CA1187249A - Production of polymer microparticles and coating compositions containing them - Google Patents
Production of polymer microparticles and coating compositions containing themInfo
- Publication number
- CA1187249A CA1187249A CA000366359A CA366359A CA1187249A CA 1187249 A CA1187249 A CA 1187249A CA 000366359 A CA000366359 A CA 000366359A CA 366359 A CA366359 A CA 366359A CA 1187249 A CA1187249 A CA 1187249A
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- weight
- derivative
- acid
- monomers
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
- C08F2/08—Organic solvent with the aid of dispersing agents for the polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/923—Treating or preparing a nonaqueous dispersion or emulsion of a solid polymer or specified intermediate condensation product
Abstract
ABSTRACT OF DISCLOSURE
The production is described of polymer microparticles, which may optionally be crosslinked, by dispersion polymerisation in aliphatic hydrocarbon liquid of a monomer mixture which comprises up to 50% of styrene or a substituted derivative there-of and up to 50% by weight of a derivative of maleic acid or fumaric acid which is soluble in the hydrocarbon liquid at the polymerisation temperature. The microparticles have a high refractive index and are suitable for incorporation in coating compositions which are based on a film-forming polymer, such as a thermosetting acrylic resin or an alkyd resin, containing a significant proportion of aromatic regidues and which are intended to be used either unpigmented or when containing only light-absorbing pigment.
The production is described of polymer microparticles, which may optionally be crosslinked, by dispersion polymerisation in aliphatic hydrocarbon liquid of a monomer mixture which comprises up to 50% of styrene or a substituted derivative there-of and up to 50% by weight of a derivative of maleic acid or fumaric acid which is soluble in the hydrocarbon liquid at the polymerisation temperature. The microparticles have a high refractive index and are suitable for incorporation in coating compositions which are based on a film-forming polymer, such as a thermosetting acrylic resin or an alkyd resin, containing a significant proportion of aromatic regidues and which are intended to be used either unpigmented or when containing only light-absorbing pigment.
Description
7'~
PRODUCTIOl~ OF POLYMER MICROP_RTICLES
A~D COATI~G COMPOSITIO~S CO~TAI~I~G THEM
This invention relates to a proc~s for ~aking polymer microparticles, and to coating compositions containing the particles.
The preparation of polymeric microparticles and their incorporation into coating compositions comprising a film-forming polymer have been described, for example in British Patents ~os. 967,051; 1,242,051, 1,451,948 and 1,538,151, in United States Patent ~o.
4,025,474, in German Offenlegungsschriften 2818093, 2818094, 2818095~ 2818100, 2818102 and in European Patent Applications ~os. 783Q0095 and 78300419. In certain of these publications the particles in question are referred to as "microgel" particles, in which case the polymer of which the particles are composed is crosslinked to a greater or le ser extent and thereby rendered insoluble in any inert liquid diluent in which the film-forming polymer of the coating composition may be carried (although it may be swollen by that diluent). In other instances, the microparticles may be non-crosslinked and retain their identity in the coating composition by reason of the q~
- ~8~72~9~
PRODUCTIOl~ OF POLYMER MICROP_RTICLES
A~D COATI~G COMPOSITIO~S CO~TAI~I~G THEM
This invention relates to a proc~s for ~aking polymer microparticles, and to coating compositions containing the particles.
The preparation of polymeric microparticles and their incorporation into coating compositions comprising a film-forming polymer have been described, for example in British Patents ~os. 967,051; 1,242,051, 1,451,948 and 1,538,151, in United States Patent ~o.
4,025,474, in German Offenlegungsschriften 2818093, 2818094, 2818095~ 2818100, 2818102 and in European Patent Applications ~os. 783Q0095 and 78300419. In certain of these publications the particles in question are referred to as "microgel" particles, in which case the polymer of which the particles are composed is crosslinked to a greater or le ser extent and thereby rendered insoluble in any inert liquid diluent in which the film-forming polymer of the coating composition may be carried (although it may be swollen by that diluent). In other instances, the microparticles may be non-crosslinked and retain their identity in the coating composition by reason of the q~
- ~8~72~9~
2 --polymer of which they are composed being inherently insoluble in the diluent.
Such microparticles are conveniently made by processes o~ dispersion polymerisation of monomers in suitable liquids in the presence of polymeric stabilisers for the particles of polymer which are formed. The microparticles are thereby sterically stabilised against flocculation or aggregation, in the manner described in "Dispersion Polymerisation in Organic Media", ed. K.E.J. Barrett (John Wiley, 1975) and in many patent specifications such as British Specifications Nos. 934,038: 941,305; 1,052,241;
1,122,397; 1,143,404 and 1,231,614.
Iwo types of such dispersion polymerisation process may be distinguished. In the first, which is described in British Patent ~o. 1,451,948 referred to above, microgel particles are formed as a minor product of a dispersion polymerisation of ethylenic-ally unsaturated monomers in the presence of a 90-called "multifunctional" stabiliser. This stabiliserpossesses the molecular structural features which are common to all sterically stabilising entities, namely a polymeric component of the molecule which is solvated by the continuous phase of the dispersion and another component which associates with the disperse phase, howe~er, it possesses in addition a plurality of groupings which are capable of copolymer-ising with the monomers undergoing dispersion polymer-isation. The main result of using such a stabiliser~
as described more generally in British Patant Spec-ification No. 1,231,614, is that the stabiliser becomes covalently linked to the disperse polymer, Z~g but a ~urther consequence is that, whilst the greater part of the polymer formed as the disperse phase is non-crosslinked, a small part of it becomes cross-linked through the intervention of the copolymeris-able groups in the stabiliser. By adding to the dispersion thus obtained a su~ficiant amount of an active solvent for the non-crosslinked disperse poly-mer, there can be produced a solution-type coating composition in which the non-crosslinked polymer constitutes the main film-forming material but in which the crosslinked microgel remains as insoluble, discrete and sterically stabilised paxticles. It is, however, difficult by this method to control the relative proportions of microgel and of non-cross linked pol~mer which are producéd, and also to control the molecular weight of the latter polymer (which may be desirable in order to optimise its film ~orming properties) without adversely affecting the yield of microgel. Furthermore it is, of course, inevitable that microgel made in this way will have essentially the same monomer composition as that of the non-crosslinked polymer.
In the second method of making micropart-icles, which is described in British Patent Specif-ication ~o. 1,538,151 and in the published German and European spe~ifications referxed to earlier, the particles are produced essentially as the sole disperse material; here crosslinking is achieved through the expedient of having present in the monomer charge being polymerised pairs of comonomers carrying mutually chemically reactive groups (in addition to the copolymerisa~le groups) b~ reaction ~1~37Z~
of which groups covalent cross-links between the polymer chains may be generated. A variety of combin-ations of mutually reactive groups has been proposed, for example epoxy and carboxyl, amine and carboxyl, epo~ide and carhoxylic anhydride, amine and carboxylic anhydride, hydroxyl and carboxylic anhydride, amine and carboxylic acid chloride, alkylene-imine and carbo~yl, and organo-alkoxysilane and carboxyl. Since the microparticles made by this procedure are not accompaniad by significant amounts of other polymeric products, they can conveniently be incorporated into coating compositions ~ased on film-forming resins of any desired type and in any desired proportion.
One class of coating composition to which polymeric microparticles can with advantage be added is that based upon solutions of thermosetting acrylic resins; these are of particular interest for the painting of car bodies and othPr metal structures which can tolerate stoving at relatively high tempex-atures following application of the composition,whereby the composition is converted to a hard, insoluble coating through reaction of the resin with a crosslinking agent such as a melamine-formaldehyde resin. It is common practice to include in the monomers, from which these thermosetting acrylic resins are derived, a proportion of up to 40~0 by weight of styrene.
This is done for two main reasons : firstly, because of the significantly higher refractive inde~ of poly-styrene as compared with that of most u~modified polymers of acrylic or methacrylic acid esters (1.59 and 1.46 - 1.49 respectively), the incorporation of styrene gives rise to a higher reflectance of light at ~L~87Z~9 the air polymer interface and hence enhances the apparent gloss of the coating; secondly, copolymers containing some styrene show improved flow during the stoving operation in comparison with methyl methacrylate homopolymers. On the other hand, a practical upper limit, of about 500~ by weight of total monomers, is set to the proportion of styrene by the strong ultra-violet light absorption properties of the latter and the consequent adverse effect on exterior durability of coatings containing it.
A general consideration affecting the incorp-oration of polymeric microparticles into coating comp-ositions is that unless the refractive index of the microparticulate polymer is fairly closely matched to that of the main film-forming resin, there will be scattering of light at the boundary between the two polymer phases and the coating film will appear cloudy.
I~is will, of course, be of little consequence in compositions containing light-scattering pigments such as titanium dioxide, but in coloured compositions of a deep hue containing light absorbing pigments, partic-ularly coloured metallic compositions containing a low level of aluminium flake~ and above all in unpigmented compositions intended for the production of clear coat-ings, it can be a serious defect. Where a thermosettingcopolymer contains a significant proportion of styrene, incorporation of micropar~icles consisting essentially of polymethyl methacrylate will have this undesirable result; the problem tends to be accentuated by the fact that the melamine-formaldehyde resins which are most commonly used as crosslinking agents in such systems themselves have relatively high refractive 2~9t indices (in the region of 1.52).
When microgel particles are produced by the first of the two dispersion polymerisation techniques described above, it follows that the microgel polymer will always have approximately the same monomer comp-osition as the main film-forming polymer which is produced along with it, so that the above-mentioned refractive index problem does not arise. A disadvan-tage of this first-described technique additional to those already mentioned is, however, that the very polymers which it is desired to use as the main film-former in many clear-coat compositions and compositions of high solids content are not readily prepared by ~on-aqueous dispersion polymerisation. For a variety of reasons, such polymerisation is most conveniently carried out in low polarity organic liquids, in particular aliphatic hydrocar~ons, and, whilst polymers based wholly or overwhelmingly upon methyl methacrylate are practically insoluble in thesa liquids, copolymers containing other monomers, such as styrene, in signif-icant proportions may be appreciably soluble in them.
This may make it difficult to obtain initially a stable dispersicn of the copolymer.
The foregoing discussion has considered the problems which arise where the main film-forming polymer is of the addition type, i.e. is one derived from ethylenically unsaturated monomers. However, the same need to match the refractive index of the microgel particles to that of the film-former may arise in the case of the use of certain alkyd or polyester resins in the latter capacity, more spec~fically those alkyd resins which are derived in part from aromatic starting ~37~
materials, such as phthalic anhydride, and which in consequence have relatively high refractive indices.
Here again, there may be used as crosslinking agents melamine-formaldehyde resins also having high refract-ive indices.
The evident way out of the di~ficulty, what-ever the nature of the film-forming polymer into which the microgel polymer is incorporated, is to make microgeL polym~r which contains a substantial propor-tion of styrene by the second of the two dispersion polymerisation methods referred to. However, as indicated above, the dispersion polymerisation of styrene in an aliphatic hydrocarbon using free radical catalysts presents certain other pro~lems : the poly-merisation proceeds slowly and the polymer formed is heavily swollen by the hydrocar~on at the polymeris-ation temperature normally employed, so that a coarse particle-size dispersion results (see "Dispersion Polymerisation in Organic Media", ed. K.E.J.Barrett :
John Wiley, London, 1975 : pages 213-214~. These problems are encountered equally in the case of monomer mixtures containing a substantial proportion of styrene, for example greater than 207/o by weight.
We have now found that dispersion polymer-isation of such monomer mixtures can be carried out without these difficulties if the monomer mixture contains, in addition to styrene, a specified deriv-ation of maleic acid or fumaric acid.
According to the present invention we provide a process for the production of addition polymer micro-particles, comprising the dispersion polymerisation in an aliphatic hydrocarbon liquid of an ethylenically Z~
-- 8 ~
unsaturated monomer mixture which gives rise to a polymer or copolymer insoluble in the hydrocarbon liquid and which comprises (i) up to 50% by weiyht of styrene or a substituted derivative thereof and (ii) up to 5~0 by weight of a derivative of maleic acid or fumaric acid which is soluble in the hydro-carbon liquid at the temperature of polymerisation, thepolymerisation being carried out in the presence in the hydrocarbon liquid o a steric dispersion stabiliser the molecule of which comprises at least one polymeric component which is solvated by the hydrocarbon liquid and at least one other component which is not solvated by the liquid and is capable of associating with the polymer produced.
Any derivative of maleic acid or fumaric acid which is soluble in the aliphatic hydrocarbon liquid i5 suitable for use in the process of the invention. This solubility requirement excludes maleic acid and fumaric acid themselves, and also maleic anhydride, but a variety of compounds derived from these, for example through the medium of the carboxyl groups, are suitable. A preferred type of derivative is one containing in the molecule at least one aromatic group, since the presence of the aromatic nucleus provides an enhancement of the refractive index of the microparticle additional to that afforded by the copolymerised styrene or styrene derivative.
One class of derivative of maleic acid or fumaric acid containing at least one aromatic nucleus ~hich is especially suitable is the class of ~-aryl-substituted maleimides of the general formula '72~
g CH - CO ~
~ Ar CH - CO
where Ar is an aromatic radical which may contain a single benzene nucleus or two or more connected or fused benzene nuclei and which may optionally carry other substituent groups. Such compounds are in general soluble in aliphatic hydrocarbons. Examples of members of this class include ~-phenylmaleimide, ~-o-tolylmaleimide, ~-m-tolylmaleimide, ~-p-tolyl-maleimide, ~-o-biphenylylmaleimide, ~-p-biphenylyl-maleimide, ~-p-~tert-butyl)phenylmaleimide, ~--p-dodecylphenylmaleimide, ~-a-naphthylmaleimide, ~-~-naphthylmaleimide, ~-o-chlorophenylmaleimide, ~-m-chlorophenylmaleimide, ~-p-chlorophenylmaleimide, ~-p-methoxyphenylmaleimide, ~-2-methyl-4-chlorophenyl-maleimide, N-2-methoxy-5-chlorophenylmaleimide, ~-4-phenoxyphenylmaleimide, ~-4-phenylcarboxyphenyl-maleimide, ~-4-(o-chlorophenoxy)phenylmaleimide, N-2, 5-dichlorophenylmaleimide, ~-2, 5-dimethoxyphenyl-. maleimide and ~-2, 4, 5-trichlorophenylmaleimide. Any of the foregoing substances may be made by the process-es described in British Patent Specifications ~os.
1~040,907 and 1,041,027.
Another class of derivative of maleic acid or fumaric acid containing at least one aromatic nuclues which is soluble in aliphatic hydrocarbons and is suitable for use according to the invention is the class of diesters of maleic acid or fumaric acid of the structure CH.CO.OX CH.CO.OX
ll or li : CH.CO.OY YO.CO.CH
~724~
where either X or Y, or both, is an aromatic radical which may contain a single benzene nuclueus or two or more connected or fused benzene nuclei and which may optionally carry other substituent groups.
Examples of members of this class include diphenyl-maleate, methyl phenyl maleate, dibenzylmaleate, di-(o-chlorobenzyl) maleate, di(p-chlorobenzyl)maleate, benzyl methyl maleate, dinaphthyl maleate, bis(di-phenylyl) maleate, diphenyl fumarate, methyl phenyl fumarate and other fumaric esters corresponding to the foregoing maleic esters.
Yet another class of suitable, aliphatic hydrocarbon-soluble derivative of maleic acid or fumaric acid comprises the diesters of those acids of the structure CH. COOR CH. COOR
CH. COORl R10. CO. C~l where R and Rl, which may be the same or different, are alk~l radicals containing two or more carbon atoms. Examples of compounds of this class include diethyl maleate, diethyl fumarate, dibutyl maleate, dibutyl fumarate, dioctyl maleate, dioctyl fumarate, di-isooctyl maleate, di-isooctyl fumarate, dicyclo-he~yl maleate and dicyclohexyl fumarate~
Of the above-described derivatives of maleic acid and umaric acid, those most preferred for use in the present process are the ~-arylsubsti-t-uted maleimides, in particular ~-o-chlorophenylmalei-mide.
Derivatives of styrene which may be employed according to the invention instead of, or in addition ~87Z~
to, styrene itself include a-methylstyrene, o-, m~
and p-vinyltoluenes, p-tert-butylstyrene and o-, m-and p- chloros~yrenes.
As defined a~ove, the addition polymer microparticles are insoluble in the aliphatic hydro-carbon liquid and consequently precipitate out therefrom as they are formed during the dispersion polymerisation;
the particles are maintained in a state of stable dis-persion by the steric stabiliser present. Insolubility of the microparticles may be achieved in either of two ways. Firstly, the choice of the monomers from which the microparticulate polymer is derived may be such that the polymer is inherently insoluble in the hydro-carbon liquid. In this case, the monomer mixture ~o be polymerised will usually include one or more ethyl-enically unsaturated monomers in addition to the monomers specified above. Such monomers may in part-icular be the acrylic monomers, that is to say the alkyl esters of acrylic acid or methacrylic acid, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, n-octylacrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acryla~e and cetostearyl acrylate. Furthermore, there may be included other "neutral" monomers not of the acrylic type, for e~ample vinyl acetate, vinyl propionate or acrylonitrile. Secondly, insolubility of the microparticles may be achieved by introducing a sufficient degree of crosslinking into a polymer which, i~ it were not crosslinked, would actually be soluble in the aliphatic hydrocarbon. Such cross-linking can be effected , for example, by including '~8~Z~9 in the monomers to be polymeri~ed a monomer which is difunctional or polyfunctional with respect to the polymerisation reaction, such as an acrylic or meth-acrylic ester of a diol or polyol, e.g. ethylene glycol dimethacrylate or trimethylolpropane trimeth-acrylate, or a difunctional or ~olyfunctional vinyl-aromatic compound, e.g. divinylbenzene~ Alternatively, crosslinking may be achieved by including in the monomers to be polymerised pairs of monomers contain-ing functional groupings which are mutually reactiveby a condensation reaction. Examples o~ such pairs of monomers include epoxy group-containing and carboxyl group-containing monomers, such as glycidyl methacrylate and methacrylic acid or glycidyl acrylate and acrylic acid; or hydxoxymethylamino- or alkoxymethylamino- group-containing and carboxyl group-containing monomers, as described in our Canadian Application No. 354,123. As a further alternative, crosslinking may be brought about by carrying out the polymerisation of the monomers in the presence of a reactive amino resin which is insoluble in the aliphatic hydrocarbon liquid, the monomers in this case including at least one beaxing a group capable of reacting with the amino resin, such as a hydroxyl o~ a carboxyl group.
This last-mentioned procedure is described in our Canadian ~atent No. 1,139,033, Where insolubility of the microparticles is achieved through crosslinking, by whichever method, it is preferred that the degree of crosslinking should not be ~reater than that necessar~ to render the polymer insoluble. As in the case of non-crosslinked .
~i~
~372~
m:Lcroparticles, the monomer mixture to be polymerised may here include additionally one or more ethylenic-ally unsaturated monomers not bearing functional groups, such as the acrylic monomers and others listed above.
In those cases where the crosslinking of the microparticles is effected by means of a di-functional or polyfunctional comonomer, or by means of a pair of comonomers carrying mutually condensible groups, as mentioned above, it is preferred that the monomer mixture w~ich is polymerised in the p~ocess of the invention comprises:-(i) from 10% to 40~/0 by weight of styrene or a homologue thereof;
(ii) from 2% to 3~0 by weight of the maleic acid or fumaric acid derivative as herein-above defined;
(iii) from 0. 2~/o to 10~/o by weight of cross-linking monomer;
(iv) from 2~/o to 87, 8~/o Of one or more other ethylenically unsaturated monomers not falling within any of the categories (i), (ii) or (iii), the total monomers being 100~/o. The expression "crosslinking monomer" above refers to either a single comonomer or the combination of two mutually reactive comonomers, as the case may be.
In the case where crosslinking of the micro-particles arises from use of a functional comonomer in con~unction with a reactive amino resin, khe preferred monomer mixture comprises:-(i) from 10~/o to 40~/0 by weight of styrene or ~87~
a homologue thereof;
(ii) from 2% to 30~/0 by weight of the maleic or fumaric acid derivative as hereinbefore defined;
(iii) from 1% to 20~/o by weight of a hydroxyl group-containing monomer;
(iv) from 1% to 5~/0 by weight of a carboxyl group-containing monomer;
(v) from 5'~0 to 86~/o by weight of one or more other ethylenically unsaturated monomers nok fall-ing within any of the categories (i) to (iv), the total monomers being lO~
and the amount of the amino resin is from 0.5/0 to 2~/o of the total weight of the monomer mixture.
Aliphatic hydrocarbon li~uids which are suitable for use in the process of the invention include hexane, heptane and commercially available petroleum fractions of various boiling point ranges: the latter may contain minor proportions of aromatic hydrocarbons.
The steric stabiliser used in the process, as defined above, is an amphipathic substance such as is conventionally employed in non-aqueous dispersion poly-merisation procedures (see ("Dispersion Polymerisation in Organic Media" ed. K.E.J. Barrett, John Wiley & Sons~
1975). The type of stabilising agent preferred for use in the invention is a block or graft copolymer containing two types of polymeric component : one type consists, as stated above, of polymer chains which are solvatable by the dispersion liquid and the other type consists of polymer chains of different polarity from the first type which accordingly are not solvatable by that liquid ~nd are capable of becoming anchored to the polymer micro-2~
particles.
A particularly useful form of such a stabilising agent is a graft copolymer comprising a polymer backbone, which is the non solvatable or "anchor" component, and a plurality of solvatable polymer chains pendant from the backbone. Specific examples of such graft copolymers include those in which the backbone is an acrylic polymer chain, derived predominantly from methyl methacrylate, and the pendant chains are residues of poly~l2-hydroxy-stearic acid) which are readily solvatable by an aliphatic hydrocarbon medium. These copolymers may be made, for example, by first reacting poly(l2-hydroxy-stearic acid) with glycidyl acrylate or glycidyl methacrylate, whereby the terminal -COOH group in the polymeric acid is converted to an ester derivative containing a polymerisable unsaturated grouping, and then copolymerising that derivative with methyl meth~
acrylate, optionally toyether with minor proportions of other copolymerisable monomers. By employing acrylic acid or methacrylic acid as such minor comonomers, it is possible to introduce carboxyl groups into the backbone chain of the graft copolymer with beneficial results inasmuch as the backbone is thereby rendered more polar than it is if composed of methyl methacrylate units alone. This increased polarity causes the ~ackbone to be even less solvatable by a non-polar diluent such as an aliphatic hydro-carbon, and in consaquence enhances the force whereby it becomes anc'hored to the microparticles.
Further details concerning suitable stabil-ising agents, and concerning dispersion polymerisation ~L8~2~) in general, are given in the re~erence ~uoted above and in the patent literature, for example in sritish Specifications Nos. 941,305; 1,052,241; 1,122,397 and 1,231,614.
The inclusion in the mixture to be polymer-ised of the derivative of maleic acid or fumaric acid as defined above has two advantageous consequences.
Firstly, it increases the rate of polymerisation as compared with monomer mixtures containing styrene but not containing one of the derivatives in question; the quality of the polymer dispersion obtained is thereby improved. Sacondly, as already mentioned, where the derivatives themselves contain one or more aromatic nuclei in the molecule, these lead to further enhance-ment of the refractive index of the disperse polymer beyond that due to the styrene incorporated, consequently the amount of styrene required, in order to achieve a given level of refractive index, can be reduced.
Polymer microparticles made by the process described above may be incorporated into any coating composition based on a ilm-forming polymer or resin.
Thus according to a further aspect of the present invention there is provided a coating comp-osition comprising a liquid diluent and film-forming constituents which comprise:-(i) a film-orming polymer, (ii) polymer microparticles made by the process hereinbefore defined.
Any of the film-forming resins convention-2~
ally used in coating compositions may be employed.
The resin may be of either the crosslinking or the non-crosslinking type, that is to say the coating composition may be either thermosetting or thermo-plastic in nature.
One class of coating co}nposition of interest is that o the thermosetting acrylic resins, including those which are known to be useful in compositions intended for automotive applications. Such resins are typically derived from one or more acrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyi methacrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, together with suitable other monomers carrying functional groups whereby the resin can subsequently be crosslinked through reaction with an amino resin, such as acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxy-ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy-propyl methacrylate, ~-(alkoxymethyl)acrylamides and ~-(alkoxymethyl)methacrylamides (where the alkoxy groups may ke, for example, a butoxy group), glycidyl acrylate and glycidyl methacrylate. Such functional monomers typically constitute from 5~/0 to 30% by weight of the total acrylic resin. The acrylic resin may also include minor proportions of other, copolymerised monomers such as vinyl acetate, vinyl propionate and acrylonitrile. In particular, as is common practice where resins for automotive use are concerned, they may include also fxom 5% to 40~/0 by weight, based on the total resin, of styrene; the present invention is especially valuable in these circumstances, on account o~ the enhancement of the refractive index o~ the resin ~L~87Z~9 which the presence of the styrene brings about. These thermosetting acrylic resins may be crosslinked in conventional fashion, after application of the compos-ition to a substrate, by the action of heat in conjunction with an amino resin crosslinking agent also present in the composition. The crosslinking agent may be any of the known materials of this type, that is to say a condensate of formaldehyde with a nitrogenous compound such as melamine, urea or benzo-guanamine, or such a condensate in which a substantialproportion of the methylol groups present have been etherified by reaction with a lower alcohol, in particular butanol. The amount of the crosslinking agent is typically from 20% to 50% of the weigh~ of the thermosetting acrylic resin taken.
Instead of being a thermosetting acrylic resin, the film-forming material in the coating composition may be a thermoplastic acrylic resin derived from any of the monomers referred to above but excluding those carrying functional groups.
As a further alternative, the film-forming material may be an alkyd resin derived in the usual way by the condensation of one or more polyhydric alcohols and one or more polycarboxylic acids and incorporating the residues of a drying oil or semi-drying oil fatty acid, whereby the resin cures by means of an autoxidation polymerisation mechanism.
Yet again, it may ba a polyester derived from similar polyfunctional starting materials but not incorpor-ating any autoxidisable residues, in which casecuring of the resin is effected by reaction of residual hydroxyl and/or carboxyl groups therein with an amino ~87;24~
resin crosslinking agent.
In certain cases, the continued stability of the polymer microparticles after their incorpor-ation into a coating composition may be enhanced if the microparticles as described above are further associated, beore their introduction into the composition, with a further, essentially non-cross-linked, polymer which is soluble in the continuous phase liquid, or diluent, of the composi~ion and which is also compatible with the film-forming polymer present therein. This non-crosslinked polymer, which may be referred to as "auxiliary"
polymer, is most conveniently brought into assoc-iation with the microparticles by following up the dispersion polymerisati.on process, after conversion of monomer and crosslinking, if any, are complete, directly with the polymerisation of further monomer, from which the auxiliary polymer is to be derived, in the original aliphatic hydrocarbon medium and in the presence of the original dispersion stabiliser (although further stabiliser may be added, if desired).
Monomers from which the auxiliary polymer may be derived include the acrylic monomers and other "neutral"
monomers referred to above in connection with the microparticles proper~ but crosslinking monomers are, of course, omitted. It will be apparent to those skilled in the art which monomers to use in order to produce a non-crosslinked polymer having the required solubility characteristics.
. .
The proportion of the polymer microparticles which is incorporated into the coating composition can vary widely, depending upon the nature 72~9 - 20 ~
of the microparticles and of the main ~ilm-forming material respectively, and upon the effect which it is desired to achieve. Thus, different proportions may be required in a particular case according to whether the microparticles are introduced in order to modify the rheological properties of the coating composition and hence influence its flow character-istics when applied to a substrate, or whether they are incorporated in order to modify the mechanical properties of the coating film after application.
The coating composition may, when approp-riate, incorporate a suitable catalyst for the cross-linking reaction betw~en the film-forming material and a cross-linking agent, for example an acid-reacting compound such as acid butyl maleate, acid butyl phosphate or p-toluene sulphonic acid. Alternatively the catalytic action may be supplied by the incorporation of free acid groups in the film-formin~
material, for example by the use of acrylic acid or methacrylic acid as a comonomer in the preparation of a crosslinkable acrylic polymer.
The coating composition may contain one or more pigments. As already mentioned, the invention is of particular interest in connection with ~5 compositions which contain pigments of a light-absorbing character (as contrasted with those which scatter light), including such compositions which additionally contain aluminium flakes and are intended for the production of "glamour metallic" type finishes o~ car bodies. The invention is, however, of greatest benefit with respect to non-pigmented, "clear" comp-ositions which ar~ normally applied over lightly ~L~t372~
pigmented metallic-type hasecoats. In this case, the possibility according to the invention of matching the refractive index of the polymer microparticles exactly to that of the film-forming resin, and thus preserving the high clarity of the unmodified resin, is a very significant advantage.
The selection of the precise monomer formul-ation to be used in making polymer microparticles according to the invention, in order to match the refractive index of a particular film-forming resin, i5 a matter of simple experimentation which can be carried out without dif~iculty by a person skilled in the coating polymer art.
The invention is illustrated but not limited by the following Examples in which parts, ratios and percentages are by weight.
Examples 1=5 and Com~arative Examples A-C
To a vessel fitted with stirrer, thermometer, reflux condenser and provision for adding a liquid 20 feed to the returning condensate there was charged:
Aliphatic hydrocarbon (boiling range 170-210C; aromatic content 5%) 10.355 parts Xexane 2.536 parts Heptane 13.561 parts The vessel and charge were purged with inert gas and then raised to re~lux temperature (100C). The follow-ing premixed ingredients were added over a short period of time:
~15 7;2gl~
~ 22 -Methyl methacrylate 0.833 part Methacrylic acid 0.017 part Azodiisobutyronitrile 0.066 part Graft copolymer stabiliser (330/0 solution, as described below) 0.310 part The contents o~ the vessel were then held under re-flux for 30 minutes to form a 'seed' dispersion, after which the following premixed ingredients were fed into 10 the hydrocarbon returning from the condenser at a uniform rate over a period of 3 hours:-Monomer mixture, as given in detail below 16.145 parts ~zodiisobutyronitrile 0.212 part Graft copolymer stabiliser (33% solution, as described below) 3.330 parts Dimethylaminoethanol 0.031 part After completion of the monomer feed, the reaction mixture was maintained under reflux for 3 hours.
The monomer mixtures used in the feed stage in these Examples and Comparative Examples had the compositions indicated in the accompanying Table I;
the first figure in each case is the amount in parts by weight and the second figure (in parentheses) indicates the weight percentage of the monomer in question in the total feed stage monomer mixture.
In each case, a fine, stable dispersion of crosslinked polymer microparticles was o~tained. The dispersion~ had solids contents in the range 38-40~.
(determined by evaporation at 150C for l hour) and insoluble gel contents in the range 21-31%. The volume average particle size of the microparticles was measured in each case by their Brownian motion and ~L~87~
autocorrelation of laser light : the sizes found are also recorded in Table I. Prior to being cooled from the reaction temperature, each dispersion was diluted finally with 12.549 parts of xylene.
The graft copolymer stabiliser solution used in the above procedure was obtained as follows.
12-Hydroxystearic acid was self-condensed to an acid value of about 31-34 mg KOH/g (corresponding to a molecular weight of 1650-1800) and then reacted with an equivalent amount of glycidyl methacrylate~ The resulting unsaturated ester was copolymerised at a weight ratio of 2~1 with a mixture of methyl meth-acrylate and acrylic acid in the proportions of 95:5.
The copolymer was used as a 330/O solution in a mixture of aliphatic hydrocarbon, toluene and ethyl acetate in the ratio 74:14:12.
7~
_ ~ _ __-- 3 _ ~ 3 1 ~3 ~1 O tr ,~. ~ . ~ 3 ~ 'C 3 ~D ~Z
Such microparticles are conveniently made by processes o~ dispersion polymerisation of monomers in suitable liquids in the presence of polymeric stabilisers for the particles of polymer which are formed. The microparticles are thereby sterically stabilised against flocculation or aggregation, in the manner described in "Dispersion Polymerisation in Organic Media", ed. K.E.J. Barrett (John Wiley, 1975) and in many patent specifications such as British Specifications Nos. 934,038: 941,305; 1,052,241;
1,122,397; 1,143,404 and 1,231,614.
Iwo types of such dispersion polymerisation process may be distinguished. In the first, which is described in British Patent ~o. 1,451,948 referred to above, microgel particles are formed as a minor product of a dispersion polymerisation of ethylenic-ally unsaturated monomers in the presence of a 90-called "multifunctional" stabiliser. This stabiliserpossesses the molecular structural features which are common to all sterically stabilising entities, namely a polymeric component of the molecule which is solvated by the continuous phase of the dispersion and another component which associates with the disperse phase, howe~er, it possesses in addition a plurality of groupings which are capable of copolymer-ising with the monomers undergoing dispersion polymer-isation. The main result of using such a stabiliser~
as described more generally in British Patant Spec-ification No. 1,231,614, is that the stabiliser becomes covalently linked to the disperse polymer, Z~g but a ~urther consequence is that, whilst the greater part of the polymer formed as the disperse phase is non-crosslinked, a small part of it becomes cross-linked through the intervention of the copolymeris-able groups in the stabiliser. By adding to the dispersion thus obtained a su~ficiant amount of an active solvent for the non-crosslinked disperse poly-mer, there can be produced a solution-type coating composition in which the non-crosslinked polymer constitutes the main film-forming material but in which the crosslinked microgel remains as insoluble, discrete and sterically stabilised paxticles. It is, however, difficult by this method to control the relative proportions of microgel and of non-cross linked pol~mer which are producéd, and also to control the molecular weight of the latter polymer (which may be desirable in order to optimise its film ~orming properties) without adversely affecting the yield of microgel. Furthermore it is, of course, inevitable that microgel made in this way will have essentially the same monomer composition as that of the non-crosslinked polymer.
In the second method of making micropart-icles, which is described in British Patent Specif-ication ~o. 1,538,151 and in the published German and European spe~ifications referxed to earlier, the particles are produced essentially as the sole disperse material; here crosslinking is achieved through the expedient of having present in the monomer charge being polymerised pairs of comonomers carrying mutually chemically reactive groups (in addition to the copolymerisa~le groups) b~ reaction ~1~37Z~
of which groups covalent cross-links between the polymer chains may be generated. A variety of combin-ations of mutually reactive groups has been proposed, for example epoxy and carboxyl, amine and carboxyl, epo~ide and carhoxylic anhydride, amine and carboxylic anhydride, hydroxyl and carboxylic anhydride, amine and carboxylic acid chloride, alkylene-imine and carbo~yl, and organo-alkoxysilane and carboxyl. Since the microparticles made by this procedure are not accompaniad by significant amounts of other polymeric products, they can conveniently be incorporated into coating compositions ~ased on film-forming resins of any desired type and in any desired proportion.
One class of coating composition to which polymeric microparticles can with advantage be added is that based upon solutions of thermosetting acrylic resins; these are of particular interest for the painting of car bodies and othPr metal structures which can tolerate stoving at relatively high tempex-atures following application of the composition,whereby the composition is converted to a hard, insoluble coating through reaction of the resin with a crosslinking agent such as a melamine-formaldehyde resin. It is common practice to include in the monomers, from which these thermosetting acrylic resins are derived, a proportion of up to 40~0 by weight of styrene.
This is done for two main reasons : firstly, because of the significantly higher refractive inde~ of poly-styrene as compared with that of most u~modified polymers of acrylic or methacrylic acid esters (1.59 and 1.46 - 1.49 respectively), the incorporation of styrene gives rise to a higher reflectance of light at ~L~87Z~9 the air polymer interface and hence enhances the apparent gloss of the coating; secondly, copolymers containing some styrene show improved flow during the stoving operation in comparison with methyl methacrylate homopolymers. On the other hand, a practical upper limit, of about 500~ by weight of total monomers, is set to the proportion of styrene by the strong ultra-violet light absorption properties of the latter and the consequent adverse effect on exterior durability of coatings containing it.
A general consideration affecting the incorp-oration of polymeric microparticles into coating comp-ositions is that unless the refractive index of the microparticulate polymer is fairly closely matched to that of the main film-forming resin, there will be scattering of light at the boundary between the two polymer phases and the coating film will appear cloudy.
I~is will, of course, be of little consequence in compositions containing light-scattering pigments such as titanium dioxide, but in coloured compositions of a deep hue containing light absorbing pigments, partic-ularly coloured metallic compositions containing a low level of aluminium flake~ and above all in unpigmented compositions intended for the production of clear coat-ings, it can be a serious defect. Where a thermosettingcopolymer contains a significant proportion of styrene, incorporation of micropar~icles consisting essentially of polymethyl methacrylate will have this undesirable result; the problem tends to be accentuated by the fact that the melamine-formaldehyde resins which are most commonly used as crosslinking agents in such systems themselves have relatively high refractive 2~9t indices (in the region of 1.52).
When microgel particles are produced by the first of the two dispersion polymerisation techniques described above, it follows that the microgel polymer will always have approximately the same monomer comp-osition as the main film-forming polymer which is produced along with it, so that the above-mentioned refractive index problem does not arise. A disadvan-tage of this first-described technique additional to those already mentioned is, however, that the very polymers which it is desired to use as the main film-former in many clear-coat compositions and compositions of high solids content are not readily prepared by ~on-aqueous dispersion polymerisation. For a variety of reasons, such polymerisation is most conveniently carried out in low polarity organic liquids, in particular aliphatic hydrocar~ons, and, whilst polymers based wholly or overwhelmingly upon methyl methacrylate are practically insoluble in thesa liquids, copolymers containing other monomers, such as styrene, in signif-icant proportions may be appreciably soluble in them.
This may make it difficult to obtain initially a stable dispersicn of the copolymer.
The foregoing discussion has considered the problems which arise where the main film-forming polymer is of the addition type, i.e. is one derived from ethylenically unsaturated monomers. However, the same need to match the refractive index of the microgel particles to that of the film-former may arise in the case of the use of certain alkyd or polyester resins in the latter capacity, more spec~fically those alkyd resins which are derived in part from aromatic starting ~37~
materials, such as phthalic anhydride, and which in consequence have relatively high refractive indices.
Here again, there may be used as crosslinking agents melamine-formaldehyde resins also having high refract-ive indices.
The evident way out of the di~ficulty, what-ever the nature of the film-forming polymer into which the microgel polymer is incorporated, is to make microgeL polym~r which contains a substantial propor-tion of styrene by the second of the two dispersion polymerisation methods referred to. However, as indicated above, the dispersion polymerisation of styrene in an aliphatic hydrocarbon using free radical catalysts presents certain other pro~lems : the poly-merisation proceeds slowly and the polymer formed is heavily swollen by the hydrocar~on at the polymeris-ation temperature normally employed, so that a coarse particle-size dispersion results (see "Dispersion Polymerisation in Organic Media", ed. K.E.J.Barrett :
John Wiley, London, 1975 : pages 213-214~. These problems are encountered equally in the case of monomer mixtures containing a substantial proportion of styrene, for example greater than 207/o by weight.
We have now found that dispersion polymer-isation of such monomer mixtures can be carried out without these difficulties if the monomer mixture contains, in addition to styrene, a specified deriv-ation of maleic acid or fumaric acid.
According to the present invention we provide a process for the production of addition polymer micro-particles, comprising the dispersion polymerisation in an aliphatic hydrocarbon liquid of an ethylenically Z~
-- 8 ~
unsaturated monomer mixture which gives rise to a polymer or copolymer insoluble in the hydrocarbon liquid and which comprises (i) up to 50% by weiyht of styrene or a substituted derivative thereof and (ii) up to 5~0 by weight of a derivative of maleic acid or fumaric acid which is soluble in the hydro-carbon liquid at the temperature of polymerisation, thepolymerisation being carried out in the presence in the hydrocarbon liquid o a steric dispersion stabiliser the molecule of which comprises at least one polymeric component which is solvated by the hydrocarbon liquid and at least one other component which is not solvated by the liquid and is capable of associating with the polymer produced.
Any derivative of maleic acid or fumaric acid which is soluble in the aliphatic hydrocarbon liquid i5 suitable for use in the process of the invention. This solubility requirement excludes maleic acid and fumaric acid themselves, and also maleic anhydride, but a variety of compounds derived from these, for example through the medium of the carboxyl groups, are suitable. A preferred type of derivative is one containing in the molecule at least one aromatic group, since the presence of the aromatic nucleus provides an enhancement of the refractive index of the microparticle additional to that afforded by the copolymerised styrene or styrene derivative.
One class of derivative of maleic acid or fumaric acid containing at least one aromatic nucleus ~hich is especially suitable is the class of ~-aryl-substituted maleimides of the general formula '72~
g CH - CO ~
~ Ar CH - CO
where Ar is an aromatic radical which may contain a single benzene nucleus or two or more connected or fused benzene nuclei and which may optionally carry other substituent groups. Such compounds are in general soluble in aliphatic hydrocarbons. Examples of members of this class include ~-phenylmaleimide, ~-o-tolylmaleimide, ~-m-tolylmaleimide, ~-p-tolyl-maleimide, ~-o-biphenylylmaleimide, ~-p-biphenylyl-maleimide, ~-p-~tert-butyl)phenylmaleimide, ~--p-dodecylphenylmaleimide, ~-a-naphthylmaleimide, ~-~-naphthylmaleimide, ~-o-chlorophenylmaleimide, ~-m-chlorophenylmaleimide, ~-p-chlorophenylmaleimide, ~-p-methoxyphenylmaleimide, ~-2-methyl-4-chlorophenyl-maleimide, N-2-methoxy-5-chlorophenylmaleimide, ~-4-phenoxyphenylmaleimide, ~-4-phenylcarboxyphenyl-maleimide, ~-4-(o-chlorophenoxy)phenylmaleimide, N-2, 5-dichlorophenylmaleimide, ~-2, 5-dimethoxyphenyl-. maleimide and ~-2, 4, 5-trichlorophenylmaleimide. Any of the foregoing substances may be made by the process-es described in British Patent Specifications ~os.
1~040,907 and 1,041,027.
Another class of derivative of maleic acid or fumaric acid containing at least one aromatic nuclues which is soluble in aliphatic hydrocarbons and is suitable for use according to the invention is the class of diesters of maleic acid or fumaric acid of the structure CH.CO.OX CH.CO.OX
ll or li : CH.CO.OY YO.CO.CH
~724~
where either X or Y, or both, is an aromatic radical which may contain a single benzene nuclueus or two or more connected or fused benzene nuclei and which may optionally carry other substituent groups.
Examples of members of this class include diphenyl-maleate, methyl phenyl maleate, dibenzylmaleate, di-(o-chlorobenzyl) maleate, di(p-chlorobenzyl)maleate, benzyl methyl maleate, dinaphthyl maleate, bis(di-phenylyl) maleate, diphenyl fumarate, methyl phenyl fumarate and other fumaric esters corresponding to the foregoing maleic esters.
Yet another class of suitable, aliphatic hydrocarbon-soluble derivative of maleic acid or fumaric acid comprises the diesters of those acids of the structure CH. COOR CH. COOR
CH. COORl R10. CO. C~l where R and Rl, which may be the same or different, are alk~l radicals containing two or more carbon atoms. Examples of compounds of this class include diethyl maleate, diethyl fumarate, dibutyl maleate, dibutyl fumarate, dioctyl maleate, dioctyl fumarate, di-isooctyl maleate, di-isooctyl fumarate, dicyclo-he~yl maleate and dicyclohexyl fumarate~
Of the above-described derivatives of maleic acid and umaric acid, those most preferred for use in the present process are the ~-arylsubsti-t-uted maleimides, in particular ~-o-chlorophenylmalei-mide.
Derivatives of styrene which may be employed according to the invention instead of, or in addition ~87Z~
to, styrene itself include a-methylstyrene, o-, m~
and p-vinyltoluenes, p-tert-butylstyrene and o-, m-and p- chloros~yrenes.
As defined a~ove, the addition polymer microparticles are insoluble in the aliphatic hydro-carbon liquid and consequently precipitate out therefrom as they are formed during the dispersion polymerisation;
the particles are maintained in a state of stable dis-persion by the steric stabiliser present. Insolubility of the microparticles may be achieved in either of two ways. Firstly, the choice of the monomers from which the microparticulate polymer is derived may be such that the polymer is inherently insoluble in the hydro-carbon liquid. In this case, the monomer mixture ~o be polymerised will usually include one or more ethyl-enically unsaturated monomers in addition to the monomers specified above. Such monomers may in part-icular be the acrylic monomers, that is to say the alkyl esters of acrylic acid or methacrylic acid, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl methacrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, n-octylacrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acryla~e and cetostearyl acrylate. Furthermore, there may be included other "neutral" monomers not of the acrylic type, for e~ample vinyl acetate, vinyl propionate or acrylonitrile. Secondly, insolubility of the microparticles may be achieved by introducing a sufficient degree of crosslinking into a polymer which, i~ it were not crosslinked, would actually be soluble in the aliphatic hydrocarbon. Such cross-linking can be effected , for example, by including '~8~Z~9 in the monomers to be polymeri~ed a monomer which is difunctional or polyfunctional with respect to the polymerisation reaction, such as an acrylic or meth-acrylic ester of a diol or polyol, e.g. ethylene glycol dimethacrylate or trimethylolpropane trimeth-acrylate, or a difunctional or ~olyfunctional vinyl-aromatic compound, e.g. divinylbenzene~ Alternatively, crosslinking may be achieved by including in the monomers to be polymerised pairs of monomers contain-ing functional groupings which are mutually reactiveby a condensation reaction. Examples o~ such pairs of monomers include epoxy group-containing and carboxyl group-containing monomers, such as glycidyl methacrylate and methacrylic acid or glycidyl acrylate and acrylic acid; or hydxoxymethylamino- or alkoxymethylamino- group-containing and carboxyl group-containing monomers, as described in our Canadian Application No. 354,123. As a further alternative, crosslinking may be brought about by carrying out the polymerisation of the monomers in the presence of a reactive amino resin which is insoluble in the aliphatic hydrocarbon liquid, the monomers in this case including at least one beaxing a group capable of reacting with the amino resin, such as a hydroxyl o~ a carboxyl group.
This last-mentioned procedure is described in our Canadian ~atent No. 1,139,033, Where insolubility of the microparticles is achieved through crosslinking, by whichever method, it is preferred that the degree of crosslinking should not be ~reater than that necessar~ to render the polymer insoluble. As in the case of non-crosslinked .
~i~
~372~
m:Lcroparticles, the monomer mixture to be polymerised may here include additionally one or more ethylenic-ally unsaturated monomers not bearing functional groups, such as the acrylic monomers and others listed above.
In those cases where the crosslinking of the microparticles is effected by means of a di-functional or polyfunctional comonomer, or by means of a pair of comonomers carrying mutually condensible groups, as mentioned above, it is preferred that the monomer mixture w~ich is polymerised in the p~ocess of the invention comprises:-(i) from 10% to 40~/0 by weight of styrene or a homologue thereof;
(ii) from 2% to 3~0 by weight of the maleic acid or fumaric acid derivative as herein-above defined;
(iii) from 0. 2~/o to 10~/o by weight of cross-linking monomer;
(iv) from 2~/o to 87, 8~/o Of one or more other ethylenically unsaturated monomers not falling within any of the categories (i), (ii) or (iii), the total monomers being 100~/o. The expression "crosslinking monomer" above refers to either a single comonomer or the combination of two mutually reactive comonomers, as the case may be.
In the case where crosslinking of the micro-particles arises from use of a functional comonomer in con~unction with a reactive amino resin, khe preferred monomer mixture comprises:-(i) from 10~/o to 40~/0 by weight of styrene or ~87~
a homologue thereof;
(ii) from 2% to 30~/0 by weight of the maleic or fumaric acid derivative as hereinbefore defined;
(iii) from 1% to 20~/o by weight of a hydroxyl group-containing monomer;
(iv) from 1% to 5~/0 by weight of a carboxyl group-containing monomer;
(v) from 5'~0 to 86~/o by weight of one or more other ethylenically unsaturated monomers nok fall-ing within any of the categories (i) to (iv), the total monomers being lO~
and the amount of the amino resin is from 0.5/0 to 2~/o of the total weight of the monomer mixture.
Aliphatic hydrocarbon li~uids which are suitable for use in the process of the invention include hexane, heptane and commercially available petroleum fractions of various boiling point ranges: the latter may contain minor proportions of aromatic hydrocarbons.
The steric stabiliser used in the process, as defined above, is an amphipathic substance such as is conventionally employed in non-aqueous dispersion poly-merisation procedures (see ("Dispersion Polymerisation in Organic Media" ed. K.E.J. Barrett, John Wiley & Sons~
1975). The type of stabilising agent preferred for use in the invention is a block or graft copolymer containing two types of polymeric component : one type consists, as stated above, of polymer chains which are solvatable by the dispersion liquid and the other type consists of polymer chains of different polarity from the first type which accordingly are not solvatable by that liquid ~nd are capable of becoming anchored to the polymer micro-2~
particles.
A particularly useful form of such a stabilising agent is a graft copolymer comprising a polymer backbone, which is the non solvatable or "anchor" component, and a plurality of solvatable polymer chains pendant from the backbone. Specific examples of such graft copolymers include those in which the backbone is an acrylic polymer chain, derived predominantly from methyl methacrylate, and the pendant chains are residues of poly~l2-hydroxy-stearic acid) which are readily solvatable by an aliphatic hydrocarbon medium. These copolymers may be made, for example, by first reacting poly(l2-hydroxy-stearic acid) with glycidyl acrylate or glycidyl methacrylate, whereby the terminal -COOH group in the polymeric acid is converted to an ester derivative containing a polymerisable unsaturated grouping, and then copolymerising that derivative with methyl meth~
acrylate, optionally toyether with minor proportions of other copolymerisable monomers. By employing acrylic acid or methacrylic acid as such minor comonomers, it is possible to introduce carboxyl groups into the backbone chain of the graft copolymer with beneficial results inasmuch as the backbone is thereby rendered more polar than it is if composed of methyl methacrylate units alone. This increased polarity causes the ~ackbone to be even less solvatable by a non-polar diluent such as an aliphatic hydro-carbon, and in consaquence enhances the force whereby it becomes anc'hored to the microparticles.
Further details concerning suitable stabil-ising agents, and concerning dispersion polymerisation ~L8~2~) in general, are given in the re~erence ~uoted above and in the patent literature, for example in sritish Specifications Nos. 941,305; 1,052,241; 1,122,397 and 1,231,614.
The inclusion in the mixture to be polymer-ised of the derivative of maleic acid or fumaric acid as defined above has two advantageous consequences.
Firstly, it increases the rate of polymerisation as compared with monomer mixtures containing styrene but not containing one of the derivatives in question; the quality of the polymer dispersion obtained is thereby improved. Sacondly, as already mentioned, where the derivatives themselves contain one or more aromatic nuclei in the molecule, these lead to further enhance-ment of the refractive index of the disperse polymer beyond that due to the styrene incorporated, consequently the amount of styrene required, in order to achieve a given level of refractive index, can be reduced.
Polymer microparticles made by the process described above may be incorporated into any coating composition based on a ilm-forming polymer or resin.
Thus according to a further aspect of the present invention there is provided a coating comp-osition comprising a liquid diluent and film-forming constituents which comprise:-(i) a film-orming polymer, (ii) polymer microparticles made by the process hereinbefore defined.
Any of the film-forming resins convention-2~
ally used in coating compositions may be employed.
The resin may be of either the crosslinking or the non-crosslinking type, that is to say the coating composition may be either thermosetting or thermo-plastic in nature.
One class of coating co}nposition of interest is that o the thermosetting acrylic resins, including those which are known to be useful in compositions intended for automotive applications. Such resins are typically derived from one or more acrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyi methacrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, together with suitable other monomers carrying functional groups whereby the resin can subsequently be crosslinked through reaction with an amino resin, such as acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxy-ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy-propyl methacrylate, ~-(alkoxymethyl)acrylamides and ~-(alkoxymethyl)methacrylamides (where the alkoxy groups may ke, for example, a butoxy group), glycidyl acrylate and glycidyl methacrylate. Such functional monomers typically constitute from 5~/0 to 30% by weight of the total acrylic resin. The acrylic resin may also include minor proportions of other, copolymerised monomers such as vinyl acetate, vinyl propionate and acrylonitrile. In particular, as is common practice where resins for automotive use are concerned, they may include also fxom 5% to 40~/0 by weight, based on the total resin, of styrene; the present invention is especially valuable in these circumstances, on account o~ the enhancement of the refractive index o~ the resin ~L~87Z~9 which the presence of the styrene brings about. These thermosetting acrylic resins may be crosslinked in conventional fashion, after application of the compos-ition to a substrate, by the action of heat in conjunction with an amino resin crosslinking agent also present in the composition. The crosslinking agent may be any of the known materials of this type, that is to say a condensate of formaldehyde with a nitrogenous compound such as melamine, urea or benzo-guanamine, or such a condensate in which a substantialproportion of the methylol groups present have been etherified by reaction with a lower alcohol, in particular butanol. The amount of the crosslinking agent is typically from 20% to 50% of the weigh~ of the thermosetting acrylic resin taken.
Instead of being a thermosetting acrylic resin, the film-forming material in the coating composition may be a thermoplastic acrylic resin derived from any of the monomers referred to above but excluding those carrying functional groups.
As a further alternative, the film-forming material may be an alkyd resin derived in the usual way by the condensation of one or more polyhydric alcohols and one or more polycarboxylic acids and incorporating the residues of a drying oil or semi-drying oil fatty acid, whereby the resin cures by means of an autoxidation polymerisation mechanism.
Yet again, it may ba a polyester derived from similar polyfunctional starting materials but not incorpor-ating any autoxidisable residues, in which casecuring of the resin is effected by reaction of residual hydroxyl and/or carboxyl groups therein with an amino ~87;24~
resin crosslinking agent.
In certain cases, the continued stability of the polymer microparticles after their incorpor-ation into a coating composition may be enhanced if the microparticles as described above are further associated, beore their introduction into the composition, with a further, essentially non-cross-linked, polymer which is soluble in the continuous phase liquid, or diluent, of the composi~ion and which is also compatible with the film-forming polymer present therein. This non-crosslinked polymer, which may be referred to as "auxiliary"
polymer, is most conveniently brought into assoc-iation with the microparticles by following up the dispersion polymerisati.on process, after conversion of monomer and crosslinking, if any, are complete, directly with the polymerisation of further monomer, from which the auxiliary polymer is to be derived, in the original aliphatic hydrocarbon medium and in the presence of the original dispersion stabiliser (although further stabiliser may be added, if desired).
Monomers from which the auxiliary polymer may be derived include the acrylic monomers and other "neutral"
monomers referred to above in connection with the microparticles proper~ but crosslinking monomers are, of course, omitted. It will be apparent to those skilled in the art which monomers to use in order to produce a non-crosslinked polymer having the required solubility characteristics.
. .
The proportion of the polymer microparticles which is incorporated into the coating composition can vary widely, depending upon the nature 72~9 - 20 ~
of the microparticles and of the main ~ilm-forming material respectively, and upon the effect which it is desired to achieve. Thus, different proportions may be required in a particular case according to whether the microparticles are introduced in order to modify the rheological properties of the coating composition and hence influence its flow character-istics when applied to a substrate, or whether they are incorporated in order to modify the mechanical properties of the coating film after application.
The coating composition may, when approp-riate, incorporate a suitable catalyst for the cross-linking reaction betw~en the film-forming material and a cross-linking agent, for example an acid-reacting compound such as acid butyl maleate, acid butyl phosphate or p-toluene sulphonic acid. Alternatively the catalytic action may be supplied by the incorporation of free acid groups in the film-formin~
material, for example by the use of acrylic acid or methacrylic acid as a comonomer in the preparation of a crosslinkable acrylic polymer.
The coating composition may contain one or more pigments. As already mentioned, the invention is of particular interest in connection with ~5 compositions which contain pigments of a light-absorbing character (as contrasted with those which scatter light), including such compositions which additionally contain aluminium flakes and are intended for the production of "glamour metallic" type finishes o~ car bodies. The invention is, however, of greatest benefit with respect to non-pigmented, "clear" comp-ositions which ar~ normally applied over lightly ~L~t372~
pigmented metallic-type hasecoats. In this case, the possibility according to the invention of matching the refractive index of the polymer microparticles exactly to that of the film-forming resin, and thus preserving the high clarity of the unmodified resin, is a very significant advantage.
The selection of the precise monomer formul-ation to be used in making polymer microparticles according to the invention, in order to match the refractive index of a particular film-forming resin, i5 a matter of simple experimentation which can be carried out without dif~iculty by a person skilled in the coating polymer art.
The invention is illustrated but not limited by the following Examples in which parts, ratios and percentages are by weight.
Examples 1=5 and Com~arative Examples A-C
To a vessel fitted with stirrer, thermometer, reflux condenser and provision for adding a liquid 20 feed to the returning condensate there was charged:
Aliphatic hydrocarbon (boiling range 170-210C; aromatic content 5%) 10.355 parts Xexane 2.536 parts Heptane 13.561 parts The vessel and charge were purged with inert gas and then raised to re~lux temperature (100C). The follow-ing premixed ingredients were added over a short period of time:
~15 7;2gl~
~ 22 -Methyl methacrylate 0.833 part Methacrylic acid 0.017 part Azodiisobutyronitrile 0.066 part Graft copolymer stabiliser (330/0 solution, as described below) 0.310 part The contents o~ the vessel were then held under re-flux for 30 minutes to form a 'seed' dispersion, after which the following premixed ingredients were fed into 10 the hydrocarbon returning from the condenser at a uniform rate over a period of 3 hours:-Monomer mixture, as given in detail below 16.145 parts ~zodiisobutyronitrile 0.212 part Graft copolymer stabiliser (33% solution, as described below) 3.330 parts Dimethylaminoethanol 0.031 part After completion of the monomer feed, the reaction mixture was maintained under reflux for 3 hours.
The monomer mixtures used in the feed stage in these Examples and Comparative Examples had the compositions indicated in the accompanying Table I;
the first figure in each case is the amount in parts by weight and the second figure (in parentheses) indicates the weight percentage of the monomer in question in the total feed stage monomer mixture.
In each case, a fine, stable dispersion of crosslinked polymer microparticles was o~tained. The dispersion~ had solids contents in the range 38-40~.
(determined by evaporation at 150C for l hour) and insoluble gel contents in the range 21-31%. The volume average particle size of the microparticles was measured in each case by their Brownian motion and ~L~87~
autocorrelation of laser light : the sizes found are also recorded in Table I. Prior to being cooled from the reaction temperature, each dispersion was diluted finally with 12.549 parts of xylene.
The graft copolymer stabiliser solution used in the above procedure was obtained as follows.
12-Hydroxystearic acid was self-condensed to an acid value of about 31-34 mg KOH/g (corresponding to a molecular weight of 1650-1800) and then reacted with an equivalent amount of glycidyl methacrylate~ The resulting unsaturated ester was copolymerised at a weight ratio of 2~1 with a mixture of methyl meth-acrylate and acrylic acid in the proportions of 95:5.
The copolymer was used as a 330/O solution in a mixture of aliphatic hydrocarbon, toluene and ethyl acetate in the ratio 74:14:12.
7~
_ ~ _ __-- 3 _ ~ 3 1 ~3 ~1 O tr ,~. ~ . ~ 3 ~ 'C 3 ~D ~Z
3 ~3 ::~ 3 ~ 3 t I'h r~ n J (D r). ~ (D J ~a trl~1 3- VJ ~ 1-- 0 ~ 3 ~ Q. o u ~c ~ J ~
W CI~ ~~ ~ D~ D) I Dl I ~ ~ 11 :Z;
H ~3 ~ ~ ~ 13 (3 ~ P) Dl N O O . O
o l l l ~ w 8 8 o w ~
O l l ~ ~ l a . _ . ~ ~ ~ _ ' ~ :
~- ~ ~
L8~
The results of particle size determination given in Table I illustrate the fact that the use of s~yrene as a comonomer, in the absence of a maleic acid or fumaric acid derivative as required according to the present invention, leads to the production of relatively coarse particles in dispersion, which in turn cause the dispersion to sediment out rapidly on storage. The process of the invention, on the other hand, yields dispersions of similar particle size to those obtained with acrylic monomers only (i.e. omit-ting styrene).
~xample 6 and Comparative Examples D-G
Thermosetting acrylic coating compositions were prepared by blending a melamine-formaldehyde resin with an acrylic solution polymer having the composition : styrene ~2.5%, butyl methacrylate 21.25/~, butyl acrylate 21.25~/o~ hydroxyethyl methacrylate 14.0%
and acrylic acid l~o~ together with (in all cases except one) insoluble microparticles prepared as 20 described in one of the preceding Examples or Comp-arative Examples. Details of the particular micropart-icles used and of the proportion of the three constit-uents taken are given in the accompanying Table II;
the amounts stated are in each case parts hy weight based on 100% non-volatile material. Each blend was then thinned with a 1:1 mixture o~ butyl acetate and xylene to a spraying viscosity of 50-60 seconds (measured in a BS.B3 cup at 25C), and sprayed on to glass panels which were afterwards stoved for 30 minutes at 127C. The appearance of th~ resulting z~9 film was then noted : the results are recorded also in Table II.
TABLE II
Example ~o.6 D E F G
- --- - - - - - - -- . . ...
M/F resin 30 30 30 30 30 Acrylic 60 60 60 60 70 polymer Micro-particles from: 10 Example 4 Comp.Ex. A - 10 " " B - - 10 - -" " C - - - 10 Appèarance clear very slightly clear clear of fLlm cloudy cloudy The above results demonstrated that the inherent clarity of the cured acrylic film (Comparat-ive Example G) is lost if microparticles which are notmatched to its re~ractive index are introduced, i.e.
microparticles containing a zero or low proportion of styrene (Comparative Examples D & E). Clarity of the film is maintained if the microparticles contain a high proportion of styrene (Comparative Example F) but this, as is demonstrated by the results presented in the previous group of Examples, is done at the e~pense of the microparticles being of a coarqe size and consequently prone to settlement from dispersion.
In contrast, the use of styrene in conjunction with a maleic acid or fumaric acid derivative according to the invention, as shown by Example 6, enables clarity ~7~
of the ~ilm to be preserved without such accompanying drawbacks.
Examples 7-8 and Comparative Example H
(a) To a vessel fitted with stirrer, thermometer, 5 reflux condenser and Dean and Stark separator there was charged:-Aliphatic hydrocarbon (boiling range 140-156C;
zero aromatic content) 25.735 parts Methyl methacrylate 1.341 "
Methacrylic acid 0.026 part Azodiisobutyronitrile 0.107 part Graft copolymer stabiliser (33% solution, as described below) 0.497 part The vessel and charge were purged with inert gas and the temperature raised to 100C and maintained there for 30 minutes in order to produce a 'seed' polymer dispersion. The following pre-mixed ingredients were then fed into the vessel at a uniform rate over a period of 3 hours, maintaining the temperature at 100C with stirring:
Monomer, as given in detail below 19.877 parts Hydroxyethyl acrylate 1.130 "
~examethoxymethylmelamine 1.130 "
Methacrylic acid 0.451 part Azodiisobutyronitrile 0.140 Graft copolymer stabiliser (33% solution, as described below) 4.664 parts Aliphatic hydrocarbon, (as described above)11.320 parts 241;9 The reaction mixture was then h41d at 100 C
for a f~lrther period of 30 minutes, after which ~he temperature was raised to 140-145C when recycling of distillate commenced; these conditions were maintained for 2 hours, during which 1.2 parts of water were removed at the separator. The contents of the vessel were then cooled to give a fine dispersion of cross-linked microparticles. The dispersions had solids contents in the range 38-39~ and insoluble gel contents in the range 31-3 2%.
The graft copolymer stabiliser used in the foregoing procedure was obtained as follows:l2-hydroxy-stearic acid was self-condensed to an acid value of about 31-34 mg KOH/g (corresponding to a molecular weight of 1650-1800) and was then reacted with an equivalent amount of glycidyl methacrylate. The result-ing unsaturated ester was copolymerised with methyl methacrylate and glycidyl methacrylate in the weight ratios 49 : 46 : 5 respectively, and the copolymer thus obtained was finally reacted with methacrylic acid and p-nitrobenzoic acid in the presence of a tertiar~ amine catalyst, in the proportions of 0.070 part o methacrylic acid and 0.019 part of p-nitro-benzoic acid for every 100 parts of the copolymer.
(b) ~0 a vessel fitted as described in step (a) above, ~ut fitted with provision ~or adding a liquid feed into the recycling distillate, there was charged 66.418 parts of the dispersion obtained in step (a).
The dispersion was heated to 145C to establish re~
cycling of distillate, and the following premixed ingredients were then fed in via the returning distillate at a steady rate over a period of 3 hours:
~87~
Reaction product of poly(12- 14.982 parts hydroxystearic acid) and glycidyl methacrylate, (50~/0 solution in aliphatic hydrocarbon, boiling xange 136-165C) Hydroxyethyl acrylate 1.972 parts Methacrylic acid 0.394 part Styrene 5.913 parts Methyl methacrylate 3.943 parts Di-tert-butyl peroxide 0.394 part Graft copolymer stabiliser5.984 parts (33% solution, as described in (a),above).
When the feed was complete, the reaction mixture was held at recycle temperature for 3 hours. The resultlng lo dispersions of crosslinked microparticles, modified with non-crosslinked auxiliary polymer, had solids contents in the range 47-48% and insoluble gel contents in the range 29 3~/0.
The monomer used in the feed stage of step (a) of the above procedure in these Examples and Comparative Example had the compositions shown in the accompanying Table III; the first figure in each case represents the parts by weight of each monomer taken, the second figure (in parentheses) the weight percent-age of the monomer in question in the to~al monomers used in the feed stage.
TABLE III
_ . , Example ~o. 7 8 H
_ ,, _ _ Methyl math-acrylate 16.283(72.0) 150 085(66.8~ 19.877(88Ø) ~-o-Chlor-phenylmaleimide 2.396(10.6) 2.396(10.6) Styren~ 1 198( 5-3) 2.396(10.6) _ __~ .
g Examples 9-10 and Comparative Example J
Air-drying alkyd coating compositions were prepared by blending 90 parts of a 52% tall oil-modified alkyd resin from pentaerythritol, p-tert-butylbenzoic acid, benzoic acid and phthalican:hydxide with 10 parts of insoluble microparticles prepared as described in one of Examples 7 or 8 or Co}.nparative Example H. Each blend was thinned to a viscosity of 24 seconds (measured in a B.S. B3 cup at 25C) with a solvent consisting of aliphatic hydro-carbon, boiling range 138-165C, 95 parts, nonanol 5 parts, and mixed terpene alcohols 1 part. The blends wsre sprayed on to glass panels, allowed to dry ovar-night and the appearance of the resulting film then noted. The particular microparticles used, and the fi.~m appearance in each case are recorded in Table IV
be;Low.
TABLE IV
_._ . _ . _ ,_ Example ~o. 9 10 ._ ~
Microparticles from Ex. 7Ex. 8 Cxmp~
, ~ ,, Appearance of film slightly very . . cloudyclearcloudy
W CI~ ~~ ~ D~ D) I Dl I ~ ~ 11 :Z;
H ~3 ~ ~ ~ 13 (3 ~ P) Dl N O O . O
o l l l ~ w 8 8 o w ~
O l l ~ ~ l a . _ . ~ ~ ~ _ ' ~ :
~- ~ ~
L8~
The results of particle size determination given in Table I illustrate the fact that the use of s~yrene as a comonomer, in the absence of a maleic acid or fumaric acid derivative as required according to the present invention, leads to the production of relatively coarse particles in dispersion, which in turn cause the dispersion to sediment out rapidly on storage. The process of the invention, on the other hand, yields dispersions of similar particle size to those obtained with acrylic monomers only (i.e. omit-ting styrene).
~xample 6 and Comparative Examples D-G
Thermosetting acrylic coating compositions were prepared by blending a melamine-formaldehyde resin with an acrylic solution polymer having the composition : styrene ~2.5%, butyl methacrylate 21.25/~, butyl acrylate 21.25~/o~ hydroxyethyl methacrylate 14.0%
and acrylic acid l~o~ together with (in all cases except one) insoluble microparticles prepared as 20 described in one of the preceding Examples or Comp-arative Examples. Details of the particular micropart-icles used and of the proportion of the three constit-uents taken are given in the accompanying Table II;
the amounts stated are in each case parts hy weight based on 100% non-volatile material. Each blend was then thinned with a 1:1 mixture o~ butyl acetate and xylene to a spraying viscosity of 50-60 seconds (measured in a BS.B3 cup at 25C), and sprayed on to glass panels which were afterwards stoved for 30 minutes at 127C. The appearance of th~ resulting z~9 film was then noted : the results are recorded also in Table II.
TABLE II
Example ~o.6 D E F G
- --- - - - - - - -- . . ...
M/F resin 30 30 30 30 30 Acrylic 60 60 60 60 70 polymer Micro-particles from: 10 Example 4 Comp.Ex. A - 10 " " B - - 10 - -" " C - - - 10 Appèarance clear very slightly clear clear of fLlm cloudy cloudy The above results demonstrated that the inherent clarity of the cured acrylic film (Comparat-ive Example G) is lost if microparticles which are notmatched to its re~ractive index are introduced, i.e.
microparticles containing a zero or low proportion of styrene (Comparative Examples D & E). Clarity of the film is maintained if the microparticles contain a high proportion of styrene (Comparative Example F) but this, as is demonstrated by the results presented in the previous group of Examples, is done at the e~pense of the microparticles being of a coarqe size and consequently prone to settlement from dispersion.
In contrast, the use of styrene in conjunction with a maleic acid or fumaric acid derivative according to the invention, as shown by Example 6, enables clarity ~7~
of the ~ilm to be preserved without such accompanying drawbacks.
Examples 7-8 and Comparative Example H
(a) To a vessel fitted with stirrer, thermometer, 5 reflux condenser and Dean and Stark separator there was charged:-Aliphatic hydrocarbon (boiling range 140-156C;
zero aromatic content) 25.735 parts Methyl methacrylate 1.341 "
Methacrylic acid 0.026 part Azodiisobutyronitrile 0.107 part Graft copolymer stabiliser (33% solution, as described below) 0.497 part The vessel and charge were purged with inert gas and the temperature raised to 100C and maintained there for 30 minutes in order to produce a 'seed' polymer dispersion. The following pre-mixed ingredients were then fed into the vessel at a uniform rate over a period of 3 hours, maintaining the temperature at 100C with stirring:
Monomer, as given in detail below 19.877 parts Hydroxyethyl acrylate 1.130 "
~examethoxymethylmelamine 1.130 "
Methacrylic acid 0.451 part Azodiisobutyronitrile 0.140 Graft copolymer stabiliser (33% solution, as described below) 4.664 parts Aliphatic hydrocarbon, (as described above)11.320 parts 241;9 The reaction mixture was then h41d at 100 C
for a f~lrther period of 30 minutes, after which ~he temperature was raised to 140-145C when recycling of distillate commenced; these conditions were maintained for 2 hours, during which 1.2 parts of water were removed at the separator. The contents of the vessel were then cooled to give a fine dispersion of cross-linked microparticles. The dispersions had solids contents in the range 38-39~ and insoluble gel contents in the range 31-3 2%.
The graft copolymer stabiliser used in the foregoing procedure was obtained as follows:l2-hydroxy-stearic acid was self-condensed to an acid value of about 31-34 mg KOH/g (corresponding to a molecular weight of 1650-1800) and was then reacted with an equivalent amount of glycidyl methacrylate. The result-ing unsaturated ester was copolymerised with methyl methacrylate and glycidyl methacrylate in the weight ratios 49 : 46 : 5 respectively, and the copolymer thus obtained was finally reacted with methacrylic acid and p-nitrobenzoic acid in the presence of a tertiar~ amine catalyst, in the proportions of 0.070 part o methacrylic acid and 0.019 part of p-nitro-benzoic acid for every 100 parts of the copolymer.
(b) ~0 a vessel fitted as described in step (a) above, ~ut fitted with provision ~or adding a liquid feed into the recycling distillate, there was charged 66.418 parts of the dispersion obtained in step (a).
The dispersion was heated to 145C to establish re~
cycling of distillate, and the following premixed ingredients were then fed in via the returning distillate at a steady rate over a period of 3 hours:
~87~
Reaction product of poly(12- 14.982 parts hydroxystearic acid) and glycidyl methacrylate, (50~/0 solution in aliphatic hydrocarbon, boiling xange 136-165C) Hydroxyethyl acrylate 1.972 parts Methacrylic acid 0.394 part Styrene 5.913 parts Methyl methacrylate 3.943 parts Di-tert-butyl peroxide 0.394 part Graft copolymer stabiliser5.984 parts (33% solution, as described in (a),above).
When the feed was complete, the reaction mixture was held at recycle temperature for 3 hours. The resultlng lo dispersions of crosslinked microparticles, modified with non-crosslinked auxiliary polymer, had solids contents in the range 47-48% and insoluble gel contents in the range 29 3~/0.
The monomer used in the feed stage of step (a) of the above procedure in these Examples and Comparative Example had the compositions shown in the accompanying Table III; the first figure in each case represents the parts by weight of each monomer taken, the second figure (in parentheses) the weight percent-age of the monomer in question in the to~al monomers used in the feed stage.
TABLE III
_ . , Example ~o. 7 8 H
_ ,, _ _ Methyl math-acrylate 16.283(72.0) 150 085(66.8~ 19.877(88Ø) ~-o-Chlor-phenylmaleimide 2.396(10.6) 2.396(10.6) Styren~ 1 198( 5-3) 2.396(10.6) _ __~ .
g Examples 9-10 and Comparative Example J
Air-drying alkyd coating compositions were prepared by blending 90 parts of a 52% tall oil-modified alkyd resin from pentaerythritol, p-tert-butylbenzoic acid, benzoic acid and phthalican:hydxide with 10 parts of insoluble microparticles prepared as described in one of Examples 7 or 8 or Co}.nparative Example H. Each blend was thinned to a viscosity of 24 seconds (measured in a B.S. B3 cup at 25C) with a solvent consisting of aliphatic hydro-carbon, boiling range 138-165C, 95 parts, nonanol 5 parts, and mixed terpene alcohols 1 part. The blends wsre sprayed on to glass panels, allowed to dry ovar-night and the appearance of the resulting film then noted. The particular microparticles used, and the fi.~m appearance in each case are recorded in Table IV
be;Low.
TABLE IV
_._ . _ . _ ,_ Example ~o. 9 10 ._ ~
Microparticles from Ex. 7Ex. 8 Cxmp~
, ~ ,, Appearance of film slightly very . . cloudyclearcloudy
Claims (8)
1. A process for the production of addition polymer microparticles, comprising the dispersion polymeris-ation in an aliphatic hydrocarbon liquid of an ethyl-enically unsaturated monomer mixture which gives rise to a polymer or copolymer insoluble in the hydrocarbon liquid and which comprises (i) up to 50% by weight of styrene or a substituted derivative thereof and (ii) up to 50% by weight of a derivative of maleic acid or fumaric acid which is soluble in the hydrocarbon liquid at the temperature of polymerisation, the polymeris-ation being carried out in the presence in the hydro-carbon liquid of a steric dispersion stabiliser the molecule of which comprises at least one polymeric component which is solvated by the hydrocarbon liquid and at least one other component which is not solvated by the liquid and is capable of associating with the polymer produced.
2. A process as claimed in claim 1, wherein the derivative of maleic acid or fumaric acid contains in the molecule at least one aromatic group.
3. A process as claimed in claim 2, wherein the derivative is N-aryl-substituted maleimide of the general formula CH.CO
N . Ar CH.CO
where R is an aromatic radical which may contain a single benzene nucleus or two or more connected or fused benzene nuclei.
N . Ar CH.CO
where R is an aromatic radical which may contain a single benzene nucleus or two or more connected or fused benzene nuclei.
4. A process as claimed in claim 3, wherein the derivative is N-o-chlorophenylmaleimide.
5. A process as claimed in claim 2, wherein the derivative is a diester of maleic acid or fumaric acid of the structure where either X or Y, or both, is an aromatic radical which may contain a single benzene nucleus or two or more connected or fused benzene nuclei.
6. A process as claimed in claim 5, wherein the derivative is dibenzyl maleate.
7. A process as claimed in claims 1, 2 or 3 for preparing crosslinked polymer micropartieles, wherein the monomer mixture being polymerised comprises:-(i) from 10% to 40% by weight of styrene or a homologue thereof;
(ii) from 2% to 30% by weight of the maleic acid or fumaric acid derivative;
(iii) from 0.2% to 10% by weight of erosslinking monomer which is either (a) a single monomer which is defunctional or poly-functional with respect to the polymerisation reaction or (b) a combination of two monomers containing functional groupings which are mutually reactive by condensation reaction;
(iv) from 20% to 87.8% of one or more other ethyl-enically unsaturated monomers not falling within any of the categories (i), (ii) or (iii), the total monomers being 100%.
(ii) from 2% to 30% by weight of the maleic acid or fumaric acid derivative;
(iii) from 0.2% to 10% by weight of erosslinking monomer which is either (a) a single monomer which is defunctional or poly-functional with respect to the polymerisation reaction or (b) a combination of two monomers containing functional groupings which are mutually reactive by condensation reaction;
(iv) from 20% to 87.8% of one or more other ethyl-enically unsaturated monomers not falling within any of the categories (i), (ii) or (iii), the total monomers being 100%.
8. A process as claimed in claims 1, 2 or 3 for preparing crosslinked polymer microparticlws, wherein the monomer mixture being polymerised comprises;
(i) from 10% to 40% by weight of styrene or a homologue thereof;
(ii) from 2% to 30% by weight of the maleic or fumaric acid derivative;
(iii) from 1% to 20% by weight of a hydroxyl group-containing monomer:
(iv) from 1% to 5% by weight of a carboxyl group-containing monomer;
(v) from 5% to 86% by weight of one or more other ethylenically unsaturated monomers not falling within any of the categories (i) to (iv), the total monomers being 100%
and the monomer mixture being polymerised in the process of from 0.5% to 20%, based on the monomer mixture, of a reactive amino resin.
A process as claimed in claims 1, 2 or 3 wherein the stabilising agent is a graft copolymer comprising an acrylic polymer backbone, which is non-solvatable by the hydrocarbon liquid, and a plurality of chains pendant from the backbone which are residues of poly(l2-hydroxystearic acid) and which are solvatable by the hydrocarbon liquid.
A coating composition comprising a liquid diluent and film-forming constituents which comprise:-(i) a film-forming polymer;
(ii) polymer microparticles made by the process as claimed in claim 1, A coating composition as claimed in claim 10, wherein the polymer microparticles have been associated, before their introduction into the composition, with an essentially non-crosslinked polymer which is soluble in the liquid diluent of the composition and is compatible with the film-forming polymer.
(i) from 10% to 40% by weight of styrene or a homologue thereof;
(ii) from 2% to 30% by weight of the maleic or fumaric acid derivative;
(iii) from 1% to 20% by weight of a hydroxyl group-containing monomer:
(iv) from 1% to 5% by weight of a carboxyl group-containing monomer;
(v) from 5% to 86% by weight of one or more other ethylenically unsaturated monomers not falling within any of the categories (i) to (iv), the total monomers being 100%
and the monomer mixture being polymerised in the process of from 0.5% to 20%, based on the monomer mixture, of a reactive amino resin.
A process as claimed in claims 1, 2 or 3 wherein the stabilising agent is a graft copolymer comprising an acrylic polymer backbone, which is non-solvatable by the hydrocarbon liquid, and a plurality of chains pendant from the backbone which are residues of poly(l2-hydroxystearic acid) and which are solvatable by the hydrocarbon liquid.
A coating composition comprising a liquid diluent and film-forming constituents which comprise:-(i) a film-forming polymer;
(ii) polymer microparticles made by the process as claimed in claim 1, A coating composition as claimed in claim 10, wherein the polymer microparticles have been associated, before their introduction into the composition, with an essentially non-crosslinked polymer which is soluble in the liquid diluent of the composition and is compatible with the film-forming polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7944210 | 1979-12-21 | ||
| GB7944210 | 1979-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1187249A true CA1187249A (en) | 1985-05-14 |
Family
ID=10510020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000366359A Expired CA1187249A (en) | 1979-12-21 | 1980-12-09 | Production of polymer microparticles and coating compositions containing them |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4427820A (en) |
| EP (1) | EP0031997B2 (en) |
| JP (1) | JPS5698210A (en) |
| AT (1) | ATE5728T1 (en) |
| AU (1) | AU533527B2 (en) |
| CA (1) | CA1187249A (en) |
| CS (2) | CS163480A2 (en) |
| DE (1) | DE3066029D1 (en) |
| ES (1) | ES497978A0 (en) |
| GB (1) | GB2065674B (en) |
| NZ (1) | NZ195725A (en) |
| ZA (1) | ZA807746B (en) |
| ZW (1) | ZW30180A1 (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461870A (en) * | 1982-01-27 | 1984-07-24 | Nippon Paint Co., Ltd. | High solid coating composition containing novel microparticles of crosslinked copolymer including amphoionic groups |
| JPH0764904B2 (en) * | 1984-04-17 | 1995-07-12 | 大日本インキ化学工業株式会社 | Resin composition for coating material containing highly gelled fine particle polymer |
| JPS614761A (en) * | 1984-06-18 | 1986-01-10 | Nippon Paint Co Ltd | Fine resin particle containing crosslinking reaction promotor and method for using the same |
| JPS6134007A (en) * | 1984-07-27 | 1986-02-18 | Nippon Oil & Fats Co Ltd | Optical resin and its production |
| GB2164050B (en) * | 1984-08-06 | 1988-09-28 | Ici Plc | Coating composition containing dispersed particles of ethyl acrylate copolymer |
| JPS61162507A (en) * | 1985-01-11 | 1986-07-23 | Sumitomo Naugatuck Co Ltd | Production of copolymer with high heat resistance and good flowability |
| US4639394A (en) * | 1985-04-01 | 1987-01-27 | Ppg Industries, Inc. | Non-aqueous dispersions prepared with styrene polymer dispersion stabilizers |
| GB8530025D0 (en) * | 1985-12-05 | 1986-01-15 | Ici Plc | Coating compositions |
| US5051469A (en) * | 1985-12-13 | 1991-09-24 | Monsanto Company | Rubber modified reaction molded nylon-6 block copolymers |
| US4882382A (en) * | 1985-12-13 | 1989-11-21 | Monsanto Company | Rubber modified reaction molded nylon-6 block copolymers |
| US4994524A (en) * | 1985-12-13 | 1991-02-19 | Monsanto Company | Rubber modified reaction moldable nylon-6 compositions |
| US5073282A (en) * | 1989-04-21 | 1991-12-17 | Hercules Incorporated | Electrorheological fluids |
| US4990279A (en) * | 1989-04-21 | 1991-02-05 | Hercules Incorporated | Electrorheological fluids |
| US4992192A (en) * | 1989-04-21 | 1991-02-12 | Hercules Incorporated | Electrorheological fluids |
| GB9013679D0 (en) * | 1990-06-19 | 1990-08-08 | Ici Plc | Curable composition comprising a crystallisable polymer |
| GB9013678D0 (en) * | 1990-06-19 | 1990-08-08 | Ici Plc | Curable composition comprising a crystallisable polymer |
| JP3099099B2 (en) * | 1992-04-20 | 2000-10-16 | 関西ペイント株式会社 | Paint composition and coating method |
| DE4331805A1 (en) * | 1993-09-18 | 1995-03-23 | Basf Ag | Matt, transparent thermoplastic resins |
| US5929140A (en) * | 1994-05-20 | 1999-07-27 | Nippon Carbide Kogyo Kabushiki Kaisha | Coating resin of aliphatic HC solvent, carboxy-functional acrylic polymer and polymer particles |
| US6248225B1 (en) | 1998-05-26 | 2001-06-19 | Ppg Industries Ohio, Inc. | Process for forming a two-coat electrodeposited composite coating the composite coating and chip resistant electrodeposited coating composition |
| US6423425B1 (en) | 1998-05-26 | 2002-07-23 | Ppg Industries Ohio, Inc. | Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating |
| EP1204701B1 (en) | 1999-07-30 | 2005-09-21 | PPG Industries Ohio, Inc. | Cured coatings having improved scratch resistance and coated substrates |
| EP1204709B1 (en) | 1999-07-30 | 2007-02-14 | PPG Industries Ohio, Inc. | Coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| US6623791B2 (en) | 1999-07-30 | 2003-09-23 | Ppg Industries Ohio, Inc. | Coating compositions having improved adhesion, coated substrates and methods related thereto |
| US6610777B1 (en) * | 1999-07-30 | 2003-08-26 | Ppg Industries Ohio, Inc. | Flexible coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| KR100760068B1 (en) | 1999-07-30 | 2007-09-18 | 피피지 인더스트리즈 오하이오, 인코포레이티드 | Coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| US6635341B1 (en) | 2000-07-31 | 2003-10-21 | Ppg Industries Ohio, Inc. | Coating compositions comprising silyl blocked components, coating, coated substrates and methods related thereto |
| DE10065492A1 (en) * | 2000-12-28 | 2003-06-26 | Roehm Gmbh | Diffusely equipped molding compounds and moldings obtainable therefrom |
| CN100375201C (en) * | 2002-06-14 | 2008-03-12 | 海珀里昂催化国际有限公司 | Electroconductive carbon fibril-based inks and coatings |
| US8044148B2 (en) * | 2004-11-25 | 2011-10-25 | Panasonic Electric Works Co., Ltd. | Modified styrene-maleic acid copolymer and use thereof |
| FI20086122A (en) * | 2008-11-24 | 2010-05-25 | Kemira Oyj | The polymeric composition |
| US8540902B2 (en) * | 2010-01-13 | 2013-09-24 | CNano Technology Limited | Carbon nanotube based pastes |
| CN112920316B (en) * | 2021-02-26 | 2023-08-15 | 上海保立佳新材料有限公司 | Acrylic emulsion for vitrified tile back glue and preparation method thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE568069A (en) | 1957-05-27 | |||
| NL124341C (en) * | 1958-11-05 | 1900-01-01 | ||
| US3232903A (en) | 1961-10-19 | 1966-02-01 | Rohm & Haas | Polymer dispersions using hydrocarbons and graft copolymer dispersing agents |
| GB1123611A (en) | 1964-08-04 | 1968-08-14 | Ici Ltd | Polymer dispersions |
| US3399164A (en) | 1965-08-04 | 1968-08-27 | Ici Ltd | Polymer dispersions |
| AU423442B2 (en) | 1967-10-27 | 1972-04-19 | Dulux Australia Limited | Dispersions of cross-linkable polymer particles inorganic liquids |
| GB1374423A (en) | 1970-11-27 | 1974-11-20 | Ici Ltd | Chemical processes |
| US3814721A (en) | 1971-03-01 | 1974-06-04 | Ford Motor Co | Nonaqueous dispersions of thermosetting film forming copolymers of ethenic monomers |
| US3745137A (en) | 1971-10-26 | 1973-07-10 | Celanese Coatings Co | Process of preparing nonaqueous dispersions of thermosetting copolymers |
| US3729451A (en) | 1972-07-10 | 1973-04-24 | Gulf Research Development Co | Process for copolymerization of maleic anhydride with 1-olefins |
| DE2501123C2 (en) | 1975-01-14 | 1984-02-09 | Bayer Ag, 5090 Leverkusen | Process for the production of suspension copolymers |
| US4074036A (en) * | 1976-11-05 | 1978-02-14 | Allied Chemical Corporation | Production of low molecular weight polyanhydrides |
| FR2408628A1 (en) * | 1977-11-15 | 1979-06-08 | Rhone Poulenc Ind | STYRENIC POLYMERS WITH IMPROVED THERMAL PROPERTIES |
| JPS54116037A (en) * | 1978-03-02 | 1979-09-10 | Dainippon Ink & Chem Inc | Thermosetting resin composition for metallic coating |
-
1980
- 1980-12-01 GB GB8038473A patent/GB2065674B/en not_active Expired
- 1980-12-01 DE DE8080304319T patent/DE3066029D1/en not_active Expired
- 1980-12-01 AT AT80304319T patent/ATE5728T1/en not_active IP Right Cessation
- 1980-12-01 EP EP80304319A patent/EP0031997B2/en not_active Expired
- 1980-12-02 NZ NZ195725A patent/NZ195725A/en unknown
- 1980-12-04 AU AU65056/80A patent/AU533527B2/en not_active Ceased
- 1980-12-05 ZW ZW301/80A patent/ZW30180A1/en unknown
- 1980-12-09 CA CA000366359A patent/CA1187249A/en not_active Expired
- 1980-12-10 ZA ZA00807746A patent/ZA807746B/en unknown
- 1980-12-19 JP JP17910180A patent/JPS5698210A/en active Granted
- 1980-12-19 ES ES497978A patent/ES497978A0/en active Granted
- 1980-12-22 CS CS801634A patent/CS163480A2/en unknown
- 1980-12-22 CS CS809154A patent/CS244659B2/en unknown
-
1982
- 1982-06-09 US US06/386,635 patent/US4427820A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE5728T1 (en) | 1984-01-15 |
| NZ195725A (en) | 1983-07-15 |
| ZA807746B (en) | 1982-01-27 |
| DE3066029D1 (en) | 1984-02-02 |
| US4427820A (en) | 1984-01-24 |
| AU6505680A (en) | 1981-06-25 |
| AU533527B2 (en) | 1983-12-01 |
| JPS5698210A (en) | 1981-08-07 |
| CS244659B2 (en) | 1986-08-14 |
| CS915480A2 (en) | 1985-09-17 |
| EP0031997B2 (en) | 1988-09-14 |
| ZW30180A1 (en) | 1982-07-14 |
| JPH0480046B2 (en) | 1992-12-17 |
| CS163480A2 (en) | 1985-09-17 |
| EP0031997B1 (en) | 1983-12-28 |
| EP0031997A1 (en) | 1981-07-15 |
| ES8200906A1 (en) | 1981-11-16 |
| ES497978A0 (en) | 1981-11-16 |
| GB2065674A (en) | 1981-07-01 |
| GB2065674B (en) | 1983-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1187249A (en) | Production of polymer microparticles and coating compositions containing them | |
| CA1126101A (en) | Spray coating process | |
| CA1139033A (en) | Production of polymer microparticles and coating compositions containing them | |
| US4180489A (en) | Coating composition | |
| US5212273A (en) | Crosslinked polymeric microparticles; their method of preparation and use in coating compositions | |
| US3686111A (en) | Non-aqueous polymeric pseudo-dispersion | |
| US3580880A (en) | Dispersions of particulate solids in either lipophilic or hydrophilic liquids stabilized with a polymeric amphipathic stabiliser and process for preparing said dispersions | |
| US3532662A (en) | Process of making dispersions of pigments coated with a polymer containing polar groups in liquids | |
| US4268547A (en) | Coating process | |
| CA1329439C (en) | Method for preparing stably dispersed nonaqueous microparticle dispersions | |
| CA1266139A (en) | Dispersion of addition (co)polymers in an organic liquid | |
| EP0185431B1 (en) | Composite resin particles, its preparation and resinous composition for coating use containing the same | |
| JPH0338282B2 (en) | ||
| US3393162A (en) | Block and graft copolymer coated pigments | |
| US5006617A (en) | Emulsion polymers free from emulsifiers and protective colloids, a process for their preparation and their use | |
| US4777199A (en) | Coating composition | |
| AU635072B2 (en) | Dispersion of fine particles of a vinyl polymer | |
| CA1126103A (en) | Coating process | |
| CA1183300A (en) | Production of polymer microparticles and coating compositions containing them | |
| US3808169A (en) | Process for the preparation of polymer solutions | |
| US4739004A (en) | Cross-linked dispersion copolymers containing vinyl acetate | |
| AU604978B2 (en) | Thickeners for physically drying paints and coating materials and preparation of the thickeners | |
| US4556686A (en) | Stable crosslinked dispersion | |
| GB2051830A (en) | Preparation of cross-linked polymer microparticles | |
| GB2025992A (en) | Production of Polymer Microparticles and Coating Compositions Containing them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |