Composite acrylic resin particles

Composite acrylic acrylic resin particles each comprising a particular metal-containing crosslinked acrylic polymer to which a number of substantially linear acrylic polymer chains are chemically bonded are provided. Such particles are specifically useful as resinous filler in curing type coating compositions because of having curing catalytic activities.

FIELD OF THE INVENTION 
The present invention relates to novel composite acrylic resin particles 
each comprising a particulate metal-containing crosslinked acrylic polymer 
to which a number of substantially linear acrylic polymer chains are 
chemically bonded, and being specifically useful in coating compositions. 
BACKGROUND OF THE INVENTION 
Granular resins are supplied in the forms of emulsions, microgels, 
non-aqueous dispersion resins (AND resins), powder resins and the like, 
and have been watched with keen interest in paint industries, especially 
in aqueous paints, high solid paints and powder paints, because of 
measuring up to the social requirements of economization of natural 
resources, energy saving and conservation of good surroundings. 
However, such a resin is usually crosslinked so that the characteristics of 
the resin particles can be fully developed, and therefore when the 
granular resin is used alone, it is unable to get a uniform or excellent 
film and the resulted film has a serious drawback of deficient film 
appearance. 
Even when the granular resin is combined with a soluble type resin, there 
is a case that the viscosity of the mixture is unduly increased, as 
compared with that of said soluble type resin alone, due to the 
considerable interaction between the surfaces of said granules and the 
soluble type resin. Therefore, a great care is often required in the 
actual use of such combination of resins. 
Furthermore, since the characteristics of crosslinked resins are greatly 
influenced by the nature of surfactant used, crosslinking degree and 
combination of constituting monomers and the like, heretofore proposed 
crosslinked resin particles are hardly dispersible in such medium as 
aliphatic hydrocarbons, high boiling aromatic hydrocarbons, high polar 
solvents or the like, and once they make agglomerates, hardly get loose to 
the primary particles. Thus, considerable difficulties are always 
encountered in the actual application thereof. 
It has also been well known to conduct the polymerization of acrylic 
monomers in multi-stages, thereby obtaining composite acrylic resin 
particles each having the so-called core-shell structure, the core being 
composed of crosslinked acrylic polymer and the shell being of crosslinked 
or non-crosslinked acrylic polymer. When the shell portion is composed of 
non-crosslinked polymer, a comparatively good dispersion may be obtained 
with these particles in a soluble type resin or a solvent type coating 
composition. However, for a better ageing stability, the shell portion 
should preferably be chemically bonded to the crosslinked core resin, 
otherwise the non-crosslinked polymer in shell portion will be gradually 
dissolved in said resin or organic solvent and the dispersion stability of 
the resin particles will be lost out in time. 
Under the circumstances, attempts have been made to effect graft 
polymerization in multi-stages, thereby chemically bonding the core and 
the shell layers, as, for example, in Kamata et al. U.S. Pat. No. 
4,362,845, Linder U.S. Pat. No. 4,2393,172 and the like. 
However, when the heretofore proposed composite resin particles were 
examined by dispersing them in butyl acetate, treating in a centrifugal 
machine to dissolve the non-crosslinked polymer into the solvent and 
measuring the remained particle weight, it was found that the grafting 
rate was generally in an extremely lower order. And, in fact, the 
dispersion stability of such resin particles in an organic solvent or 
resinous varnish was found to be rather poor. 
Therefore, it has long been desired to provide novel composite acrylic 
resin particles each comprising a particulate crosslinked acrylic polymer 
to which a number of substantially linear acrylic polymer chains are 
chemically bonded in a high grafting rate, which are free from the 
drawbacks possessed by the heretofore proposed composite resin particles. 
The inventors, having studied hard on the way for chemically bonding linear 
polymer chains to the surface of particulate crosslinked acrylic polymer, 
have succeeded in attaining said object by utilizing the selective 
addition of particular substituted ethylenic bonds and applied for patent 
on it, as, for example, Japanese Patent Application 90827/86 (now laid 
open as Kokai No. 246916/87), U.S. patent application 40476, EPC 
87303493.8 and the like. 
The said method comprises a combination of steps of effecting an emulsion 
polymerization of a monomer mixture of 
(A) at least one crosslinking monomer having in its molecule two or more 
radically polymerizable mono- or 1,1-di-substituted ethylenic unsaturation 
bonds, or a combination of at least two monomers each having a mutually 
reactive functional group and one or more radically polymerizable mono- or 
1,1-di-substituted ethylenic unsaturation bonds, 
(B) at least one mono-functional polymerizable monomer other than aromatic 
compound, and 
(C) at least one monomer having in its molecule one or more radically 
polymerizable mono- or 1,1-di-substituted ethylenic unsaturation bonds and 
one or more radically polymerizable 1,2-di-, 1,1,2-tri- or 
1,1,2,2-tetra-substituted ethylenic unsaturation bonds, to obtain an 
emulsion of crosslinked polymer particles on which radically polymerizable 
1,2-di-, 1,1,2-tri- or 1,1,2,2-tetra-substituted ethylenic unsaturation 
bonds are still remained, and effecting a graft-polymerization of said 
polymer particles with a polymerizable aromatic compound together with 
other optional mono-functional polymerizable monomers. 
Thus obtained composite resin particles are indeed prominent in that they 
can be used either singularly or in combination form with other soluble 
resins customarily used in paint industries, to give excellent coating 
compositions with good application characteristics and storage stability 
and capable of resulting a uniform coating with excellent film appearance, 
but further developments are still demanded both on said coating 
compositions and said composite resin particles. 
That is, in such coating composition, a hardener is usually compounded and 
the composition is subjected to curing reaction. At that time, a catalyst 
is usually added to the composition to promote said curing, but the 
presence of such catalyst may cause additional problem of decrease in 
durability of cured coating. 
The proposed composite resin particles are useless in that subject matter. 
Beside the application in coating composition, the proposed composite resin 
particles may be used as, for example, molding material, additives for 
agricultural products or plastic film and the like. 
In these applications, fungicidal activities or bioactivities are often 
required, and however, since the resin particles are just developed as 
resinous filler for coating compositions, such additional functions could 
not be expected with the composite resin particles themselves. It is, 
therefore, an object of the invention to provide novel class of composite 
resin particles each comprising a particulate crosslinked acrylic polymer 
to which a number of substantially linear acrylic polymer chains are 
chemically bonded and having other desired activities as, for example, 
curing catalytic activity, bioactivities and the like. Additional object 
of the invention is to provide an industrially advantageous method for the 
preparation of such resin particles. 
SUMMARY OF THE INVENTION 
According to the invention, the aforesaid objects can be attained with 
composite acrylic resin particles each comprising a particulate 
metal-containing crosslinked acrylic polymer to which a number of 
substantially linear acrylic polymer chains are chemically bonded. The 
present composite acrylic resin particles may advantageously be prepared 
by either one of the following methods. 
The first method comprises a combination of steps of effecting an emulsion 
polymerization of a monomer mixture of 
(A) at least one crosslinking monomer having in its molecule two or more 
radically polymerizable mono- or 1,1-di-substituted ethylenic unsaturation 
bonds, or a combination of at least two monomers each having a mutually 
reactive functional group and one or more radically polymerizable mono- or 
1,1-di-substituted ethylenic unsaturation bonds, 
(B) at least one mono-functional polymerizable monomer other than aromatic 
compound, and metal-containing monomer hereinunder defined, 
(C) at least one metal-containing monomer, and 
(D) at least one monomer having in its molecule one or more radically 
polymerizable mono- or 1,1-di-substituted ethylenic unsaturation bonds and 
one or more radically polymerizable 1,2-di-, 1,1,2-tri- or 
1,1,2,2-tetra-substituted ethylenic unsaturation bonds, to obtain an 
emulsion of metal-containing crosslinked polymer particles on which 
radically polymerizable 1,2-di-, 1,1,2-tri- or 1,1,2,2-tetra-substituted 
ethylenic unsaturation bonds are still remained, and effecting a 
graft-polymerization of said polymer particles with a polymerizable 
aromatic compound together with other optional mono-functional 
polymerizable monomers. 
The second method comprises a combination of steps of effecting an emulsion 
polymerization of a monomer mixture of 
(A) at least one crosslinking monomer having in its molecule two or more 
radically polymerizable mono- or 1,1-di-substituted ethylenic unsaturation 
bonds, or a combination of at least two monomers each having a mutually 
reactive functional group and one or more radically polymerizable mono- or 
1,1-di-substituted ethylenic unsaturation bonds, 
(B) at least one mono-functional polymerizable monomer other than aromatic 
compound, and acid group containing monomer hereinunder defined, 
(D) at least one monomer having in its molecule one or more radically 
polymerizable mono- or 1,1-di-substituted ethylenic unsaturation bonds and 
one or more radically polymerizable 1,2-di-, 1,1,2-tri- or 
1,1,2,2-tetra-substituted ethylenic unsaturation bonds, and 
(E) at least one acid group containing polymerizable monomer, to obtain an 
emulsion of crosslinked polymer particles containing acid groups and 
radically polymerizable 1,2-di-, 1,1,2-tri- or 1,1,2,2-tetra-substituted 
ethylenic unsaturation bonds, 
reacting thus obtained emulsion with an organic metallic compound in an 
organic solvent, while removing water from the reaction mixture, to obtain 
metal-containing crosslinked polymer particles on which radically 
polymerizable 1,2-di-, 1,1,2-tri- or 1,1,2,2-tetra-substituted ethylenic 
unsaturation bonds are still remained, and effecting a 
graft-polymerization of said polymer particles with a polymerizable 
aromatic compound together with other optional mono-functional 
polymerizable monomers. 
In the present specification and claims, the term "metal" or "metal 
element" shall mean the element which is located in the left side of the 
line that links B, Si, As, Te with At in the long form of the periodic 
table, providing excluding said B, Si, As, Te and At. 
The present composite acrylic resin particles are, thus, characterized in 
that particulate crosslinked acrylic polymer bears metal elements and a 
number of substantially linear acrylic polymer chains are chemically 
bonded to said particulate crosslinked acrylic polymer, and that the 
desired catalytic activities, bioactivities or the like can be expected 
with said metal elements contained. 
The linear polymer chain may be somewhat branched or crosslinked as 
desired. Therefore, in the specification and claims, the term 
"substantially linear" shall mean the polymer chains which are essentially 
of linear type polymer, admitting the presence of a certain degree of 
branching or crosslinking therein. 
As already stated, the present composite acrylic resin particles are 
advantageously prepared by the following two or three steps. 
1. Preparation of core portion of metal-containing crosslinked acrylic 
polymer: 
In this step, the following monomer mixture is polymerized in a 
conventional emulsion polymerization means 
(A) at least one crosslinking monomer having in its molecule two or more 
radically polymerizable mono- or 1,1-di-substituted ethylenic unsaturation 
bonds, or a combination of at least two monomers each having a mutually 
reactive functional group and one or more radically polymerizable mono- or 
1,1-di-substituted ethylenic unsaturation bonds, 
(B) at least one mono-functional polymerizable monomer other than aromatic 
compound, and metal-containing monomer, 
(C) at least one metal-containing monomer, and 
(D) at least one monomer having in its molecule one or more radically 
polymerizable mono- or 1,1-di-substituted ethylenic unsaturation bonds and 
one or more radically polymerizable 1,2-di-, 1,1,2-tri- or 
1,1,2,2-tetrasubstituted ethylenic unsaturation bonds. Examples of 
crosslinking monomer having in its molecule two or more radically 
polymerizable mono- or 1,1-di-substituted ethylenic unsaturation bonds, 
are polymerizable unsaturated monocarboxylic acid esters of polyhydric 
alcohols, polymerizable unsaturated alcohol esters of polycarboxylic acids 
and aromatic compounds substituted with two or more vinyl groups. 
More specifically, they are, for example, ethyleneglycol diacrylate, 
ethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 
tetraethyleneglycol dimethacrylate, 1,3-butyleneglycol dimethacrylate, 
trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 
1,4-butanediol diacrylate, neopentylglycol diacrylate, 1,6-hexanediol 
diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, 
pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, 
pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 
glycerol dimethacrylate, glycerol diacrylate, glycerol alloxy 
dimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 
1,1,1-trihydroxymethylethane triacrylate, 1,1,1-trishydroxymethylethane 
dimethacrylate, 1,1,1-trishydroxymethylethane trimethacrylate, 
1,1,1-trishydroxymethylpropane diacrylate, 1,1,1-trishydroxymethylpropane 
triacrylate, 1,1,1-trishydroxymethylpropane dimethacrylate, 
1,1,1-trishydroxymethylpropane trimethacrylate, triallyl cyanurate, 
triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, 
diallyl phthalate and divinyl benzene. 
Examples of the combination of monomers each having a mutually reactive 
functional group and one or more radically polymerizable mono- or 
1,1-di-substituted ethylenic unsaturation bonds are epoxy containing 
ethylenically unsaturated monomer (e.g. glycidyl acrylate, glycidyl 
methacrylate and the like) and carboxyl containing ethylenically 
unsaturated monomer (e.g. acrylic acid, methacrylic acid, crotonic acid 
and the like). Various combination of reactive groups are proposed as, for 
example, amine and carbonyl, epoxy and carboxylic anhydride, amine and 
acid chloride, alkyleneimine and carbonyl, organoalkoxysilane and 
carboxyl, hydroxyl and isocyanate and the like, and they are 
satisfactorily used in the present invention. 
As the mono-functional polymerizable monomer other than aromatic compound 
and metal-containing monomer, the following may be used. 
(1) carboxyl group containing monomer 
as, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic 
acid, maleic acid, fumaric acid and the like, 
(2) hydroxyl group containing monomer 
as, for example, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 
2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl 
acrylate, hydroxybutyl methacrylate, allyl alcohol, methallyl alcohol and 
the like, 
(3) nitrogen containing alkyl acrylate or methacrylate 
as, for example, dimethyl aminoethyl acrylate, dimethyl aminoethyl 
methacrylate and the like, 
(4) polymerizable amide 
as, for example, acryl amide, methacryl amide and the like, 
(5) polymerizable nitrile 
as, for example, acrylonitrile, methacrylonitrile and the like, 
(6) alkyl acrylate or methacrylate 
as, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, 
n-butyl acrylate, n-butyl methacrylate, 2-ethyl hexyl acrylate and the 
like, 
(7) polymerizable glycidyl compound 
as, for example, glycidyl acrylate, glycidyl methacrylate and the like, 
(8) .alpha.-olefin 
as, for example, ethylene, propylene and the like, 
(9) vinyl compound 
as, for example, vinyl acetate, vinyl propionate and the like, 
(10) reaction compounds of the abovesaid monomers 
as, for example, reaction compound of hydroxyl containing monomer (2) with 
isocyanate compound, reaction compound of carboxyl containing monomer (1) 
with glycidyl containing compound and the like. 
Among various mono-functional polymerizable monomers, aromatic compounds 
(e.g. styrene, styrene derivative and the like) should not be used at this 
stage, since they are selectively reactive with 1,2-di-, 1,1,2-tri- or 
1,1,2,2-tetra-substituted ethylenic unsaturation bonds and hence, are not 
suitable for the preparation of core portion of metal-containing 
crosslinked acrylic polymer still having a number of grafting points (i.e. 
1,2-di-, 1,1,2-tri- or 1,1,2,2-tetra-substituted ethylenic unsaturations) 
thereof. Metal-containing polymerizable monomers are likewise omitted from 
this group of monomers, because they are defined as an essential monomer 
separately. 
Examples of metal-containing monomers are metal esters or metal salts of 
polymerizable organic acids as, for example, acrylic acid, methacrylic 
acid, itaconic acid, maleic acid and the like; vinyl metals; styryl metals 
and the like. The metal element may also bear other groups as hydroxyl 
group, organic acid residue, substituted or unsubstituted alkyl group and 
the like. 
More specifically, said metal-containing monomers are exemplified by zinc 
mono-acrylate, zinc mono-methacrylate, zinc diacrylate, zinc 
dimethacrylate, tributyl tin acrylate, tributyl tin methacrylate, dibutyl 
tin diacrylate, dibutyl tin dimethacrylate, dihydroxy aluminium acrylate, 
dihydroxy aluminium methacrylate, hydroxy aluminium diacryalte, hydroxy 
aluminium dimethacrylate, acryloyl ferrocene, methacryloyl ferrocene, 
furyl acryloyl ferrocene, furyl methacryloyl ferrocene, acryloyl zirconium 
octate, methacryloyl zirconium octate, acryloxy zirconium laurate, 
methacryloxy zirconium laurate, isopropyl acryloyl diisostearoyl titanate, 
isopropyl methacryloyl diisostearoyl titanate, isopropyl diacryroyl 
isostearoyl titanate, isopropyl dimethacryroyl isostearoyl titanate, 
triethyl germanium acrylate, triethyl germanium methacrylate, styryl 
triethyl germane, vinyl triethyl germane, diphenyl lead diacrylate, 
diphenyl lead methacrylate, styryl triethyl lead and the like. They may be 
represented by either one of the formulae: 
##STR1## 
(wherein M stands for metal element, R is substituted or unsubstituted 
alkyl, substituted or unsubstituted phenyl or hydroxyl, R' represents 
hydrogen atom or methyl group, n is valency of said metal, and x is an 
integer which is smaller than n). 
Examples of the monomer having in its molecule one or more radically 
polymerizable mono- or 1,1-di-substituted ethylenic unsaturation bonds and 
one or more radically polymerizable 1,2-di-, 1,1,2-tri- or 
1,1,2,2-tetra-substituted ethylenic unsaturation bonds, are addition 
product of maleic acid and glycidyl acrylate, addition product of maleic 
acid and glycidyl methacrylate, addition product of fumaric acid and 
glycidyl acrylate, addition product of fumaric acid and glycidyl 
methacrylate, addition product of maleic acid monoester and glycidyl 
acryalte, maleic acid monoester and glycidyl methacrylate, addition 
product of fumaric acid monoester and glycidyl acrylate, addition product 
of fumaric acid monoester and glycidyl methacrylate, addition product of 
substituted maleic acid and glycidyl (meth) acrylate, addition product of 
substituted maleic acid monoester and glycidyl (meth) acrylate, addition 
product of substituted fumaric acid and glycidyl (meth) acrylate, and 
addition product of substituted fumaric acid monoester and glycidyl (meth) 
acrylate. 
The emulsion polymerization may be carried out in a conventional way, using 
a polymerization initiator and an appropriate emulsifier. Particularly 
preferable emulsifiers are acrylic, polyester, alkyd or poxy resin having 
in its molecule an amphoionic group of the formula: 
##STR2## 
wherein R represents C.sub.1 to C.sub.6 alkylene or phenylene and 
Y.sup..crclbar. stands for --COO.sup..crclbar. or 
--SO.sub.3.sup..crclbar., as disclosed in Japanese Patent Application 
Kokai No. 129066/83. 
In this first step of polymerization, only mono- or 1,1-di-substituted 
ethylenic bonds may participate in the reaction, giving crosslinked 
acrylic polymer particles still having unreacted 1,2-di-, 1,1,2-tri- or 
1,1,2,2-tetra-substituted ethylenic unsaturation bonds on the surfaces 
thereof. Such core portion of metal-containing crosslinked acrylic polymer 
may also be prepared in two steps, comprising polymerizing, in an emulsion 
polymerization, a monomer mixture of 
(A) at least one crosslinking monomer having in its molecule two or more 
radically polymerizable mono- or 1,1-disubstituted ethylenic unsaturation 
bonds, or a combination of at least two monomers each having a mutually 
reactive functional group and one or more radically polymerizable mono- or 
1,1-di-substituted ethylenic unsaturation bonds, 
(B) at least one mono-functional polymerizable monomer other than aromatic 
compound and acid group containing monomer hereinunder defined, 
(D) at least one monomer having in its molecule one or more radically 
polymerizable mono- or 1,1-di-substituted ethylenic unsaturation bonds and 
one or more radically polymerizable 1,2-di-, 1,1,2-tri- or 
1,1,2,2-tetrasubstituted ethylenic unsaturation bonds, and 
(E) at least one acid group containing polymerizable monomer, to obtain an 
emulsion of crosslinked polymer particles containing acid groups and 
radically polymerizable 1,2-di-, 1,1,2-tri- or 1,1,2,2-tetra-substituted 
ethylenic unsaturation bonds, and then 
reacting thus obtained emulsion with at least one metallic compound in an 
organic solvent, while removing water from the reaction mixture, to obtain 
metal-containing crosslinked polymer particles on which radically 
polymerizable 1,2-di-, 1,1,2-tri- or 1,1,2,2-tetra-substituted ethylenic 
unsaturation bonds are still remained. 
In the first step reaction, the same monomeric compounds (A), (B) and (D) 
as already mentioned in connection with the preceding one step method are 
used, together with acid group containing polymerizable monomer (E). 
Examples of such monomer (E) are acrylic acid, methacrylic acid, crotonic 
acid, itaconic acid, maleic acid, fumaric acid and the like. 
And thus obtained crosslinked polymer particles having on their surfaces 
acid groups and radically polymerizable ethylenic unsaturation bonds are 
then reacted with at least one metallic compound in an organic solvent in 
the second step. At that time, the desired metal element may be introduced 
to the polymer particles by any of the known techniques. However, the most 
preferable and advantageous method is to use esterification or 
ester-exchange reaction between said acid group and metallic compound. As 
the metallic compounds to be used in that reaction, mention is made of 
metal oxides, metal halogenides and metal hydroxides as, for example, 
magnesium chloride, calcium oxide, chromium chloride, zinc oxide, tributyl 
tin oxide, dibutyl tin oxide, triethyl tin chloride, tribenzyl tin 
chloride, diethyl aluminium chloride, aluminium hydroxide, sodium 
hydroxide, potassium hydroxide, calcium hydroxide and the like. 2. 
Preparation of the present composite acrylic resin particles each 
comprising a particulate metal-containing crosslinked acrylic polymer to 
which a number of substantially linear acrylic polymer chains are 
chemically bonded: 
To thus obtained core particle emulsion, a polymerizable aromatic compound 
is added and polymerization is continued to effect a graft polymerization 
between the remaining ethylenic unsaturation bonds and the polymerizable 
aromatic compound. Since 1,2-di-, 1,1,2-tri- or 1,1,2,2-tetra-substituted 
ethylenic bond has a selective reactivity towards polymerizable aromatic 
compound as styrene, .alpha.-methyl styrene, vinyl toluene, t-butyl 
styrene and the like, a higher grafting rate can be attained with the 
aforesaid particulate metal-containing crosslinked polymer coupled with 
the polymerizable aromatic compound. 
It is of course possible to use, besides the required polymerizable 
aromatic compound, other polymerizable monomers for the preparation of 
said linear polymer chains as desired. Any of the mono-functional 
polymerizable monomers hereinbefore stated under the column "preparation 
of core portion of crosslinked acrylic polymer " may satisfactorily be 
used. 
Furthermore, since a certain degree of branching or crosslinking is 
permissible according to circumstances, a limited amount of crosslinking 
monomer may be used together, as desired. 
In any case, the shell portion of the present composite resin particles 
should be composed of substantially linear acrylic polymer and grafted to 
the crosslinked polymer core. Various desired properties may be given to 
the present composite resin particles by the selection of grafting 
monomers. For example, when the aforesaid monomers (1) or (3) are 
selected, the composite resin particles having carboxyl or amino 
containing polymer chains can be obtained, said particles having 
self-catalytic function in curing, high reactivity with an epoxy compound 
and being useful in an anionic or cationic electrodeposition use. When 
hydroxyl containing monomers are used, the resulted composite resin 
particles may be crosslinked with a melamine resin and/or isocyanate 
compound to give a tough coating. When the aforesaid monomers (4), 
addition products of hydroxyl containing monomers and monoisocyanate 
compounds or addition products of isocyanate containing monomers and 
monoamine compounds are used, it is possible to obtain the composite 
crosslinked resin particles with highly crystalline polymer chains, which 
are useful in having structural viscosity and rheology control in a 
coating composition. 
It is also possible to carry on the linear polymer chains various 
functional groups and utilize the characteristic properties thereof. 
The present composite acrylic resin particles are excellent in 
dispersibilities in various solvents and resinous varnishes and possess 
self-film forming properties. 
Various functional polymers can be chemically bonded on the surface of the 
particulate crosslinked acrylic polymer. Since the desired metal elements 
can be carried on the core portions of these particles, curing catalytic 
activities or bioactivities are given to the present composite acrylic 
resin particles themselves. Therefore, they are specifically useful in 
paint and other chemical industries. The invention shall be now more fully 
explained in the following Examples. Unless otherwise being stated, all 
parts and percentages are by weight.

Reference Example 1 
Preparation of dispersion stabilizer 
Into a 2 liters flask fitted with a stirrer, a nitrogen gas inlet tube, a 
thermoregulator, a condenser and a decanter, were placed 134 parts of 
bishydroxy ethyl taurine, 130 parts of neopentylglycol, 236 parts of 
azelaic acid, 186 parts of phthalic anhydride and 27 parts of xylene and 
the mixture was heated while removing the formed water azeotropically with 
xylene. The temperature was raised to 190.degree. C. in about 2 hours from 
the commencement of reflux and the reaction was continued under stirring 
and dehydration until the acid value (based on carboxylic acid group) 
reached 145. Thereafter, the reaction mixture was allowed to cool to 
140.degree. C. and to this, 314 parts of Cardura E-10 (glycidyl versatate, 
trademark of Shell) were dropwise added in 30 minutes at 140.degree. C. 
The mixture was stirred at the same temperature for 2 hours and then the 
reaction was stopped to obtain a polyester resin having an acid value of 
59, a hydroxyl value of 90 and a number average molecular weight of 1054. 
Reference Example 2 
Preparation of dispersion stabilizer 
Into a similar reaction vessel as used in Reference Example 1, were placed 
73.5 parts of taurine Na salt, 100 parts of ethyleneglycol, and 200 parts 
of ethyleneglycol monomethyl ether, and the mixture was heated, under 
stirring, to 120.degree. C. At the stage when a uniform solution was 
obtained, a mixture of 470 parts of Epicohto 1001 (bisphenol A diglycidyl 
ether type epoxy resin, epoxy equivalent 470, trademark of Shell Chem.) 
and 400 parts of ethyleneglycol monomethyl ether was dropwise added in 2 
hours. After completion of said addition, the combined mixture was heated 
and stirred for 20 hours. Thus obtained product was then purified and 
dried to obtain 518 parts of modified epoxy resin, whose acid value 
(measured by KOH titration method) was 49.4 and sulfur content (measured 
by fluorescent X ray analysis) was 2.8%. 
Reference Example 3 
Preparation of dispersion stabilizer 
Into a 1 liter flask fitted with a stirrer, a thermoregulator, dropping 
funnels, a nitrogen gas inlet tube and a condenser, were placed 140 parts 
of ethyleneglycol monomethyl ether and 140 parts of xylene, and the 
mixture was heated to 120.degree. C. To this, a monomer mixture of 74 
parts of methyl methacrylate, 70 parts of 2-ethylhexylacrylate, 24 parts 
of 2-hydroxyethyl methacrylate, and 12 parts of methacrylic acid, added 
with 5 parts of azobis-isobutyronitrile and a solution of 20 parts of 
N-(3-sulfopropyl)-N-methacryloyloxyethyl-N,N-dimethyl ammonium betaine in 
150 parts of ethyleneglycol monoethyl ether were simultaneously and 
dropwise added in 3 hours. After elapsing 30 minutes from the completion 
of said addition, a solution of 0.4 part of t-butylperoxy-2-ethylhexanoate 
in 8 parts of ethylene glycol monomethyl ether was added and the combined 
mixture was kept at 120.degree. C. for 1 hour and thereafter, the solvent 
was removed off to obtain an amphoionic group containing acrylic resin 
having a non-volatile content of 92%. 
Reference Example 4 
Preparation of monomer containing two polymerizable ethylenic groups each 
having different co-reactivity 
Into a 1 liter flask fitted with a stirrer, an air inlet tube, a 
thermoregulator, and a condenser, were placed 430 parts of n-butyl maleate 
and 1.6 parts of hydroquinone and the mixture was heated to 150.degree. C. 
To this, were dropwise added 373 parts of glycidyl methacrylate in 20 
minutes and the combined mixture was maintained at 150.degree. C. for 60 
minutes. The reaction was stopped at the stage when the resinous acid 
value reached 3 KOH mg/g. 
Example 1 
Into a 1 liter flask fitted with a stirrer, a thermoregulator, a dropping 
funnel, a nitrogen gas inlet tube and a condenser, were placed 306 parts 
of deionized water and the temperature was raised to 80.degree. C. 
Separately, a pre-emulsion was prepared by providing an aqueous dispersion 
stabilizer solution comprising 30 parts of the amphoionic group containing 
polyester resin obtained in Reference Example 1, 3 parts of 
dimethylethanolamine and 170 parts of deionized water, and gradually 
adding, while stirring in a Disper, a mixture of 40 parts of methyl 
methacrylate, 4 parts of n-butyl acrylate, 20 parts of monomer of 
Reference Example 4, 48 parts of ethyleneglycol dimethacrylate, and 8 
parts of tributyl tin methacrylate thereto. 
An aqueous initiator solution was also prepared in a separate vessel, by 
mixing 2 parts of azobiscyanovaleric acid, 1.2 parts of 
dimethylethanolamine and 40 parts of deionized water. To the aforesaid 
reaction flask, the initiator solution and the pre-emulsion were dropwise 
added, in 80 minutes and 60 minutes, respectively. However, the addition 
of said pre-emulsion was started after elapsing 10 minutes from the 
commencement of addition of said initiator solution. Then, the combined 
mixture was kept standing at 80.degree. C. for 30 minutes, dropwise added 
with a mixture of 32 parts of styrene, 24 parts of methyl methacrylate, 
12.8 parts of n-butyl acrylate and 11.2 parts of 2-hydroxyethyl 
methacrylate, and a solution of 1.0 part of azobis-cyanovaleric acid, 0.6 
part of dimethylethanolamine and 20 parts of deionized water in 40 
minutes, and the combined mixture was kept at the same temperature for 1 
hour. Average grain diameter of thus obtained composite crosslinked resin 
particles in emulsion, determined by light-scattering photometer, was 94 
nm. Thus obtained emulsion was then subjected to a freeze-drying to obtain 
composite, tin-containing crosslinked resin particles. The composite, 
crosslinked resin particles were easily dispersed in xylene and butyl 
acetate. The average grain diameters of the resin particles in xylene and 
in butyl acetate were 186 nm and 198 nm, respectively. 
The abovementioned organic solvent dispersions were applied on glass plates 
by using a doctor blade (20 mils), and dried to obtain clear coatings. 
Tin content of the respective composite resin particle was 11,000 ppm 
(measured by fluorescent X ray analyzer). 
Example 2 
Into a similar reaction vessel as used in Example 1, were placed 292 parts 
of deionized water and the content was heated to 80.degree. C. Separately, 
a pre-emulsion was prepared by providing an aqueous dispersion stabilizer 
solution comprising 24 parts of the amphoionic group containing epoxy 
resin obtained in Reference Example 2, 2.4 parts of dimethylethanolamine 
and 170 parts of deionized water, and gradually adding, while stirring in 
a disper, a mixture of 40 parts of methyl methacrylate, 2 parts of n-butyl 
acrylate, 70 parts of 1,6-hexanediol dimethacrylate, 20 parts of monomer 
of Reference Example 4, and 8 parts of zinc monomethacrylate thereto. 
An aqueous initiator solution was also prepared in a separate vessel, by 
mixing 2 parts of azobiscyanovaleric acid, 1.2 parts of 
dimethylethanolamine and 40 parts of deionized water. To the aforesaid 
reaction flask, the initiator solution and the pre-emulsion were dropwise 
added, in 70 minutes and 60 minutes, respectively. However, the addition 
of said pre-emulsion was started after elapsing 10 minutes from the 
commencement of addition of said initiator solution. Then, the combined 
mixture was kept standing at 80.degree. C. for 30 minutes, dropwise added 
with a mixture of 20 parts of styrene, 20 parts of n-butyl acrylate, and 
20 parts of methyl methacrylate, and a solution of 1.0 part of 
azobiscyanovaleric acid, 0.6 part of dimethylethanolamine and 20 parts of 
deionized water in 30 minutes, and the combined mixture was kept at the 
same temperature for 1 hour. Average grain diameter of thus obtained 
composite crosslinked resin particles in emulsion was 104 nm (measured by 
light-scattering photometer). 
Thus obtained emulsion was then subjected to spray-drying to obtain 
composite, zinc-containing crosslinked resin particles. These particles 
could be easily dispersed in 30% solid concentration in both xylene and 
butyl acetate. The average grain diameters in these dispersing mediums 
were 178 nm and 197 nm, respectively. 
The abovementioned organic solvent dispersions were applied by using a 
Doctor blade (20 mils) on glass plates and dried to obtain clear coatings. 
Zn content of the respective resin particle was, when analyzed by 
fluorescent X-ray analyzer, 15000 ppm in solid. 
Example 3 
Into a similar reaction vessel as used in Example 1, were placed 292 parts 
of deionized water and the content was heated to 80.degree. C. Separately, 
a pre-emulsion was prepared by providing an aqueous dispersion stabilizer 
solution comprising 24 parts of the amphoionic group containing acryl 
resin obtained in Reference Example 3, 2.4 parts of dimethylethanolamine 
and 170 parts of deionized water, and gradually adding, while stirring in 
a disper, a mixture of 20 parts of methyl methacrylate, 12 parts of 
n-butyl acrylate, 60 parts of 1,6-hexanediol dimethacrylate, 20 parts of 
monomer of Reference Example 4, and 8 parts of methacryloxy zirconium 
octate thereto. 
An aqueous initiator solution was also prepared in a separate vessel, by 
mixing 2 parts of azobiscyanovaleric acid, 1.2 parts of 
dimethylethanolamine and 40 parts of deionized water. To the aforesaid 
reaction flask, the initiator solution and the pre-emulsion were dropwise 
added, in 80 minutes and 70 minutes, respectively. However, the addition 
of said pre-emulsion was started after elapsing 10 minutes from the 
commencement of addition of said initiator solution. Then, the combined 
mixture was kept standing at 80.degree. C. for 30 minutes, dropwise added 
with a mixture of 24 parts of styrene, 32 parts of n-butyl acrylate, and 
24 parts of methyl methacrylate, and a solution of 1.0 part of 
azobiscyanovaleric acid, 0.6 part of dimethylethanolamine and 20 parts of 
deionized water in 30 minutes, and the combined mixture was kept at the 
same temperature for 1 hour. Average grain diameter of thus obtained 
composite crosslinked resin particles in emulsion was 106 nm (measured by 
light-scattering photometer). 
Thus obtained emulsion was then subjected to freeze-drying to obtain 
composite, zirconium-containing crosslinked resin particles. These 
particles could be easily dispersed in 30% solid concentration in both 
xylene and butyl acetate. The average grain diameters in these dispersing 
mediums were 201 nm and 224 nm, respectively. 
The abovementioned organic solvent dispersions were applied by using a 
Doctor blade (20 mils) on glass plates and dried to obtain clear coatings. 
Zr content of the respective resin particle was, when analyzed by 
fluorescent X-ray analyzer, 10,000 ppm in solid. 
Example 4 
Into a similar reaction vessel as used in Example 1, were placed 306 parts 
of deionized water and the content was heated to 80.degree. C. Separately, 
a pre-emulsion was prepared by providing an aqueous dispersion stabilizer 
solution comprising 30 parts of the amphoionic group containing polyester 
resin obtained in Reference Example 1, 3 parts of dimethylethanolamine and 
190 parts of deionized water, and gradually adding, while stirring in a 
disper, a mixture of 80 parts of methyl methacrylate, 18 parts of n-butyl 
acrylate, 80 parts of ethylene glycol dimethacrylate, 2 parts of 
methacrylic acid and 20 parts of monomer of Reference Example 4 thereto. 
An aqueous initiator solution was also prepared in a separate vessel, by 
mixing 2 parts of azobiscyanovaleric acid, 1.2 parts of 
dimethylethanolamine and 40 parts of deionized water. To the aforesaid 
reaction flask, the initiator solution and the pre-emulsion were dropwise 
added, in 80 minutes and 70 minutes, respectively. However, the addition 
of said pre-emulsion was started after elapsing 10 minutes from the 
commencement of addition of said initiator solution. Then, the combined 
mixture was kept standing at 80.degree. C. for 1 hour. 
In a round bottom flask, were placed 383 parts of thus obtained crosslinked 
resin particle emulsion, 3.5 parts of tributyl tin oxide and 200 parts of 
butyl acetate and the combined mixture was stirred at 70.degree. C. in an 
evaporator until no more water had come out, to obtain a dispersion in 
butyl acetate having a solid content of 40%. 
Next, in a similar reaction vessel as used in Example 1, were placed 296 
parts of said dispersion, 117 parts of butyl acetate, 10 parts of styrene, 
10 parts of methyl methacrylate and 10 parts of n-butyl acrylate and the 
combined mixture was heated to 110.degree. C. and then dropwise added with 
an initiator solution comprising 1 part of t-butyl peroxy 2-ethyl 
hexanoate and 50 parts of butyl acetate in 30 minutes. After completion 
of said addition, the combined mixture was aged for 3 hours, to obtain 30% 
dispersion of tin-containing composite crosslinked resin particles in 
butyl acetate. Thus obtained dispersion was applied by using a Doctor 
blade (20 mils) on a glass plate and dried to obtain a clear coating. The 
tin content of the respective particle was 9200 ppm in solid. 
Comparative Example 1 
Into a similar reaction vessel as used in Example 1, were placed 292 parts 
of deionized water and the content was heated to 80.degree. C. Separately, 
a pre-emulsion was prepared by providing an aqueous dispersion stabilizer 
solution comprising 24 parts of the amphoionic group containing epoxy 
resin obtained in Reference Example 2, 2.4 parts of dimethylethanolamine 
and 170 parts of deionized water, and gradually adding, while stirring in 
a disper, a mixture of 40 parts of methyl methacrylate, 2 parts of n-butyl 
acrylate, 70 parts of 1,6-hexanediol dimethacrylate, and 8 parts of zinc 
monomethacrylate thereto. 
An aqueous initiator solution was also prepared in a separate vessel, by 
mixing 2 parts of azobiscyanovaleric acid, 1.2 parts of 
dimethylethanolamine and 40 parts of deionized water. To the aforesaid 
reaction flask, the initiator solution and the pre-emulsion were dropwise 
added, in 70 minutes and 60 minutes, respectively. However, the addition 
of said pre-emulsion was started after elapsing 10 minutes from the 
commencement of addition of said initiator solution. Then, the combined 
mixture was kept standing at the same temperature for 1 hour. 
The average grain diameter of thus obtained crosslinked resin particles in 
emulsion was 94 nm (determined by light-scattering photometer). The 
emulsion was then subjected to spray-drying to obtain Zn containing 
crosslinked resin particles. Thus obtained resin particles were 
re-dispersed in 30% solid content, in xylene and in butyl acetate and 
however, uniform dispersions could not be obtained. When applied by 20 mil 
Doctor blade on a glass plate and dried, the applied dispersions failed to 
form coatings in both cases. 
Comparative Example 2 
The same procedures as stated in Example 1 were repeated excepting omitting 
the monomer of Reference Example 4. The average grain diameter of the 
resin particles in emulsion was 85 nm. Thus obtained emulsion was then 
subjected to freeze-drying, and the resin particles thus obtained were 
re-dispersed in 30% solid content in xylene and butyl acetate. In either 
case, good dispersion could not be obtained. Then the dispersion was 
applied onto a glass plate by the help of 20 mils doctor blade and dried, 
considerable agglomerates were found in the formed coating. The coating 
was translucent and there was a clear phase separation in it.