to be storage stable for several weeks, and up to several months.
This has significant commercial benefit, allowing users in warm climates to take advantage of the low unblocking temperatures whilst retaining adequate storage stability.
The dispersions are formed by, for example, stirring or agitating a mixture of water and the blocked isocyanate.
Typically the dispersion is formed using an anchor stirrer at 250 to 300 rpm. It is also possible to use a high speed "Greaves" mixer to disperse the product.
The dispersions may additionally comprise at least one of an emulsifier, a detergent, a colourant, a pigment, a resin, a surfactant, a catalyst or an antioxidant.
Preferably the dispersions contain only water and blocked -isocyanate. Generally the dispersion comprises from 5 to 95~ by weight, based on the weight of the dispersion, of blocked polyisocyanate, preferably 30 to 70~, more preferably 35 to 60~ by weight of blocked polyisocyanates.
The present invention further provides a water-based coating composition which comprises an aqueous dispersion as defined above and at least one compound containing an active hydrogen, selected from, for example, alcohols, amines, polyhydroxy-polyesters, polyhydroxy polyethers, polylactones, hydroxypolycarbonates, polythioethers, polyacetals, polyether esters, polyester amides and polyamide-polyamine resins, e.g. the product from a dimer fatty acid and an aliphatic polyamide.
Preferably the compound containing an active. hydrogen atom is an acrylic resin containing a carboxylic acid group and hydroxy groups, a water dispersible polyester or polyether resin or a hydroxyacrylic resin containing a tertiary amine group, or polymers thereof.
Generally the coating composition comprises from 10 to 90~ by weight based on the weight of the composition of the compound containing an active hydrogen atom.
Typically the coating composition may comprise at least one of an emulsifier, a detergent, a colourant, a pigment, a resin, a surfactant, a catalyst, an antioxidant, a dispersing aid, a fungicide, a viscosity modifier, a defoamer, a flow additive or a coalescing solvent.
The coating compositions of the present invention conveniently provide one component storage stable coating formulations, which are generally stable for at least four months at room temperature, that is at a temperature between 15 and 22oC, generally, 16, 17 or l8oC.
Typically a coating composition according to the invention will comprise components in the following proportions:
Component Parts by weicrht 1 ) Water 8 . 0 2) Dispersing Aid 0.3 3) Dimethylaminoethanol 0.6 4) Fungicide 0.1 5) Titanium Dioxide 18.0 6) Viscosity Modifier 3.0 7) Defoamer 0.3 8) Flow Additive 0.3 9) Acrylic Emulsion (45~ solids) 47.0 10) Bloclted Isocyanate 22.0 11) Coalescing Solvent 0.4 According to a further embodiment of this invention, the coating is a paint composition comprising a pigment carrier containing active hydrogen groups, a pigment and an aqueous dispersion of a compound of formula I.
These paints usually comprise a pigment dispersed in an aqueous dispersion of a pigment carrier. Preferably the pigment carrier is a resin containing an active hydrogen, which resin is to be crosslinked by the polyisocyanate.
Preferably the paint contains 0.5 to 2 blocked isocyanate groups per active hydrogen containing group. Suitable active hydrogen containing resins include polyamide-polyamine resins, e.g. the product from a dimer fatty acid and an aliphatic polyamide, carboxylic acid group containing acrylic resins, or tertiary amine group containing hydroxyacrylic resins and polymers thereof.
The total concentration of the dispersed solid will, of course, depend upon the process for which the paint is to be used. Various standard additives such as surface active agents, catalysts and anti-oxidants may also be incorporated.
The coatings according to the invention may be deposited electrophoretically or conventionally e.g. by spray depositing, dipping, applying with a roller or brush, transfer coating, screen painting, electrostatic spraying, using a doctor blade or electrocoating or by other means onto the articles to be coated and then subsequently ' hardened by heating the deposited coating to crosslink the compound containing an active hydrogen.
The electrophoretic deposition process is well known and involves the use of a cathode and an anode in contact with a bath containing the paint. The surface to be coated r is the surface of one of the electrodes. On applying a voltage of generally 1 to 3,000 volts across the electrodes the paint is deposited onto the surface of one of the electrodes.
The coated article is removed from the bath and stoved e.g. baked in an oven. The blocking groups dissociate from the isocyanate groups, which then react with the compound containing the active hydrogen. This results in crosslinking and hardening of the coating. Coating compositions according to this invention are generally hardened at temperatures from 100 to 180oC, for instance at up to 140C or, preferably, up to 120C.
The present invention further provides the use of an aqueous dispersion of a blocked isocyanate as defined herein as a coating composition, such as a paint.
Other uses of the aqueous dispersions and coating compositions of the invention include clear coatings (similar to paints but lacking opaque pigments) and water based textile coatings and crosslinkers for fabrics. The low unblocking temperature permits the aqueous dispersions and coating compositions to be used to coat relative heat sensitive substrates such as plastics which would melt or degrade at higher storing temperature. A preferred use of the aqueous dispersions and coating compositions is in the automotive industry, for instance in or as primers, WO 97/12924 PCT/GB96/03440 ~ ~ . .
basecoats, topcoats and lacquers for automobiles.
The present invention further provides a coating process which comprises applying the coating to an item and heating it to achieve hardening of the coating.
The invention is illustrated by the following Examples.
EXAMPLES
Example 1 - Production of aqueous dispersion of blocked isocyanate.
The following reactants were used:
Weight %
1) 1,6-Hexamethylene diisocyanate trimer 30 2) Polyoxyalkylene amine (Jeffamine* M-1000) g 3) 3,5-Dimethyl pyrazole (Blocking agent) 16 4) Butyl glycol ether (solvent) 7 5) Sodium sulphosuccinate (Disponil* SUS 87) 4 6) Water 40 (1) was added to a reaction vessel. (2) was slowly added to the reaction vessel. The vessel was heated to 60 to 70oC until an isocyanate content of 20 to 21 mol % was reached. The temperature was maintained at 60 to 70oC
while (3) was added slowly until an isocyanate content of zero was reached. (4) and (5) were added and mixed for 5 minutes. Water was added and a dispersion was formed using * trade marks a high speed mixer.
Jeffamine M-1000 is the active hydrogen-containing compound which reacts with the HMDI trimer to form a polyisocyanate prepolymer. Sodium sulphosuccinate is an ionic surfactant which helps to control the particle size of the dispersion.
Example 2 - Production of aqueous dispersion of blocked isocyanate The following reactants were used:
Weight ~
1) 1,6 Hexamethylene disocyanate trimer 26.7 2) n-Methyl pyrrolidone 6.0 3) Dimethyl pyrazole 11.3 4) Dimethylol propionic acid 1.9 5) DMAMP 80 (Angus Chemie) 2.0 6) Water 52.1 1) was added to a reaction vessel. (2) was added and the vessel heated to 60-70°C. The temperature was maintained at 60-70°C while (3) was added slowly until an isocyanate content of 2.8~ was reached. (4) was added and the reaction continued until an isocyanate content of zero was reached. The batch was cooled to 60°C before adding (5) ' and ( 6 ) .
WO 97/12914 PCT/GB96/02940 ~ , ';
Example 3 - Production of white paint composition.
Component weight Parts by 1) Water, 8.0 2) Dispersing aid (Dispex* 40) 0.3 3) Dimethylaminoethanol 0.6 4) Fungicide (Acticide* SPX) 0.1 5) Titanium dioxide 18.0 6) Viscosity modifier (Rheovis* CR2) 3.0 7) Defoamer (Foamex* 1488) 0.3 8) Flow additive (Aerosol* OT75) 0.3 9) Acrylic emulsion (Xenacryl*
(45~ solids) DP 98/1283) 47.0 10) Blocked isocyanate 22.0 11) Coalescing solvent (Extrapro EEP) 0.4 Components (1), (2), (4), (5), (7), 0.06 parts by weight of component (3) and 1.5 parts by weight of component (6) were formed into a premixture under high shear in order to achieve good pigment dispersion (maximum particle size:
Hegmann S). The titanium dioxide was added slowly to assist wetting. Components (8) to (11) and the remainder of components (3) and (6) were added and mixed under high shear for 10 minutes.
The components (2), (4),,(6), (7}, (8). (9). (10) and (I1) were obtained from the following manufacturers:
* trade marks 2 Dispersing aid Dispex* 90 Allied Colloids 4 Fungicide Acticide* SPX Thor Industrial Hiocides .
6 Viscosity modifier Rheovis* CR2 Allied Colloids 7 Defoamer ~ Foamex* 1988 Tego Chemie Service 8 Flow additives Aerosol* OT75 Cytec Industries 9 Acrylic Emulsion Xenacryl* Baxenden Chemicals DP9B/1283 Ltd.
10 Blocked Obtained by reaction of ~I
isocyanate trimer with DMPA and blocked with 3,5-dimethylpyrazole (see example 2) 11 Coalescing Extrapro EEP Eastman Chemical solvent Ltd.
* trade marks Example 4 Coatings The white paint composition of Example 3 was coated onto various substrates and stored at 120°C for 45 minutes. The .
resultant coatings were tested with the following results Table 1 TEST RESULT TEST METHOD
Opacity 96$ R+D Method 22 1 Gloss 20 51$ R+D Method 22 60 82$
Reverse Impact: PASSED ASTM D2794-92 l.8kg weight (l.Om) Steel Panels Bend Test: PASSED BS3900 Part E1 Shim steel panels (3mm cylindrical mandrel) Cross cut adhesion: Rating BS3900 Part E6 Substrate Smooth steel 0 ISO 2409 2 Matt steel 0 Tin plate steel 0 Aluminium 0 Chrome treated 0 aluminium 2 Pencil Hardness ASTM D3363-92a Gouge Hardness 3H
Scratch Hardness 2H
Weathering after 280 ASTM 65388 hours Gloss retention 95$ 4hrs UVB ~ 60C
3 Observations on steel No rusting 4hrs condensation t~
substrate Acetone resistance >100 units Standard (double rubs) 35 Unless otherwise stated, substrates were standard steel test panels.
Examt~le 5 - Production of clear coat formulation Component Parts by weight r 1) Xenacryl DP 9B/1345 54.1 2) Blocked polyisocyanate 25.4 of Example 2 3) Tegowet KL 245 0.5 4) Estasol 5.0 5) Ectapro EEP 2.0 6) Water 13.0 Method (1) and (2) were added to a vessel and mixed well. (3), (4) and (5) were added and mixed thoroughly before adding {6) .
Suppliers 1) Xenacryl DP9B/1345 Acrylic emulsion Baxenden Chemicals 3) Tegowet KL245 Flow additive Tego Chemie 4) Estasol Coalescing solvent Chemoxy International
The present invention relates to water dispersible blocked polyisocyanates, methods for making them, water-based storage stable materials, and coatings containing them.
Blocked polyisocyanates are commonly used in coatings, such as paints, which also contain active hydrogen containing compounds e.g. amines and alcohols. These coatings are'deposited onto the article to be coated and tr.en subsequently hardened by heating, often referred to as stoving. During stowing the blocked polyisocyanates dissociate so that the isocyanate groups become available to react with the active hydrogen containing compounds.
This leads to crosslinking and hardening of the coating.
A blocked polyisocyanate coating composition ideally has two properties: (a) a dissociation temperature low enough to allow hardening without heating to temperatures which degrade the coated item and (b) water dispersibility so that the use of organic solvents can be kept to a minimum or eliminated. However, generally a blocked polyisocyanate having a low dissociation temperature will be highly reactive and thus will be inherently unstable in water so that the two properties are incompatible.
' Various means for increasing water dispersibility have been described.
US 4,522,851 describes a water-dispersible blocked isocyanate in which a hydrophilic group such as an anionic group is chemically incorporated into the polyisocyanate component to make the blocked polyisocyanate water-dispersible. US-A-4,507,427 describes aqueous blocked polyisocyanate solutions or dispersions produced by mixing °
the blocked polyisocyanate with water in the presence of enough base to guarantee the solubility or dispersibility of the polyisocyanates. US 4,098,933 describes water-dispersible blocked polyisocyanates in which the blocking groups contain a hydrophilic group such as a carboxylic acid salt or polyethylene oxide units.
Most conventional blocked polyisocyanates dissociate at temperatures of around 160°C. EP-A-0159117 discloses pyrazole blocked polyisocyanates which dissociate at a temperature significantly lower than this. Since the pyrazole blocked polyisocyanates are more reactive than conventional blocked isocyanates, they are inherently less stable.
The present inventors have now established that, despite their high reactivity, certain pyrazole blocked polyisocyanates can be used in aqueous dispersion coating compositions and that the compositions have good storage stability. Accordingly the present invention provides a water dispersible blocked polyisocyanate of the formula {I) R-~'m { I ) where R is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and comprising at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid, and each group Y, which may be the same or different, is a group of formula ( II ) N--NH-CO-N (R')n (li) where R1 a.s an alkyl, alkenyl, aralkyl, N-substituted carbamyl, phenyl, NOa, halogen or a group -C(O)-O-R2 where R2 is hydrogen or an alkyl group;
n is 1, 2 or 3; and m is an integer of 2 or more.
Preferably m is an integer from 2 to 6, for example 2, 3, 4, 5 or 6. When n is 2 or 3, the groups Rl may be the same or different. When R-Ym contains more than one group -C (O) OR2, the groups Ra may be the same or different.
In addition the present invention provides a water dispersible mixture of blocked polyisocyanates each of the formula R-Ym where the groups R are the same or different and each is an m valent group comprising an aliphatic, cycloaliphatic ' heterocyclic or aromatic group and wherein from 5 to 100 eq.wt~ (preferably from 10 to 100 eq.wt~) of groups R
comprise at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid, and each group Y, which may be the same or different, is a group of formula (II) as defined above.
According to a further embodiment, the invention provides a water dispersible product obtainable by (a) contacting a polyisocyanate of formula (III) R$(NCO)Q (III) wherein Ra is a q valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and q is an'integer greater than 2, with an active hydrogen-containing compound bearing a hydrophilic group which is -(CHZCH20)~,- where p is 3 or more or with a polyhydroxy carboxylic acid group or derivative thereof to form a water dispersible polyisocyanate of formula R(NCO)m where R is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group comprising at least three consecutive ethylene oxide groups or a residue of a polyhydroxycarboxylic acid; and (b) blocking the water dispersible polyisocyanate produced in step (a) with a pyrazole of formula (IV) N-HN (R~)n wherein R1 and n are as defined in relation to formula (I) above. ' A substance is considered to be water dispersible for the purposes of the present invention if it forms a dispersion in water which is uniform on a macroscopic scale but consists of particles or droplets of the substance in water. Preferably the dispersion is a colloid, in which, for example, the particles or droplets of the dispersed ~ substance have a diameter which is about the wavelength of light, for example about 500 nm. In general the particle or droplet is an aggregate of numerous molecules, but is too small to be seen with an optical microscope. The particles or droplets generally pass through most filter papers but can usually be detected by light-scattering, sedimentation and osmosis. Preferably the dispersion is an emulsion or sol of blocked polyisocyanate in water. An emulsion is generally a dispersion of liquid in liquid. A
sol is generally a dispersion of a solid in a liquid.
An alkyl, alkenyl or aralkyl group may be a branched or straight chain group and may be substituted, for example with a halogen, such as fluorine, chlorine or bromine, or -OH. An alkyl group is preferably a C1 to C6 alkyl group, more preferably a C1 to C4 alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl. Most preferably it is methyl. An alkenyl group is preferably a C2 to C6 alkenyl group, for example C2, C3, C4, CS or C6 alkenyl. An aralkyl group preferably has substituted or unsubstituted phenyl as the aryl portion.
' The alkyl portion is generally an alkyl group as defined above.
A polyhydroxy carboxylic acid is a compound having 2 or more hydroxyl groups and one or more carboxylic acid groups, such as dimethylolpropionic acid.
Preferably n is 2 or 3.
Preferably m is an integer from 2 to 6. More preferably m is 2 or 3.
A halogen is, for example chlorine, bromine or fluorine. Preferably it is chlorine or bromine.
An N-substituted carbamyl group is generally of formula -C (O) NR3R4, where R3 and R4 may be the same or different and each is hydrogen or an alkyl or alkenyl group, provided that R3 and R4 are not both hydrogen.
According to one embodiment the group R in the blocked isocyanate of formula (I) comprises at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid. According to a second embodiment, from 5 to 100 by equivalent weight of groups R
comprise at least three consecutive ethylene oxide groups or at least one residue of a.polyhydroxycarboxylic acid.
Consecutive ethylene oxide groups are groups bonded directly together. Three consecutive ethylene oxide groups can be represented as - (CH2CH20) 3-. When R comprises consecutive ethylene oxide groups, it preferably comprises at least five, for example at least 7, 9 or 12 consecutive ethylene oxide groups. Preferably R comprises 0.01 to 25~
by~weight, based on the weight of the unblocked ' polyisocyanate, of ethylene oxide units, more preferably 0.5 to 25~ by weight. R may comprise further ethylene oxide groups which are not consecutive with or bonded _ 7 _ directly to the three consecutive ethylene oxide groups.
When R comprises residues of polyhydroxy carboxylic acid, it preferably comprises at least 2 residues, ' preferably at least 3, for example 5, 8, 12 or more residues of polyhydroxy carboxylic acid. Preferably R
comprises 0.01 to 25~ by weight, based on the weight of the unblocked polyisocyanate of polyhydroxy carboxylic acid residues, more preferably o.5 to 25~ by weight.
R may comprise residues of polyhydroxy carboxylic acid as well as at least three consecutive ethylene oxide groups. When less than 100 wt~ of groups R comprise at least one residue of polyhydroxy carboxylic acid or at least three consecutive ethylene oxide groups, preferably at least 15 wt~, for example, at least 20, 30, 40, 50 or 60 wt~ of groups R comprise at least one residue of polyhydroxy carboxylic acid or at least three consecutive ethylene oxide groups. When the polyhydroxy carboxylic acid is dimethylol propionic acid (DMPA) the ratio of isocyanate/hydroxyl groups is generally 0.05 to 0.7, preferably 0.2 to 0.3 on an equivalent weight basis, so isocyanate is in excess.
Preferably at least one group Y is _ g _ N N
-NH-CO-N -NH-CO -N
N N
-NH-CO -N -NH-CO -N
~3 'N02 CH3 \Hr More preferably at least one group Y is ~3 N
i NH CO N
The present invention provides a process for producing a water dispersible blocked polyisocyanate which process comprises contacting a polyisocyanate of formula R(NCO)m with a blocking agent, where R and m are defined as for the blocked isocyanate of formula (I). Preferably the resulting blocked polyisocyanate contains no free isocyanate groups.
The present invention further provides a process which comprises (a) contacting a conventional polyisocyanate of formula (III) as defined above with an active hydrogen-containing compound bearing a hydrophilic group which is -(CH2CH20)p- where p is 3 or more - g _ or a carboxylic acid group or derivative thereof to form a water dispersible polyisocyanate of formula R(NCO)m; and (b) blocking the water dispersible polyisocyanate produced in step (a) with a pyrazole of formula (IV) as defined above.
The blocking agents used in the present invention are pyrazoles of the formula (IV) as defined above.
Examples of suitable pyrazoles include 3,5-dimethylpyrazole, 3-methylpyrazole, 4-nitro-3,5-dimethylpyrazole and 4-bromo-3,5-dimethyl-pyrazole. The preferred blocking agent is 3,5-dimethylpyrazole.
The polyisocyanate of formula R(NCO)m which is to be blocked is a water dispersible organic polyisocyanate suitable for crosslinking compounds containing active hydrogen. Suitable polyisocyanates comprise, for example, aliphatic groups including cycloaliphatic, aromatic, heterocyclic, and mixed aliphatic aromatic groups. The polyisocyanates contain 2, 3 or more isocyanate groups.
The polyisocyanate of formula R(NCO)m may be, for example, selected from those described in US 4,522,851 or may be a polyisocyanate prepolymer obtained by reacting a conventional polyisocyanate, such as a diisocyanate, with a compound comprising at least three consecutive ethylene oxide units or at least one polyhydroxy carboxylic acid residue.
The conventional polyisocyanates are generally C1 to Cl2 alkylene diisocyanates, or dimers or trimers thereof, aryl diisocyanates or cycloalkyl diisocyanates. The conventional polyisocyanates include, for example toluene diisocyanate, such as 2,4- and 2,6-toluene diisocyanate ethylene diisocyanate and mixtures thereof, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate,~ 2,4,4-trimethylhexamethylene-1,6 diisocyanate, phenylene diisocyanate, tolylene or naphthylene diisocyanate, 4,4'-methylene-bis(phenyl isocyanate), 4,4'-ethylene-bis(phenyl isocyanate), w,w'-diisocyanato-1,3-dimethyl benzene, w,w'-diisocyanato-1,4-dimethylcyclohexane, w,w'-diisocyanato-1,4-dimethyl benzene, w,w'-diisocyanato-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanatocyclohexane, 4,4'-methylene-bis(cyclohexyl isocyanate), 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, dimer acid-diisocyanate, w,w'-diisocyanatodiethyl benzene, w,w'-diisocyanatodimethyl toluene, w,w'-diisocyanatodiethyl toluene, fumaric acid bis(2-isocyanato ethyl) ester, triphenylmethane triisocyanate, 1,4-bis(2-isocyanato-prop-2-yl) benzene and 1,3-bis(2-isocyanato prop-2-yl) benzene.
Particularly preferred conventional polyisocyanates ' are the biuret, uretdione or isocyanurate of a C1 to Cla alkylene diisocyanate, such as 1,6-hexamethylene diisocyanate (HMDI). The isocyanurate of HINDI is the isocyanate "trimer" and has the structure , (CH2)~NCO
O
N
N N
OCN(CH2)G/ ~ \(~2~C0 O
The uretdione of HMDI is the "dimer" and has the structure O
/C~
O~ (~~6 ~ j (~2)6 NCO
C
O
The polyisocyanate prepolymers may be obtained by reaction of an excess amount of the conventional polyisocyanate with an active hydrogen containing compound, for example, a polyol or a polyamine, such as a lower molecular weight polyol or polyamine, for example having a molecular weight of 300 or less, or a medium molecular weight polyol or polyamine, for example a polyol or polyamine having a molecular weight of 300 to 8000.
In addition to the at least one residue of polyhydroxy WO 97/12924 PCT/GB96/02440 - ' carboxylic acid or at least three consecutive ethylene oxide groups, the polyol or polyamine preferably comprises, for example, dimers, trimers or polymers of one or more of ethylene glycol, propylene glycol, 1,3-butylene glycol neopentyl glycol, 2,2,4-trimethyl-1,3-pentane diol, hexamethylene glycol, cyclohexane diethanol, hydrogenated bisphenol-A, trimethylol propane, trimethylol ethane, 1,2,6-hexane triol, glycerine, sorbitol or pentaerythritol.
Preferably the polyol or polyamine comprises residues of at least one of diethylene glycol, triethylene glycol or polyethylene glycol, preferably in an amount that the resulting unblocked polyisocyanate comprises 0.01 to 25% by weight of ethylene oxide units. Preferably the active hydrogen containing compound is a polyoxyalkylene amine such as Jeffamine* M-1000.
The di- or polyisocyanate obtained by the above reaction may comprise a biuret group having the structure CONH
CONH
or an allophanate group having the structure NCOO
CONH - -The polyisocyanate may be cyclic, for example a derivative, * trade mark such as an ester, of isocyanuric acid.
Preferably the isocyanate group of the polyisocyanate is not bonded directly to an aromatic nucleus in the group R.
The reaction between the polyisocyanate R(NCO)m and the blocking group is exothermic. Since the reaction product will dissociate if the temperature is raised sufficiently, cooling may be required to keep the temperature of the reaction mixture down, preferably to 80°C or less. The resulting blocked polyisocyanate is then recovered and may be isolated or purified.
The present invention further provides an aqueous dispersion of at least one blocked isocyanate as defined herein. Surprisingly the aqueous dispersions are storage stable for at least four months at room temperature whilst providing blocked polyisocyanates which dissociate at relatively low temperatures.
At 40°C these dispersions have been found to be storage stable for several weeks, and up to several months.
This has significant commercial benefit, allowing users in warm climates to take advantage of the low unblocking temperatures whilst retaining adequate storage stability.
The dispersions are formed by, for example, stirring or agitating a mixture of water and the blocked isocyanate.
Typically the dispersion is formed using an anchor stirrer at 250 to 300 rpm. It is also possible to use a high speed "Greaves" mixer to disperse the product.
The dispersions may additionally comprise at least one of an emulsifier, a detergent, a colourant, a pigment, a resin, a surfactant, a catalyst or an antioxidant.
Preferably the dispersions contain only water and blocked -isocyanate. Generally the dispersion comprises from 5 to 95~ by weight, based on the weight of the dispersion, of blocked polyisocyanate, preferably 30 to 70~, more preferably 35 to 60~ by weight of blocked polyisocyanates.
The present invention further provides a water-based coating composition which comprises an aqueous dispersion as defined above and at least one compound containing an active hydrogen, selected from, for example, alcohols, amines, polyhydroxy-polyesters, polyhydroxy polyethers, polylactones, hydroxypolycarbonates, polythioethers, polyacetals, polyether esters, polyester amides and polyamide-polyamine resins, e.g. the product from a dimer fatty acid and an aliphatic polyamide.
Preferably the compound containing an active. hydrogen atom is an acrylic resin containing a carboxylic acid group and hydroxy groups, a water dispersible polyester or polyether resin or a hydroxyacrylic resin containing a tertiary amine group, or polymers thereof.
Generally the coating composition comprises from 10 to 90~ by weight based on the weight of the composition of the compound containing an active hydrogen atom.
Typically the coating composition may comprise at least one of an emulsifier, a detergent, a colourant, a pigment, a resin, a surfactant, a catalyst, an antioxidant, a dispersing aid, a fungicide, a viscosity modifier, a defoamer, a flow additive or a coalescing solvent.
The coating compositions of the present invention conveniently provide one component storage stable coating formulations, which are generally stable for at least four months at room temperature, that is at a temperature between 15 and 22oC, generally, 16, 17 or l8oC.
Typically a coating composition according to the invention will comprise components in the following proportions:
Component Parts by weicrht 1 ) Water 8 . 0 2) Dispersing Aid 0.3 3) Dimethylaminoethanol 0.6 4) Fungicide 0.1 5) Titanium Dioxide 18.0 6) Viscosity Modifier 3.0 7) Defoamer 0.3 8) Flow Additive 0.3 9) Acrylic Emulsion (45~ solids) 47.0 10) Bloclted Isocyanate 22.0 11) Coalescing Solvent 0.4 According to a further embodiment of this invention, the coating is a paint composition comprising a pigment carrier containing active hydrogen groups, a pigment and an aqueous dispersion of a compound of formula I.
These paints usually comprise a pigment dispersed in an aqueous dispersion of a pigment carrier. Preferably the pigment carrier is a resin containing an active hydrogen, which resin is to be crosslinked by the polyisocyanate.
Preferably the paint contains 0.5 to 2 blocked isocyanate groups per active hydrogen containing group. Suitable active hydrogen containing resins include polyamide-polyamine resins, e.g. the product from a dimer fatty acid and an aliphatic polyamide, carboxylic acid group containing acrylic resins, or tertiary amine group containing hydroxyacrylic resins and polymers thereof.
The total concentration of the dispersed solid will, of course, depend upon the process for which the paint is to be used. Various standard additives such as surface active agents, catalysts and anti-oxidants may also be incorporated.
The coatings according to the invention may be deposited electrophoretically or conventionally e.g. by spray depositing, dipping, applying with a roller or brush, transfer coating, screen painting, electrostatic spraying, using a doctor blade or electrocoating or by other means onto the articles to be coated and then subsequently ' hardened by heating the deposited coating to crosslink the compound containing an active hydrogen.
The electrophoretic deposition process is well known and involves the use of a cathode and an anode in contact with a bath containing the paint. The surface to be coated r is the surface of one of the electrodes. On applying a voltage of generally 1 to 3,000 volts across the electrodes the paint is deposited onto the surface of one of the electrodes.
The coated article is removed from the bath and stoved e.g. baked in an oven. The blocking groups dissociate from the isocyanate groups, which then react with the compound containing the active hydrogen. This results in crosslinking and hardening of the coating. Coating compositions according to this invention are generally hardened at temperatures from 100 to 180oC, for instance at up to 140C or, preferably, up to 120C.
The present invention further provides the use of an aqueous dispersion of a blocked isocyanate as defined herein as a coating composition, such as a paint.
Other uses of the aqueous dispersions and coating compositions of the invention include clear coatings (similar to paints but lacking opaque pigments) and water based textile coatings and crosslinkers for fabrics. The low unblocking temperature permits the aqueous dispersions and coating compositions to be used to coat relative heat sensitive substrates such as plastics which would melt or degrade at higher storing temperature. A preferred use of the aqueous dispersions and coating compositions is in the automotive industry, for instance in or as primers, WO 97/12924 PCT/GB96/03440 ~ ~ . .
basecoats, topcoats and lacquers for automobiles.
The present invention further provides a coating process which comprises applying the coating to an item and heating it to achieve hardening of the coating.
The invention is illustrated by the following Examples.
EXAMPLES
Example 1 - Production of aqueous dispersion of blocked isocyanate.
The following reactants were used:
Weight %
1) 1,6-Hexamethylene diisocyanate trimer 30 2) Polyoxyalkylene amine (Jeffamine* M-1000) g 3) 3,5-Dimethyl pyrazole (Blocking agent) 16 4) Butyl glycol ether (solvent) 7 5) Sodium sulphosuccinate (Disponil* SUS 87) 4 6) Water 40 (1) was added to a reaction vessel. (2) was slowly added to the reaction vessel. The vessel was heated to 60 to 70oC until an isocyanate content of 20 to 21 mol % was reached. The temperature was maintained at 60 to 70oC
while (3) was added slowly until an isocyanate content of zero was reached. (4) and (5) were added and mixed for 5 minutes. Water was added and a dispersion was formed using * trade marks a high speed mixer.
Jeffamine M-1000 is the active hydrogen-containing compound which reacts with the HMDI trimer to form a polyisocyanate prepolymer. Sodium sulphosuccinate is an ionic surfactant which helps to control the particle size of the dispersion.
Example 2 - Production of aqueous dispersion of blocked isocyanate The following reactants were used:
Weight ~
1) 1,6 Hexamethylene disocyanate trimer 26.7 2) n-Methyl pyrrolidone 6.0 3) Dimethyl pyrazole 11.3 4) Dimethylol propionic acid 1.9 5) DMAMP 80 (Angus Chemie) 2.0 6) Water 52.1 1) was added to a reaction vessel. (2) was added and the vessel heated to 60-70°C. The temperature was maintained at 60-70°C while (3) was added slowly until an isocyanate content of 2.8~ was reached. (4) was added and the reaction continued until an isocyanate content of zero was reached. The batch was cooled to 60°C before adding (5) ' and ( 6 ) .
WO 97/12914 PCT/GB96/02940 ~ , ';
Example 3 - Production of white paint composition.
Component weight Parts by 1) Water, 8.0 2) Dispersing aid (Dispex* 40) 0.3 3) Dimethylaminoethanol 0.6 4) Fungicide (Acticide* SPX) 0.1 5) Titanium dioxide 18.0 6) Viscosity modifier (Rheovis* CR2) 3.0 7) Defoamer (Foamex* 1488) 0.3 8) Flow additive (Aerosol* OT75) 0.3 9) Acrylic emulsion (Xenacryl*
(45~ solids) DP 98/1283) 47.0 10) Blocked isocyanate 22.0 11) Coalescing solvent (Extrapro EEP) 0.4 Components (1), (2), (4), (5), (7), 0.06 parts by weight of component (3) and 1.5 parts by weight of component (6) were formed into a premixture under high shear in order to achieve good pigment dispersion (maximum particle size:
Hegmann S). The titanium dioxide was added slowly to assist wetting. Components (8) to (11) and the remainder of components (3) and (6) were added and mixed under high shear for 10 minutes.
The components (2), (4),,(6), (7}, (8). (9). (10) and (I1) were obtained from the following manufacturers:
* trade marks 2 Dispersing aid Dispex* 90 Allied Colloids 4 Fungicide Acticide* SPX Thor Industrial Hiocides .
6 Viscosity modifier Rheovis* CR2 Allied Colloids 7 Defoamer ~ Foamex* 1988 Tego Chemie Service 8 Flow additives Aerosol* OT75 Cytec Industries 9 Acrylic Emulsion Xenacryl* Baxenden Chemicals DP9B/1283 Ltd.
10 Blocked Obtained by reaction of ~I
isocyanate trimer with DMPA and blocked with 3,5-dimethylpyrazole (see example 2) 11 Coalescing Extrapro EEP Eastman Chemical solvent Ltd.
* trade marks Example 4 Coatings The white paint composition of Example 3 was coated onto various substrates and stored at 120°C for 45 minutes. The .
resultant coatings were tested with the following results Table 1 TEST RESULT TEST METHOD
Opacity 96$ R+D Method 22 1 Gloss 20 51$ R+D Method 22 60 82$
Reverse Impact: PASSED ASTM D2794-92 l.8kg weight (l.Om) Steel Panels Bend Test: PASSED BS3900 Part E1 Shim steel panels (3mm cylindrical mandrel) Cross cut adhesion: Rating BS3900 Part E6 Substrate Smooth steel 0 ISO 2409 2 Matt steel 0 Tin plate steel 0 Aluminium 0 Chrome treated 0 aluminium 2 Pencil Hardness ASTM D3363-92a Gouge Hardness 3H
Scratch Hardness 2H
Weathering after 280 ASTM 65388 hours Gloss retention 95$ 4hrs UVB ~ 60C
3 Observations on steel No rusting 4hrs condensation t~
substrate Acetone resistance >100 units Standard (double rubs) 35 Unless otherwise stated, substrates were standard steel test panels.
Examt~le 5 - Production of clear coat formulation Component Parts by weight r 1) Xenacryl DP 9B/1345 54.1 2) Blocked polyisocyanate 25.4 of Example 2 3) Tegowet KL 245 0.5 4) Estasol 5.0 5) Ectapro EEP 2.0 6) Water 13.0 Method (1) and (2) were added to a vessel and mixed well. (3), (4) and (5) were added and mixed thoroughly before adding {6) .
Suppliers 1) Xenacryl DP9B/1345 Acrylic emulsion Baxenden Chemicals 3) Tegowet KL245 Flow additive Tego Chemie 4) Estasol Coalescing solvent Chemoxy International
Claims (15)
1. A water dispersible blocked polyisocyanate of formula (I) R-Y m (I) where R is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and comprising at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid, and each group Y, which may be the same or different, is a group of formula (II) where each R1 is the same or different when n is more than 1 and each R1 is an alkyl, alkenyl, aralkyl, N-substituted carbamyl, phenyl, NO2, halogen or a group -C(O)-O-R2 where R2 is hydrogen or an alkyl group;
n is 0, 1, 2 or 3; and m is an integer of 2 or more.
n is 0, 1, 2 or 3; and m is an integer of 2 or more.
2. A water dispersible mixture of blocked polyisocyanates each of the formula R-Y m where the groups R are the same or different and each is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and wherein from 5 to 100 eq. wt % by weight of R groups comprise at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid, and each group Y, which may be the same or different, is a group of formula (II) where the groups R1 are the same or different when n is more than 1 and each R1 is an alkyl, alkenyl, aralkyl, N-substituted carbamyl, phenyl, NO2, halogen or a group -C(O)-O-R2 where R2 is hydrogen or an alkyl group;
n is 0, 1, 2 or 3; and m is an integer of 2 or more.
n is 0, 1, 2 or 3; and m is an integer of 2 or more.
3. A blocked polyisocyanate according to claim 1 or 2 wherein at least one group Y is
4. A blocked polyisocyanate according to claim 3 wherein at least one group Y is
5. A blocked polyisocyanate according to any one of claims 1, 2, 3 or 4 wherein m is from 2 to 6.
6. A water dispersible product obtained by (a) contacting a polyisocyanate of formula (III) R a(NCO)q (III) wherein R a is an q valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and q is an integer greater than 2 with an active hydrogen-containing compound bearing a hydrophilic group which is -(CH2CH2O)p- where p is 3 or more or with a polyhydroxy carboxylic acid group or derivative thereof to form a water dispersible polyisocyanate of formula R(NCO)m wherein R is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group, comprising at least three consecutive ethylene oxide groups or a residue of a polyhydroxy carboxylic acid; and (b) blocking the water dispersible polyisocyanate produced in step (a) with a pyrazole of formula (IV) wherein each R1 is the same or different when n is more than 1 and each R1 is an alkyl, alkenyl, aralkyl, N-substituted carbamyl, phenyl, NO2, halogen or a group -C(O)-O-R2 where R2 is hydrogen or an alkyl group, n is 0, 1, 2 or 3; and m is an integer of 2 or more.
7. A process for producing a water dispersible blocked polyisocyanate as claimed in any one of claims 1, 2, 3, 4, 5 or 6 which process comprises contacting a polyisocyanate of formula R(NCO)m wherein R is an m valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and comprising at least three consecutive ethylene oxide groups or at least one residue of a polyhydroxy carboxylic acid and m is an integer of 2 or more with a pyrazole of formula (IV) where each R1 is the same or different when n is more than 1 and each R1 is an alkyl, alkenyl, aralkyl, N-substituted carbamyl, phenyl, NO2, halogen or a group -C(O)-O-R2 where R2 is hydrogen or an alkyl group and n is 0, 1, 2 or 3 such that the reaction product contains no free isocyanate groups.
8. A process according to claim 7 which comprises the initial step of contacting a polyisocyanate of formula (III) R a (NCO)q (III) wherein R a is a q valent group comprising an aliphatic, cycloaliphatic, heterocyclic or aromatic group and q is an integer greater than 2 with an active hydrogen-containing compound bearing a hydrophilic group which is -(CH2CH2O)p- where p is 3 or more or a carboxylic acid group or derivative thereof to form a water dispersible polyisocyanate of formula R(NCO)m.
9. An aqueous dispersion of at least one blocked polyisocyanate as claimed in any one of claims 1 to 6.
10. A coating composition which comprises a dispersion as claimed in claim 9 and a compound containing an active hydrogen.
11. A coating composition according to claim 10 which is a paint.
12. A coating composition according to claim 10 or claim 11 which comprises a pigment and a pigment carrier, wherein the pigment carrier is the compound containing an active hydrogen.
13. A composition according to any one of claims l0, 11 and 12 which contains O.S to 2 blocked isocyanate groups per active hydrogen containing group.
14. A method of coating a substrate which comprises applying a composition as claimed in any one of claims 10 to 13 to a substrate and then heating the deposited composition to crosslink the coating.
15. A method according to claim 14 wherein the composition is applied by electrodeposition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9520317.0A GB9520317D0 (en) | 1995-10-05 | 1995-10-05 | Water dispersable blocked isocyanates |
| GB9520317.0 | 1995-10-05 | ||
| PCT/GB1996/002440 WO1997012924A1 (en) | 1995-10-05 | 1996-10-04 | Water dispersible blocked isocyanates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2234246A1 CA2234246A1 (en) | 1996-10-04 |
| CA2234246C true CA2234246C (en) | 2007-01-23 |
Family
ID=10781800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002234246A Expired - Fee Related CA2234246C (en) | 1995-10-05 | 1996-10-04 | Water dispersible blocked isocyanates |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US6063860A (en) |
| EP (1) | EP0853639B1 (en) |
| JP (1) | JP3970926B2 (en) |
| KR (1) | KR100447491B1 (en) |
| AT (1) | ATE187973T1 (en) |
| AU (1) | AU703953B2 (en) |
| CA (1) | CA2234246C (en) |
| DE (1) | DE69605814T2 (en) |
| DK (1) | DK0853639T3 (en) |
| ES (1) | ES2142092T3 (en) |
| GB (1) | GB9520317D0 (en) |
| GR (1) | GR3032857T3 (en) |
| PT (1) | PT853639E (en) |
| WO (1) | WO1997012924A1 (en) |
| ZA (1) | ZA968395B (en) |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2770846B1 (en) * | 1997-11-07 | 2000-01-28 | Rhodia Chimie Sa | POLYISOCYANATE EMULSION MASKING PROCESS |
| FR2772385B1 (en) * | 1997-08-27 | 2000-01-21 | Rhodia Chimie Sa | SYNTHESIS IN EMULSION OF (POLY) ISOCYANATES MASKS, EMULSION SO OBTAINED, USE OF EMULSIONS WITH A VIEW TO MAKING COMPOSITIONS USEFUL FOR COATING AND COATING THUS OBTAINED |
| EP1007579B1 (en) * | 1997-08-27 | 2003-06-04 | Rhodia Chimie | Method for masking polyisocyanates in emulsion |
| DE19810660A1 (en) | 1998-03-12 | 1999-09-16 | Bayer Ag | Aqueous polyisocyanate crosslinker with hydroxypivalic acid and dimethylpyrazole blocking |
| CN1149245C (en) | 1998-04-09 | 2004-05-12 | 克拉瑞特金融(Bvi)有限公司 | Blocked oligomeric isocyanates, their production and use |
| DE19914885A1 (en) * | 1999-04-01 | 2000-10-05 | Bayer Ag | Polyurethane and/or polyurea resin dispersions, useful for the coating of glass fibers, wood, metal, plastic, leather and textiles, are modified with dimethylpyrazole |
| AU2001246427A1 (en) * | 2000-02-22 | 2001-09-03 | Sunyx Surface Nanotechnologies Gmbh | Water-dispersible isocyanates used in the production of ultraphobic coatings |
| US20030109627A1 (en) * | 2000-02-28 | 2003-06-12 | Beate Baumbach | Aqueous coating agents for baking enamels with a high solid content |
| DE10052875A1 (en) * | 2000-08-14 | 2002-02-28 | Bayer Ag | Aqueous dispersions |
| DE10134238A1 (en) | 2001-07-13 | 2003-01-23 | Bayer Ag | An aqueous and/or water dilutible blocked polyisocyanate crosslinking agent, useful for preparation of stoving enamels and automobile finishing, comprises polyisocyante, diisopropylamine, hydrophilizing agent and chain lengthening agent |
| DE10226925A1 (en) * | 2002-06-17 | 2003-12-24 | Bayer Ag | Blocked polyisocyanates |
| US7176254B2 (en) | 2002-06-17 | 2007-02-13 | Bayer Aktiengesellschaft | Sizing composition |
| DE10226927A1 (en) * | 2002-06-17 | 2003-12-24 | Bayer Ag | Blocked polyisocyanates |
| JP4433661B2 (en) | 2002-08-08 | 2010-03-17 | 関西ペイント株式会社 | Light-colored water-based intermediate coating |
| DE10308104A1 (en) * | 2003-02-26 | 2004-09-09 | Bayer Ag | Polyurethane coating systems |
| DE10308105A1 (en) * | 2003-02-26 | 2004-09-09 | Bayer Aktiengesellschaft | Polyurethane coating systems |
| DE10328064A1 (en) * | 2003-06-23 | 2005-01-13 | Bayer Materialscience Ag | Blocked polyisocyanates |
| DE10328994A1 (en) * | 2003-06-27 | 2005-01-13 | Bayer Materialscience Ag | Blocked polyisocyanates |
| DE10328993A1 (en) | 2003-06-27 | 2005-01-20 | Bayer Materialscience Ag | Blocked polyisocyanates |
| EP1664161A1 (en) * | 2003-09-12 | 2006-06-07 | Teijin Twaron B.V. | Two-step method for dipping synthetic fiber |
| DE102004057916A1 (en) * | 2004-11-30 | 2006-06-01 | Bayer Materialscience Ag | Blocked polyisocyanate for dual-cure coating, contains radiation-curable group(s) and specific structural unit(s) |
| DE102005057683A1 (en) | 2005-12-01 | 2007-06-06 | Basf Ag | Radiation curable water emulsifiable polyisocyanates |
| DE102006025313A1 (en) * | 2006-05-31 | 2007-12-06 | Bayer Materialscience Ag | Low-solvent or solvent-free crosslinker dispersion with pyrazole-blocked isocyanate groups |
| JP2008248237A (en) * | 2007-03-08 | 2008-10-16 | Kansai Paint Co Ltd | Water-based one-package coating and method for forming multilayer coating film |
| EP2058355A1 (en) | 2007-11-08 | 2009-05-13 | Bayer MaterialScience AG | Polysiloxane modified polyisocyanate |
| FR2923834B1 (en) * | 2007-11-20 | 2011-01-21 | Rhodia Operations | NOVEL HYDRODISPERSIBLE POLYSICOCYANATE COMPOSITIONS. |
| EP2236532A1 (en) | 2009-03-31 | 2010-10-06 | Bayer MaterialScience AG | Nanoparticle modified hydrophilic polyisocyanate |
| JP5620831B2 (en) * | 2011-01-12 | 2014-11-05 | 日華化学株式会社 | Curable aqueous resin composition, aqueous coating agent and aqueous adhesive |
| US8940853B2 (en) | 2011-03-16 | 2015-01-27 | Asahi Kasei Chemicals Corporation | Cationic blocked polyisocyanate and aqueous composition comprising the same |
| KR101593855B1 (en) | 2011-10-25 | 2016-02-12 | 아사히 가세이 케미칼즈 가부시키가이샤 | Blocked polyisocyanate water dispersion, fiber processing agent composition, and fabric |
| EP2855548B1 (en) | 2012-05-24 | 2017-11-22 | Covestro Deutschland AG | Aqueous blocked polyurethane uric dispersion |
| JP6328875B2 (en) * | 2012-09-26 | 2018-05-23 | 旭化成株式会社 | Aqueous block polyisocyanate, fiber treating agent composition, and fiber |
| JP2018515369A (en) * | 2015-05-06 | 2018-06-14 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing a composite material |
| EP3999570A1 (en) * | 2019-07-18 | 2022-05-25 | Basf Se | Allophanate based dispersing agent |
| US11827795B2 (en) | 2019-08-13 | 2023-11-28 | Purdue Research Foundation | Cellulose nanomaterial (CN) based waterborne polyurethane coating |
| EP3875512A1 (en) | 2020-03-05 | 2021-09-08 | Covestro Deutschland AG | Nonionically hydrophilicized crosslinker dispersion with thermolatently bonded urethane / urea groups |
| EP3875511A1 (en) | 2020-03-05 | 2021-09-08 | Covestro Deutschland AG | High temperature cross-linking dispersion |
| WO2022224927A1 (en) | 2021-04-21 | 2022-10-27 | 旭化成株式会社 | Blocked isocyanate composition, aqueous dispersion, coating composition and coating film |
| WO2024069154A1 (en) | 2022-09-26 | 2024-04-04 | Fujifilm Speciality Ink Systems Limited | Printing ink |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4008247A (en) * | 1973-11-02 | 1977-02-15 | The B. F. Goodrich Company | Ethylenically unsaturated blocked aromatic diisocyanates |
| DE2456469C2 (en) * | 1974-11-29 | 1983-01-13 | Bayer Ag, 5090 Leverkusen | Process for the preparation of water-soluble or water-dispersible blocked polyisocyanates and their use as coating agents |
| JPS5215596A (en) * | 1975-07-28 | 1977-02-05 | Kao Corp | Process for preparing cationic polyuretane emulsion |
| DE2729704A1 (en) * | 1977-07-01 | 1979-01-11 | Veba Chemie Ag | METHOD FOR PRODUCING BLOCKED POLYISOCYANATE |
| US4322327A (en) * | 1979-10-19 | 1982-03-30 | Mitsubishi Petrochemical Co., Ltd. | Slow-curing water-curable urethane prepolymer composition |
| US4522851A (en) * | 1982-09-30 | 1985-06-11 | Mobay Chemical Corporation | Process for coating aqueous dispersion of epoxy resin and blocked polyisocyanate containing chemically incorporated anionic hydrophilic groups |
| DE3326188A1 (en) * | 1983-07-20 | 1985-01-31 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF ORGANIC POLYISOCYANATES WITH AT LEAST PARTLY BLOCKED ISOCYANATE GROUPS, THE COMPOUNDS AVAILABLE AFTER THE METHOD AND THE USE THEREOF FOR THE PRODUCTION OF POLYURETHANES, BURNING LACQUES OR WATER POWDERED POLYURATES. -DISPERSIONS |
| GB8405320D0 (en) * | 1984-02-29 | 1984-04-04 | Baxenden Chem | Blocked isocyanates |
| EP0500495A3 (en) * | 1991-02-21 | 1993-04-07 | Ciba-Geigy Ag | Thermosetting composition |
| DE4221924A1 (en) * | 1992-07-03 | 1994-01-13 | Bayer Ag | Water-soluble or dispersible polyisocyanate mixtures and their use in stoving lacquers |
| ATE213257T1 (en) * | 1993-03-31 | 2002-02-15 | Rhodia Chimie Sa | METHOD FOR PRODUCING AQUEOUS EMULSIONS OF OILS AND/OR RUBBER AND/OR PREFERABLY MASKED (POLY)ISOCYANATE RESINS, AND RESULTING EMULSIONS |
| DE69427374T2 (en) * | 1993-09-03 | 2002-01-03 | Arco Chem Tech | USE OF PYRAZOLE-BLOCKED POLYISOCYANATES IN SINGLE-COMPONENT CLEAR VARNISHES |
-
1995
- 1995-10-05 GB GBGB9520317.0A patent/GB9520317D0/en active Pending
-
1996
- 1996-10-04 AU AU71400/96A patent/AU703953B2/en not_active Ceased
- 1996-10-04 PT PT96932724T patent/PT853639E/en unknown
- 1996-10-04 US US09/051,218 patent/US6063860A/en not_active Expired - Lifetime
- 1996-10-04 ZA ZA968395A patent/ZA968395B/en unknown
- 1996-10-04 AT AT96932724T patent/ATE187973T1/en not_active IP Right Cessation
- 1996-10-04 CA CA002234246A patent/CA2234246C/en not_active Expired - Fee Related
- 1996-10-04 JP JP51408097A patent/JP3970926B2/en not_active Expired - Fee Related
- 1996-10-04 EP EP96932724A patent/EP0853639B1/en not_active Expired - Lifetime
- 1996-10-04 WO PCT/GB1996/002440 patent/WO1997012924A1/en active IP Right Grant
- 1996-10-04 KR KR10-1998-0702541A patent/KR100447491B1/en not_active IP Right Cessation
- 1996-10-04 ES ES96932724T patent/ES2142092T3/en not_active Expired - Lifetime
- 1996-10-04 DE DE69605814T patent/DE69605814T2/en not_active Expired - Lifetime
- 1996-10-04 DK DK96932724T patent/DK0853639T3/en active
-
2000
- 2000-03-03 GR GR20000400549T patent/GR3032857T3/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AU7140096A (en) | 1997-04-28 |
| GR3032857T3 (en) | 2000-07-31 |
| EP0853639B1 (en) | 1999-12-22 |
| ES2142092T3 (en) | 2000-04-01 |
| JP3970926B2 (en) | 2007-09-05 |
| KR19990064062A (en) | 1999-07-26 |
| ATE187973T1 (en) | 2000-01-15 |
| EP0853639A1 (en) | 1998-07-22 |
| GB9520317D0 (en) | 1995-12-06 |
| WO1997012924A1 (en) | 1997-04-10 |
| US6063860A (en) | 2000-05-16 |
| DE69605814D1 (en) | 2000-01-27 |
| PT853639E (en) | 2000-05-31 |
| ZA968395B (en) | 1997-05-13 |
| DK0853639T3 (en) | 2000-05-08 |
| JPH11512772A (en) | 1999-11-02 |
| AU703953B2 (en) | 1999-04-01 |
| DE69605814T2 (en) | 2000-05-25 |
| KR100447491B1 (en) | 2005-01-15 |
| CA2234246A1 (en) | 1996-10-04 |
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| EEER | Examination request | ||
| MKLA | Lapsed |
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| MKLA | Lapsed |
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