CA1323459C - Aqueous sheet silicate dispersions, use of these dispersions as coating assistants and water-dilutable coating compositions containing sheet silicates - Google Patents
Aqueous sheet silicate dispersions, use of these dispersions as coating assistants and water-dilutable coating compositions containing sheet silicatesInfo
- Publication number
- CA1323459C CA1323459C CA000560537A CA560537A CA1323459C CA 1323459 C CA1323459 C CA 1323459C CA 000560537 A CA000560537 A CA 000560537A CA 560537 A CA560537 A CA 560537A CA 1323459 C CA1323459 C CA 1323459C
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- Prior art keywords
- water
- dilutable
- dispersion
- weight
- sheet silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
Abstract
Abstract of the Disclosure The invention relates to dispersions which are obtainable from sheet silicates, a protective colloid and an aqueous dispersant and are suitable for the incor-poration of sheet silicates into water-dilutable coating compositions. The dispersions according to the invention are obtainable using poly(propylene oxide) as the protec-tive colloid, and the poly(propylene oxide) contains no hydrophobic terminal groups, has on average at least one hydroxyl group per molecule and may optionally contain up to 40% by weight of -CH2-CH2-O- units.
Description
1 32345q ~ASF Lacke ~ Farben Aktiengesellschaft, Munster Aoueous sheet sili~ate dispersions, use of these d;spers;ons as coating assis~ants and water-dilutable co ting compositions containing sheet silicates The invention relates to d;spersions which are obta;nable from sheet s;l;cates, a protect;ve colloid and an aqueous dispersant and are su;table for incor-porat;on of sheet s;licates into water-dilutable coat-;ng compositions.
~ ater-d;lutable coating compositions, in par-ticular those ~hich are to be processed by spray appli-cation, for example in automotive coating, must have very particular rheological propert;es~ An espec;ally important role ;s played by the rheolog;cal properties in the case of water-d;lutable coat;ng compos;t;ons ~h;ch conta;n metal pigments and are used for the production of the base coat of a t~o-coat system of the base coat/
clear coat type (cf. for example European Patent 38 127~.
The rheological properties of ~ater-dllutable coat;ng compos;tions very decisively ;nfluence the appli-cat;on properties of the coating compositions. In~the case of wàter-dilutable coat;n~ compos;tions conta~ining metal p;gments, the or;entat;on of the metal pigment particles and hence the achievable metallic effect depend very substantially on the rheological properties ~f the coating compositions.
`. ' ' ' : ,.'`
, .
-. " ', .' :
. .
~ . . . . . . . . .
. . - , , . , . , - . .
. - 2 - 1 3 2 34 5 9 To control the rheological properties of aqueous coat;ng compositions, sheet silicates are extensively used. The sheet silicates swell in water and form gels, which have a high flow limit and low plastic v;scosity S when subjected to shearing.
Incorporation of the sheet silicates into the water-dilutable coating compos;tions is preferably effec-ted via d;spers;ons which are prepared from a sheet s;licate, modified with an anionic protective colloid (for example tetrasodium pyrophosphate), and water. These dispersians have a sol character instead of a gel charac-ter and can be incorporated into the water-dilutable coating compositions simply by metering in~ On mixing, the effect of the protective colloid is eliminated, and the sheet silicate can display its act;on as a v;scosity assistant.
If the dispersions described above are incorporated into water-dilutable coating compositions, coating com-positions are obtained which have poor spray application properties and give moisture-sensitive, poorly adhering coat;ngs. These d;ff;culties occur to a greater extent in the case of water-dilutable coitin;g compos~it;ons wh;ch contain metal pigments, preferably aluminum pigments in flake form, and are int~nded to be ùsed for the produc-tion of the base coat of a two-coat system of the ~ase coat/clear coat type. In these cases, moisture-sens;tive, poorly adhering coatings which have only an inadequate metall;c effect are obtained~
It is the object of the invention to provide sheet ` . ~ ~ .
' ' ` ' . : : -. " ' , . .
.. , ~ , . .
'' 272g3-19 sllicate dlspersions ~hich can be readily incorporated lnto water-dllutable coating composltions and can be used to obtaln water-dllutable coat~ng compositions which have optimum rheological properties and good spray applicatlon properties and which glve molsture-insensltlve coatlngs havlng good adheslon. It is the particular ob~ect of the invention to provide sheet sllicate disperslons which can readily be incorporated into water-dllutable coating compositions contalnlng metal plgments sultable for the production of the base coat of a two-coat system of the base coat/clear co~t type and whlch can be used to obtain water-dllutable coating compositlons which contaln metal plgments and have optimum rheological propertles and good spray appllcatlon propertles and can be processed to give molsture-lnsensitlve two-coat metallic effect coatlngs of the base coat/clear coat type whlch have a good effect and good adheslon.
Accordingly, the present inventlon provides a disperslon which comprises a sheet sillcate whlch is suitable for controlling the rheological propertles of a~ueous coatlng composltions, a protective collold, water and, optionally, water dilutable organic solvents and ls su.ttable for use in lncorporating the sheet sllicate lnto water-dllutable coatlng composltions, wherein the protective colloid is a poly(propylene o~lde) that contains no hydrophobic terminal groups has an average of at least one hydroxyl group per molecule and may optionally contain up to 40 by weight of -CH2-CH2-0- units.
The inventlon also relates to water-dilutable coatlng ~r ~ .
composltlons whlch contaln a sheet sllicate, water, blnders, if necessary plgments, organlc solvents and further conventlonal addltives and whlch are obtainable by lncorporatlng the sheet sillcate into the coatlng 3a ~4 ~
: ' :
. , ~ ' ~-,, ' :'~, . ' ' ' ' - , . . .. .
.
i, : , - 4 - l 32~4 5q compositions via a dispersion ~hich is obtainable from a sheet sil;cate, a protective c~lloid and an aqueous d;spersant, wherein the sheet sili~ate is incorporated into the coating compositions via a dispersion which is S obtainable using poly(propylene oxide) as a protective colloid, and the poly~proPylene o~ide) conta;ns no hydro-phobic terminal groups, has on average at least one hydroxyl group per molecule and may optionally conta;n up to 40X by ~eight of -CHz-CH2-0- un;ts~
The invention also relates to a process fo~ in-corporating sheet silicates into water-dilutable coating compositions, in which the sheet silicates are incorporated into the coating compositions by incorporating dispersions which are obtainable from the sheet silicate, a protective colloid and an aqueous dispersant, wherein the sheet sili-cates are incorporated via dispersions which are obtain-able using poly(propylene oxide) as a protective colloid, and the poly~propylene oxide) contains no hydrophobic ter-minal groups, has on average at least one hydroxyl group per molecule and may optionally contain up to 40~ by weight of -CH2-CH2-0- units.
The invention also relates to the use of the dis-persions described above as coating assistants for incor-porating sheet silicates into vater-dilutable coating com-posit;ons~ in partiçular into vater-dilutable coating com-pos;tions which co.ntain pigments - preferably metall.ic pigments - and are suitable for the production of base coats of tvo-coat systems of the base coat/clear coat type.
_ 5 _ 1323459 U.S. Patent 3,687,885 d;scloses water-dilutable coating compos;tions wh;ch cons;st of a d;spersion of a polymer prepared from ethylenically unsaturated monomers, of a sheet sil-icate, of a nonionic surfactant and of a S thickener. The non;onic surfactants used are alkoxylated alkyLphenols and alkoxylated alcohols wh;ch are composed of 8 to Z2 carbon atoms~ The coating compositions des-cribed ;n U.s. Patent 3,687,885 contain no metall;c pig-ments and are completely unsuitable for the product;on of the base coat of a metallic effect coating of the base coat/clear coat type. U.S. Patent 3,687,885 does not provide the skilled worker with any ;nformation at all for achieving the object of the present invent;on.
Sheet silicates which are suitable for control-ling the rheological properties of aqueous coating com-positions are very familiar to the skilled ~orker (cf.
for example H. Kittel, Lehrbuch der Beschichtungen, Vol.
II, page 340, and Vol. III, page 272 to page 274; Verlag ~.A. Colomb 1974, 1976). These are, in particular, aLu-minum magnesium silicate compounds of the montmorillonite type, for example attapulgite, bentonite or hectorite~
Hectorite is often described by the approximate empirical formu~a Na0~67(M9~Li)6Si8020(oH~F)4~ where Li and F may also be absent.
According to the invention, both natural and syn-thetic sheet siLicates can be used. Synthetic sodium mag-nesium and sodium magnesium fluorine l;thium sheet silicates OT the montmorillonite type are preferably used.
Mixtures of different sheet sil;cates can of course .
.
- 6 - ~323459 also be used.
According to the invention, the protective colloid used is poly(propylene oxide) which contains no hydrophobic terminal groups, has on average at least one hydroxyl g~oup per molecule and may optionally contain up to 40% by weight of -CHz-CHz-0- units.
The term polytpropylene oxide) is understood as meaning compounds which are composed of at least two struc-tural units of the formula -CHCH3-CH20-.
Hydrophobic terminal groups are understood as meaning groups which have an important effect on the sur-factant properties of the poly(propylene oxide~ and which 3S a rule are derived from hydrophobic compounds wh;ch contain more than 6 carbon atoms. Alkylphenols, long-chain aliphatic alcohols, such as, for example, fatty al-cohols, long-cha;n aliphatic amines, such as, for exam-pLe, fatty amlnes, long-chain aliphatic carboxylic acids, such as, for example, fatty acids, and long-chain ali-phatic carboxamides, such as, for example, fatty acid amides, may be mentioned as examples of such terminal group formers~
The -CH2-CH~-0- units which may be incorporated can be randomly distributsd, but block copolymers may al-so be present, the latter being preferred to the ~ormer.
Suitable block copolymers are copolymers ~hich have a mean molecular weight of from 500 to 8,000, preferably from 1,000 to 5,000, and which contain up to 40, prefer-ably from 10 to 30, particularly preferably from 10 to 20, % by weight of -CH2-CH2-0- units. Among the block 1 323~59 copolymers which are solid under normal conditions, only those which are water~soluble are suitable. The block copolymers which are liquids under normal cond;tions need not necessariLy be soluble ;n water.
Preferably used protective colloids are poly-(propylene ox;de) homopolymers. Poly(propylene oxide) homopolymers ~hich have a mean molecular weight of from 400 to 1,000, very particularly preferably about 900, are preferably composed of straight-chain molecules and on average preferably contain two hydroxyl groups per molecule are part;cularly preferably used.
Polytpropylene oxide) homopolymers are understood as meaning compounds which - with the exception of any incorporated terminal groups or initiator compounds -are essentially composed only of -CHCH3-CH20- units.
The term "essentially" is intended to express the fact that the use of poly(propylene oxide) homopolymers which contain small amounts of foreign monomers (for example butylene oxide) may also lead to usable sheet s;licate dispers;ons.
The polyl(propylene oxides) (sic) to be used ac-cording to the invention can be prepared in a known man-ner by polymerization of propylene oxide or by propo%y-lation of suitable initiator molecules, such as, for example, glyceroL, trimethylolpropane, hexanetriol, pen-taerythritol, sorbitol~ sucrose, ethylenediamine, car-boxyLic acids, carboxamides, etc. (-CH2-CH2-0- groups are introduced by copolymerization with ethylene oxide) and are available commercially in a wide varietya - 8 - l 32 3 4 5 9 The sheet silicates are dispersed in an aqueous dispersant. Preferably, exclus;vely water, very particu-larly preferably deionized water, is used as the disper-sant. The water can, if necessary, preferably conta;n water-dilutable organic solvents, such as, for example, butanol, butylglycol, ethylene glycol dimethyl ether, cyclohexanone, acetone, etc.
To prepare the dispersions according to the ;n-vention, the sheet silicate is mixed intimately with the poly(propylene oxide) as such or, preferably, in the presence of the aqueous dispersant. This mixing is pre-ferab~y effected using high shear forces (dissolver).
The dispersions according to the invention con-sist of from 1 to 10% by weight of sheet silicate, from 0.3 to 15X by weight of poly(propylene oxide~ and from 98.7 to 75% by weight of aqueous dispersant. From 0~3 to 2 parts by weight of poly(propylene oxide) are used per 1 part by weight of sheet sil;cate.
In a preferred method of preparation of the dis-persions to be used according to the invention, the sheetsilicate to be dispersed is first dispersed in some of the total amount of water to be used, with the aid of a d;ssolver. The appropriate amount of the poly(propylene oxide) to be used is then added to this dispersion, and dispersing ;s continued using very high shear forces~
Finally, the remaining water is added with very v;gorous st;rring (dissolver), and a ready-to-use sheet silicate dispersion which can be readily incorporated into water-dilutable coating compositions is obtained straightaway.
_ 9 _ Water-dilutable coating composit;ons contain water, water-dilutable b;nders, ;f necessary pigments, organ;c solvents and further conventional additives.
These are preferably baking finishes, ie. water-djlutable coating compositions which are cured on the substrate un-der the action of heat.
The water-d;lutable coating compos;t;ons can ;n principle contain all binders which are suitabLe for water-dilutable coating compositions. Water-dilutable polyester, pùlyacrylate, polyurethane or am;noplast res;ns may be mentioned as examples.
The sheet silicate dispersions according to the invention are preferably incorporated into water-dilutable coating compositions which contain pigments - preferably metallic pigments, particularly preferably aluminum pig-ments in flake form - and which are suitable for the pro-duction of the base coat of the two-coat system of the base coat/clear coat type. Examples of such coating com-positions are to be found in U.S. Patent 4,558,090 and ~uropean Patent Applicat;on 158,099. Preferred coating compositions`of this type contain water-dilutable poly-urethane resins, with or ~ithout water-dilutable poly-ester and/or polyacrylate resins, as binders, and suit-able crosslinking agents.
The d;spersions according to the invention are added to the water-dilutable coating compositions in amounts such that the water-d;lutable coating composi-tions contain from 0.5 to 10% by we~ght, based on the b;nder solids, of sheet silicate. In case~ in wh;ch , ' `: ' ' . ': . ~
-- 10 - 1 32 345q no metalLic pigments are present, from 0.5 to 5~ by weignt, preferably from 1.4 to 3% by weight, based on the binder solids, of sheet silicate are used. In coating composi-tions containing metallic pigments, from 2 to 10% by S weight, preferably from 4 to 6~ by weight~ based on the binder solids, of sheet silicate are used.
Incorporation of the dispersions according to the ;nvention into the water-dilutable coating composi-tions can be effected by generally well known methods, as a rule at any time during the production process for the water-dilutable coating compositions.
If the sheet s;licate dispersions according to the invent;on are incorporated into water-dilutable coat-;ng compos;tions, coat;ng compos;t;ons are obtained which have excellent spray application properties and give moisture-insensitive coatings having good adhesionO The sheet silicate dispersions according to the invention have a particularly advantageous action if they are in-corporated into water-dilutable coating compos;tions which contain metallic p;g~ents and are su;table for the production of the base coat of a two-coat system of the base coat/clear coa~ type. The coating compositions ob-tained ;n this manner have optimum rheological properties and good spray application properties and can be processed to give moisture-insensitive t~o-coat metalLic effect sys-tems of the base coat/clear coat type which d;splay a good effect and have good adhesion.
The E~amples which follo~ illustrate the inven-tion in more detail. AL~ parts and percentages stated .
- - 11 - 1323~59 are by weight unless expressly stated otherwise.
Example 1 4 parts by weight of a purified sodium magnes;um fluorine lithium sheet silicate of the montmorillon;te type are added slowly to S0 parts by weight of deionized water w;th v;gorous stirring ~dissolver: 3,000 to 4,000 revolut;ons per m;nute). Thereafter, 4 parts by weight of a stra;ght-chain poly(propylene oxide) having a mean molecular weight of 900 and an OH number of 125 are added with v;gorous stirring, and st;rring ;s continued for a further 15 minutes. A further 42 parts by weight of de-ionized ~ater are then added, and stirring is cont;nued for a further 15 m;nutes.
Example 2 4 parts by weight of a purified sodium magnesium fluorine lithium sheet silicate of the montmsriLlonite type which has been modified with tetrasod;um pyrophos-phate as a protective colloid are added to 50 parts by weight of deionized water with vigorous stirring ~dis-solver: 3,00U to 4,000 revolutions per minute)~ After the addition, stirring is continued for a further 15 m;nutes. A further 46 parts by weight of deionized water are then added with vigorous stirring, and stir-ring is continued for a further 15 minutes~
Example 3 The sheet silicate dispsrsions obtained accord-;ng to Example 1 and 2 are incorporated ;nto the water-d;lutable basecoating compositions described in the patent examples of EP-A-89,497 and U.S. Patents 4,489~135 and `': ' ' ~' `, `
`
- 12 - 1323~59 4,558,090 under equivalent cond;tions.
The basic coating compositions thus prepared are applied to bondered steel sheets by spray application and, after drying in the air for 15 minutes at room temperature (about 2ûC), are coated w;th a clear coat and baked, as described in EP-A-89,497 and U.S. Patents 4,489,135 and 4,558,090.
The basic coating compositions prepared using the sheet silicate dispersions prepared according to Example 1 are clearly superior to the basic coating compositions which have been prepared using the sheet silicate disper-sion prepared in Example 2, in the follo~ing respects:
a) tendency of the base coat to run, b) metallic effect, c) resistance of the two-coat system to moisture (damp heat constant atmosphere: 10 days, 40C, 100% relative humidity), and d) adhesion o~ the coating after exposure ~o moisture.
, .
~ ater-d;lutable coating compositions, in par-ticular those ~hich are to be processed by spray appli-cation, for example in automotive coating, must have very particular rheological propert;es~ An espec;ally important role ;s played by the rheolog;cal properties in the case of water-d;lutable coat;ng compos;t;ons ~h;ch conta;n metal pigments and are used for the production of the base coat of a t~o-coat system of the base coat/
clear coat type (cf. for example European Patent 38 127~.
The rheological properties of ~ater-dllutable coat;ng compos;tions very decisively ;nfluence the appli-cat;on properties of the coating compositions. In~the case of wàter-dilutable coat;n~ compos;tions conta~ining metal p;gments, the or;entat;on of the metal pigment particles and hence the achievable metallic effect depend very substantially on the rheological properties ~f the coating compositions.
`. ' ' ' : ,.'`
, .
-. " ', .' :
. .
~ . . . . . . . . .
. . - , , . , . , - . .
. - 2 - 1 3 2 34 5 9 To control the rheological properties of aqueous coat;ng compositions, sheet silicates are extensively used. The sheet silicates swell in water and form gels, which have a high flow limit and low plastic v;scosity S when subjected to shearing.
Incorporation of the sheet silicates into the water-dilutable coating compos;tions is preferably effec-ted via d;spers;ons which are prepared from a sheet s;licate, modified with an anionic protective colloid (for example tetrasodium pyrophosphate), and water. These dispersians have a sol character instead of a gel charac-ter and can be incorporated into the water-dilutable coating compositions simply by metering in~ On mixing, the effect of the protective colloid is eliminated, and the sheet silicate can display its act;on as a v;scosity assistant.
If the dispersions described above are incorporated into water-dilutable coating compositions, coating com-positions are obtained which have poor spray application properties and give moisture-sensitive, poorly adhering coat;ngs. These d;ff;culties occur to a greater extent in the case of water-dilutable coitin;g compos~it;ons wh;ch contain metal pigments, preferably aluminum pigments in flake form, and are int~nded to be ùsed for the produc-tion of the base coat of a two-coat system of the ~ase coat/clear coat type. In these cases, moisture-sens;tive, poorly adhering coatings which have only an inadequate metall;c effect are obtained~
It is the object of the invention to provide sheet ` . ~ ~ .
' ' ` ' . : : -. " ' , . .
.. , ~ , . .
'' 272g3-19 sllicate dlspersions ~hich can be readily incorporated lnto water-dllutable coating composltions and can be used to obtaln water-dllutable coat~ng compositions which have optimum rheological properties and good spray applicatlon properties and which glve molsture-insensltlve coatlngs havlng good adheslon. It is the particular ob~ect of the invention to provide sheet sllicate disperslons which can readily be incorporated into water-dllutable coating compositions contalnlng metal plgments sultable for the production of the base coat of a two-coat system of the base coat/clear co~t type and whlch can be used to obtain water-dllutable coating compositlons which contaln metal plgments and have optimum rheological propertles and good spray appllcatlon propertles and can be processed to give molsture-lnsensitlve two-coat metallic effect coatlngs of the base coat/clear coat type whlch have a good effect and good adheslon.
Accordingly, the present inventlon provides a disperslon which comprises a sheet sillcate whlch is suitable for controlling the rheological propertles of a~ueous coatlng composltions, a protective collold, water and, optionally, water dilutable organic solvents and ls su.ttable for use in lncorporating the sheet sllicate lnto water-dllutable coatlng composltions, wherein the protective colloid is a poly(propylene o~lde) that contains no hydrophobic terminal groups has an average of at least one hydroxyl group per molecule and may optionally contain up to 40 by weight of -CH2-CH2-0- units.
The inventlon also relates to water-dilutable coatlng ~r ~ .
composltlons whlch contaln a sheet sllicate, water, blnders, if necessary plgments, organlc solvents and further conventlonal addltives and whlch are obtainable by lncorporatlng the sheet sillcate into the coatlng 3a ~4 ~
: ' :
. , ~ ' ~-,, ' :'~, . ' ' ' ' - , . . .. .
.
i, : , - 4 - l 32~4 5q compositions via a dispersion ~hich is obtainable from a sheet sil;cate, a protective c~lloid and an aqueous d;spersant, wherein the sheet sili~ate is incorporated into the coating compositions via a dispersion which is S obtainable using poly(propylene oxide) as a protective colloid, and the poly~proPylene o~ide) conta;ns no hydro-phobic terminal groups, has on average at least one hydroxyl group per molecule and may optionally conta;n up to 40X by ~eight of -CHz-CH2-0- un;ts~
The invention also relates to a process fo~ in-corporating sheet silicates into water-dilutable coating compositions, in which the sheet silicates are incorporated into the coating compositions by incorporating dispersions which are obtainable from the sheet silicate, a protective colloid and an aqueous dispersant, wherein the sheet sili-cates are incorporated via dispersions which are obtain-able using poly(propylene oxide) as a protective colloid, and the poly~propylene oxide) contains no hydrophobic ter-minal groups, has on average at least one hydroxyl group per molecule and may optionally contain up to 40~ by weight of -CH2-CH2-0- units.
The invention also relates to the use of the dis-persions described above as coating assistants for incor-porating sheet silicates into vater-dilutable coating com-posit;ons~ in partiçular into vater-dilutable coating com-pos;tions which co.ntain pigments - preferably metall.ic pigments - and are suitable for the production of base coats of tvo-coat systems of the base coat/clear coat type.
_ 5 _ 1323459 U.S. Patent 3,687,885 d;scloses water-dilutable coating compos;tions wh;ch cons;st of a d;spersion of a polymer prepared from ethylenically unsaturated monomers, of a sheet sil-icate, of a nonionic surfactant and of a S thickener. The non;onic surfactants used are alkoxylated alkyLphenols and alkoxylated alcohols wh;ch are composed of 8 to Z2 carbon atoms~ The coating compositions des-cribed ;n U.s. Patent 3,687,885 contain no metall;c pig-ments and are completely unsuitable for the product;on of the base coat of a metallic effect coating of the base coat/clear coat type. U.S. Patent 3,687,885 does not provide the skilled worker with any ;nformation at all for achieving the object of the present invent;on.
Sheet silicates which are suitable for control-ling the rheological properties of aqueous coating com-positions are very familiar to the skilled ~orker (cf.
for example H. Kittel, Lehrbuch der Beschichtungen, Vol.
II, page 340, and Vol. III, page 272 to page 274; Verlag ~.A. Colomb 1974, 1976). These are, in particular, aLu-minum magnesium silicate compounds of the montmorillonite type, for example attapulgite, bentonite or hectorite~
Hectorite is often described by the approximate empirical formu~a Na0~67(M9~Li)6Si8020(oH~F)4~ where Li and F may also be absent.
According to the invention, both natural and syn-thetic sheet siLicates can be used. Synthetic sodium mag-nesium and sodium magnesium fluorine l;thium sheet silicates OT the montmorillonite type are preferably used.
Mixtures of different sheet sil;cates can of course .
.
- 6 - ~323459 also be used.
According to the invention, the protective colloid used is poly(propylene oxide) which contains no hydrophobic terminal groups, has on average at least one hydroxyl g~oup per molecule and may optionally contain up to 40% by weight of -CHz-CHz-0- units.
The term polytpropylene oxide) is understood as meaning compounds which are composed of at least two struc-tural units of the formula -CHCH3-CH20-.
Hydrophobic terminal groups are understood as meaning groups which have an important effect on the sur-factant properties of the poly(propylene oxide~ and which 3S a rule are derived from hydrophobic compounds wh;ch contain more than 6 carbon atoms. Alkylphenols, long-chain aliphatic alcohols, such as, for example, fatty al-cohols, long-cha;n aliphatic amines, such as, for exam-pLe, fatty amlnes, long-chain aliphatic carboxylic acids, such as, for example, fatty acids, and long-chain ali-phatic carboxamides, such as, for example, fatty acid amides, may be mentioned as examples of such terminal group formers~
The -CH2-CH~-0- units which may be incorporated can be randomly distributsd, but block copolymers may al-so be present, the latter being preferred to the ~ormer.
Suitable block copolymers are copolymers ~hich have a mean molecular weight of from 500 to 8,000, preferably from 1,000 to 5,000, and which contain up to 40, prefer-ably from 10 to 30, particularly preferably from 10 to 20, % by weight of -CH2-CH2-0- units. Among the block 1 323~59 copolymers which are solid under normal conditions, only those which are water~soluble are suitable. The block copolymers which are liquids under normal cond;tions need not necessariLy be soluble ;n water.
Preferably used protective colloids are poly-(propylene ox;de) homopolymers. Poly(propylene oxide) homopolymers ~hich have a mean molecular weight of from 400 to 1,000, very particularly preferably about 900, are preferably composed of straight-chain molecules and on average preferably contain two hydroxyl groups per molecule are part;cularly preferably used.
Polytpropylene oxide) homopolymers are understood as meaning compounds which - with the exception of any incorporated terminal groups or initiator compounds -are essentially composed only of -CHCH3-CH20- units.
The term "essentially" is intended to express the fact that the use of poly(propylene oxide) homopolymers which contain small amounts of foreign monomers (for example butylene oxide) may also lead to usable sheet s;licate dispers;ons.
The polyl(propylene oxides) (sic) to be used ac-cording to the invention can be prepared in a known man-ner by polymerization of propylene oxide or by propo%y-lation of suitable initiator molecules, such as, for example, glyceroL, trimethylolpropane, hexanetriol, pen-taerythritol, sorbitol~ sucrose, ethylenediamine, car-boxyLic acids, carboxamides, etc. (-CH2-CH2-0- groups are introduced by copolymerization with ethylene oxide) and are available commercially in a wide varietya - 8 - l 32 3 4 5 9 The sheet silicates are dispersed in an aqueous dispersant. Preferably, exclus;vely water, very particu-larly preferably deionized water, is used as the disper-sant. The water can, if necessary, preferably conta;n water-dilutable organic solvents, such as, for example, butanol, butylglycol, ethylene glycol dimethyl ether, cyclohexanone, acetone, etc.
To prepare the dispersions according to the ;n-vention, the sheet silicate is mixed intimately with the poly(propylene oxide) as such or, preferably, in the presence of the aqueous dispersant. This mixing is pre-ferab~y effected using high shear forces (dissolver).
The dispersions according to the invention con-sist of from 1 to 10% by weight of sheet silicate, from 0.3 to 15X by weight of poly(propylene oxide~ and from 98.7 to 75% by weight of aqueous dispersant. From 0~3 to 2 parts by weight of poly(propylene oxide) are used per 1 part by weight of sheet sil;cate.
In a preferred method of preparation of the dis-persions to be used according to the invention, the sheetsilicate to be dispersed is first dispersed in some of the total amount of water to be used, with the aid of a d;ssolver. The appropriate amount of the poly(propylene oxide) to be used is then added to this dispersion, and dispersing ;s continued using very high shear forces~
Finally, the remaining water is added with very v;gorous st;rring (dissolver), and a ready-to-use sheet silicate dispersion which can be readily incorporated into water-dilutable coating compositions is obtained straightaway.
_ 9 _ Water-dilutable coating composit;ons contain water, water-dilutable b;nders, ;f necessary pigments, organ;c solvents and further conventional additives.
These are preferably baking finishes, ie. water-djlutable coating compositions which are cured on the substrate un-der the action of heat.
The water-d;lutable coating compos;t;ons can ;n principle contain all binders which are suitabLe for water-dilutable coating compositions. Water-dilutable polyester, pùlyacrylate, polyurethane or am;noplast res;ns may be mentioned as examples.
The sheet silicate dispersions according to the invention are preferably incorporated into water-dilutable coating compositions which contain pigments - preferably metallic pigments, particularly preferably aluminum pig-ments in flake form - and which are suitable for the pro-duction of the base coat of the two-coat system of the base coat/clear coat type. Examples of such coating com-positions are to be found in U.S. Patent 4,558,090 and ~uropean Patent Applicat;on 158,099. Preferred coating compositions`of this type contain water-dilutable poly-urethane resins, with or ~ithout water-dilutable poly-ester and/or polyacrylate resins, as binders, and suit-able crosslinking agents.
The d;spersions according to the invention are added to the water-dilutable coating compositions in amounts such that the water-d;lutable coating composi-tions contain from 0.5 to 10% by we~ght, based on the b;nder solids, of sheet silicate. In case~ in wh;ch , ' `: ' ' . ': . ~
-- 10 - 1 32 345q no metalLic pigments are present, from 0.5 to 5~ by weignt, preferably from 1.4 to 3% by weight, based on the binder solids, of sheet silicate are used. In coating composi-tions containing metallic pigments, from 2 to 10% by S weight, preferably from 4 to 6~ by weight~ based on the binder solids, of sheet silicate are used.
Incorporation of the dispersions according to the ;nvention into the water-dilutable coating composi-tions can be effected by generally well known methods, as a rule at any time during the production process for the water-dilutable coating compositions.
If the sheet s;licate dispersions according to the invent;on are incorporated into water-dilutable coat-;ng compos;tions, coat;ng compos;t;ons are obtained which have excellent spray application properties and give moisture-insensitive coatings having good adhesionO The sheet silicate dispersions according to the invention have a particularly advantageous action if they are in-corporated into water-dilutable coating compos;tions which contain metallic p;g~ents and are su;table for the production of the base coat of a two-coat system of the base coat/clear coa~ type. The coating compositions ob-tained ;n this manner have optimum rheological properties and good spray application properties and can be processed to give moisture-insensitive t~o-coat metalLic effect sys-tems of the base coat/clear coat type which d;splay a good effect and have good adhesion.
The E~amples which follo~ illustrate the inven-tion in more detail. AL~ parts and percentages stated .
- - 11 - 1323~59 are by weight unless expressly stated otherwise.
Example 1 4 parts by weight of a purified sodium magnes;um fluorine lithium sheet silicate of the montmorillon;te type are added slowly to S0 parts by weight of deionized water w;th v;gorous stirring ~dissolver: 3,000 to 4,000 revolut;ons per m;nute). Thereafter, 4 parts by weight of a stra;ght-chain poly(propylene oxide) having a mean molecular weight of 900 and an OH number of 125 are added with v;gorous stirring, and st;rring ;s continued for a further 15 minutes. A further 42 parts by weight of de-ionized ~ater are then added, and stirring is cont;nued for a further 15 m;nutes.
Example 2 4 parts by weight of a purified sodium magnesium fluorine lithium sheet silicate of the montmsriLlonite type which has been modified with tetrasod;um pyrophos-phate as a protective colloid are added to 50 parts by weight of deionized water with vigorous stirring ~dis-solver: 3,00U to 4,000 revolutions per minute)~ After the addition, stirring is continued for a further 15 m;nutes. A further 46 parts by weight of deionized water are then added with vigorous stirring, and stir-ring is continued for a further 15 minutes~
Example 3 The sheet silicate dispsrsions obtained accord-;ng to Example 1 and 2 are incorporated ;nto the water-d;lutable basecoating compositions described in the patent examples of EP-A-89,497 and U.S. Patents 4,489~135 and `': ' ' ~' `, `
`
- 12 - 1323~59 4,558,090 under equivalent cond;tions.
The basic coating compositions thus prepared are applied to bondered steel sheets by spray application and, after drying in the air for 15 minutes at room temperature (about 2ûC), are coated w;th a clear coat and baked, as described in EP-A-89,497 and U.S. Patents 4,489,135 and 4,558,090.
The basic coating compositions prepared using the sheet silicate dispersions prepared according to Example 1 are clearly superior to the basic coating compositions which have been prepared using the sheet silicate disper-sion prepared in Example 2, in the follo~ing respects:
a) tendency of the base coat to run, b) metallic effect, c) resistance of the two-coat system to moisture (damp heat constant atmosphere: 10 days, 40C, 100% relative humidity), and d) adhesion o~ the coating after exposure ~o moisture.
, .
Claims (18)
1. A dispersion which comprises a sheet silicate which is suitable for controlling the rheological properties of aqueous coating compositions, a protective colloid, water and, optionally, water dilutable organic solvents and is suitable for use in incorporating the sheet silicate into water-dilutable coating compositions, wherein the protective colloid is a poly(propylene oxide) that contains no hydrophobic terminal groups has an average of at least one hydroxyl group per molecule and may optionally contain up to 40% by weight of -CH2-CH2-O- units.
2. A dispersion as claimed in claim 1 wherein the poly(propylene oxide) is a homopolymer.
3. A dispersion as claimed in claim 2 wherein the homopolymer has a mean molecular weight of from 400 to 1,000.
4. A dispersion as claimed in claim 2 wherein the homopolymer is composed of straight chain molecules.
5. A dispersion as claimed in claim 2 wherein the homopolymer contains an average two hydroxyl groups per molecule.
6. A dispersion as claimed in claim 2 wherein the poly(propylene oxide) homopolymer has a mean molecular weight of about 900.
7. A dispersion as claimed in any one of claims 1 to 6 which comprises from 1 to 10% by weight of sheet silicate, from 0.3 to 15% by weight of poly(propylene oxide) and from 98.7 to 75%
by weight of water, and optionally, water dilutable organic solvents.
by weight of water, and optionally, water dilutable organic solvents.
8. A dispersion as claimed in claim 7 containing 98.7 to 75% by weight of water.
9. A dispersion as claimed in any one of claims 1 to 6 which contains from 0.3 to 2 parts by weight of poly(propylene oxide) per one part by weight of sheet silicate.
10. A water-dilutable coating composition which contains a sheet silicate, water or a binder, and is obtainable by incorporating the sheet silicate into the coating composition by means of a dispersion as claimed in any one of claims 1 to 6.
11. A water-dilutable coating composition as claimed in claim 10 which further comprises a pigment and an organic solvent.
12. A water-dilutable coating composition as claimed in claim 10, which coating composition contains a metallic pigment and is suitable for the production of the base coat of a two-coat system of the base coat/clear coat type.
13. A water-dilutable coating composition as claimed in claim 10, which composition is free of water-dilutable organic solvents.
14. A water-dilutable coating composition as claimed in claim 10 wherein the said dispersion comprises from 1 to 10% by weight of sheet silicate, from 0.3 to 15% by weight of poly-(propylene oxide) and from 98.7 to 75% by weight of water, and, optionally, water dilutable organic solvents.
15. A process for incorporating a sheet silicate which is suitable for controlling the rheological properties of aqueous coating compositions into a water-dilutable coating composition, which process comprises incorporating the sheet silicate by introducing the sheet silicate into the water-dilutable coating composition as a component of a dispersion as claimed in any one of claims 1 to 6.
16. Use of a dispersion as claimed in any one of claims 1 to 6 as a coating assistant for incorporating sheet silicate into a water-dilutable coating composition.
:
:
17. Use of a dispersion as claimed in any one of claims 1 to 6 as a coating assistant for incorporating sheet silicate into a water-dilutable coating composition which contains a pigment and is suitable for the production of a base coat of a two-coat system of the base coat/clear coat type.
18. Use as claimed in claim 17 wherein the pigment is a metallic pigment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3707388.5 | 1987-03-07 | ||
| DE19873707388 DE3707388A1 (en) | 1987-03-07 | 1987-03-07 | AQUEOUS LAYERED SILICATE DISPERSIONS, USE OF THESE DISPERSIONS AS LACQUERING AGENTS AND WATER-DISCOVERABLE COATING COMPOSITIONS CONTAINING LAYERED SILICATES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1323459C true CA1323459C (en) | 1993-10-19 |
Family
ID=6322530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000560537A Expired - Fee Related CA1323459C (en) | 1987-03-07 | 1988-03-04 | Aqueous sheet silicate dispersions, use of these dispersions as coating assistants and water-dilutable coating compositions containing sheet silicates |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US5198490A (en) |
| EP (2) | EP0348415A1 (en) |
| JP (1) | JPH0692553B2 (en) |
| KR (1) | KR930004699B1 (en) |
| AT (1) | ATE76889T1 (en) |
| AU (1) | AU615434B2 (en) |
| CA (1) | CA1323459C (en) |
| DE (2) | DE3707388A1 (en) |
| ES (1) | ES2032885T3 (en) |
| WO (1) | WO1988007070A1 (en) |
| ZA (1) | ZA881597B (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3919940A1 (en) * | 1989-06-19 | 1990-12-20 | Merck Patent Gmbh | DISPERSIONS OF SPHERICAL INORGANIC PARTICLES |
| GB9013702D0 (en) * | 1990-06-20 | 1990-08-08 | Ici Plc | Protective barriers |
| US5665822A (en) | 1991-10-07 | 1997-09-09 | Landec Corporation | Thermoplastic Elastomers |
| DE4139993A1 (en) * | 1991-12-04 | 1993-06-09 | Merck Patent Gmbh, 6100 Darmstadt, De | PIGMENT PREPARATION |
| EP0679699A1 (en) * | 1994-04-29 | 1995-11-02 | Basf Corporation | Polyether-siloxane paint additive |
| US5631080A (en) * | 1995-03-27 | 1997-05-20 | The Mead Corporation | Method for flocculating clay and composition produced thereby |
| US5989696A (en) * | 1996-02-13 | 1999-11-23 | Fort James Corporation | Antistatic coated substrates and method of making same |
| US6086991A (en) * | 1996-06-12 | 2000-07-11 | Hoechst Trespaphan Gmbh | Method of priming poly(ethylene terephthalate) articles for coating |
| ATE256711T1 (en) | 1996-06-12 | 2004-01-15 | Trespaphan Gmbh | METHOD FOR PRIMERING POLYOLE ITEMS FOR COATING |
| ID19111A (en) | 1996-06-12 | 1998-06-18 | Hoechst Celanese Corp | METHOD OF MAKING POLYLELEFIN MATERIALS FOR COATING |
| ID19516A (en) * | 1996-06-12 | 1998-07-16 | Hoechst Celanese Corp | Vapor Barrier Coatings for Polyimetic Objects |
| CN1100098C (en) * | 1996-06-12 | 2003-01-29 | 赫彻斯特－特拉丝帕番有限公司 | Vapor barrier coating for polymeric articles |
| US6077608A (en) * | 1996-09-19 | 2000-06-20 | Ppg Industries Ohio, Inc. | Multilayered coating with powder clear coating and substrates therewith and method |
| DE19726814A1 (en) * | 1997-06-25 | 1999-01-07 | Murjahn Amphibolin Werke | Coating agent to reduce the tendency to soiling on facades |
| DE19754182C2 (en) * | 1997-12-06 | 2001-09-06 | Herberts Gmbh | Aqueous sheet silicate dispersions and their use in the production of rheology-optimized aqueous coating media |
| DE19841976A1 (en) * | 1998-09-14 | 2000-03-30 | Herberts & Co Gmbh | Two-coat coating of aqueous basecoat and clearcoat with an improved clearcoat wetting limit |
| US6107387A (en) * | 1999-02-22 | 2000-08-22 | Ppg Industries Ohio, Inc. | Acidified aqueous dispersions of high aspect ratio clays |
| US20040162378A1 (en) * | 2002-06-12 | 2004-08-19 | Armin Goebel | Aqueous binders containing layered silicate, process for the production thereof and use thereof in aqueous coating compositions |
| US20040028822A1 (en) * | 2002-08-08 | 2004-02-12 | Wilfried Dutt | Continuous process for applying a tricoat finish on a vehicle |
| US20070166512A1 (en) * | 2004-08-25 | 2007-07-19 | Jesch Norman L | Absorbent Release Sheet |
| WO2007002896A2 (en) * | 2005-06-29 | 2007-01-04 | Graphic Packaging International, Inc. | Packaging material for food items containing permeating oils |
| US20070292569A1 (en) * | 2005-06-29 | 2007-12-20 | Bohme Reinhard D | Packaging material for food items containing permeating oils |
| US8826959B2 (en) | 2006-06-29 | 2014-09-09 | Graphic Packaging International, Inc. | Heat sealing systems and methods, and related articles and materials |
| US8753012B2 (en) * | 2006-06-29 | 2014-06-17 | Graphic Flexible Packaging, Llc | High strength packages and packaging materials |
| ES2611591T3 (en) * | 2006-07-20 | 2017-05-09 | Basf Se | Water-based varnishes with highly functional, highly branched or hyperbranched polycarbonates |
| US20090263048A1 (en) * | 2008-04-16 | 2009-10-22 | Iannelli Ii Michael Louis | Bag Structures And Methods Of Assembling The Same |
| EP2143743A1 (en) | 2008-07-08 | 2010-01-13 | Akzo Nobel Coatings International B.V. | Use of derivatives of dianhydrohexitol in the preparation of resins |
| ITMI20122261A1 (en) * | 2012-12-28 | 2014-06-29 | Indesit Co Spa | STAINLESS STEEL SURFACE TREATMENT PROCESS |
| EP2952545A1 (en) * | 2014-06-04 | 2015-12-09 | STO SE & Co. KGaA | Low reflection paint composition |
| CN112020543B (en) | 2018-04-27 | 2022-05-24 | 巴斯夫涂料有限公司 | Surface-modified alumina hydroxide particles as rheological additives in aqueous coating compositions |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3687885A (en) * | 1970-04-15 | 1972-08-29 | Du Pont | Water base paints having an improved balance of anti-drip and leveling qualities |
| DE2613099B2 (en) * | 1975-03-28 | 1981-04-30 | Dai Nippon Toryo Co., Ltd., Osaka | Aqueous dispersion coating compositions |
| US3998973A (en) * | 1975-04-07 | 1976-12-21 | R. T. Vanderbilt Company, Inc. | Thickening composition |
| US4017452A (en) * | 1975-04-30 | 1977-04-12 | Presto Products, Incorporated | Polymer modified hydrophilic inorganic fillers for thermoplastic polymeric materials |
| DE2850609A1 (en) * | 1978-11-22 | 1980-06-12 | Basf Ag | METHOD FOR PRODUCING STABLE FILLER-POLYOL DISPERSIONS |
| US4351754A (en) * | 1979-09-17 | 1982-09-28 | Rohm And Haas Company | Thickening agent for aqueous compositions |
| JPS572367A (en) * | 1980-06-07 | 1982-01-07 | Kansai Paint Co Ltd | Water-dispersed thermosetting resin slurry paint composition |
| US4476271A (en) * | 1981-05-07 | 1984-10-09 | Dai Nippon Toryo Co., Ltd. | Aqueous dispersion type thermosetting coating composition |
| DE3311518A1 (en) * | 1983-03-30 | 1984-10-04 | Basf Farben + Fasern Ag, 2000 Hamburg | HEAT-CURABLE COATING AGENTS AND THEIR USE |
| US4436862A (en) * | 1983-06-14 | 1984-03-13 | Nl Industries, Inc. | Thermally stable thickener |
-
1987
- 1987-03-07 DE DE19873707388 patent/DE3707388A1/en not_active Withdrawn
-
1988
- 1988-03-03 EP EP88902131A patent/EP0348415A1/en active Pending
- 1988-03-03 AU AU14285/88A patent/AU615434B2/en not_active Ceased
- 1988-03-03 US US07/399,482 patent/US5198490A/en not_active Expired - Lifetime
- 1988-03-03 JP JP63502200A patent/JPH0692553B2/en not_active Expired - Lifetime
- 1988-03-03 DE DE8888103254T patent/DE3871560D1/en not_active Expired - Lifetime
- 1988-03-03 KR KR1019880701407A patent/KR930004699B1/en not_active IP Right Cessation
- 1988-03-03 AT AT88103254T patent/ATE76889T1/en not_active IP Right Cessation
- 1988-03-03 EP EP19880103254 patent/EP0281936B1/en not_active Expired - Lifetime
- 1988-03-03 ES ES198888103254T patent/ES2032885T3/en not_active Expired - Lifetime
- 1988-03-03 WO PCT/EP1988/000155 patent/WO1988007070A1/en not_active Application Discontinuation
- 1988-03-04 CA CA000560537A patent/CA1323459C/en not_active Expired - Fee Related
- 1988-03-07 ZA ZA881597A patent/ZA881597B/en unknown
-
1992
- 1992-12-01 US US07/984,151 patent/US5290845A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR930004699B1 (en) | 1993-06-03 |
| ES2032885T3 (en) | 1993-03-01 |
| ZA881597B (en) | 1988-08-30 |
| DE3871560D1 (en) | 1992-07-09 |
| EP0281936A1 (en) | 1988-09-14 |
| US5290845A (en) | 1994-03-01 |
| EP0348415A1 (en) | 1990-01-03 |
| DE3707388A1 (en) | 1988-09-15 |
| JPH0692553B2 (en) | 1994-11-16 |
| EP0281936B1 (en) | 1992-06-03 |
| AU615434B2 (en) | 1991-10-03 |
| US5198490A (en) | 1993-03-30 |
| JPH01503628A (en) | 1989-12-07 |
| ATE76889T1 (en) | 1992-06-15 |
| WO1988007070A1 (en) | 1988-09-22 |
| AU1428588A (en) | 1988-10-10 |
| KR890700649A (en) | 1989-04-26 |
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