Water-based neutralized tertiary amino and/or acidic vinyl polymer and epoxy and hydrolyzable silyl-containing compound

A curable resin composition of use in water-based paints comprises a water-based product obtained by dispersing or dissolving in water a vinyl polymer (II) containing tertiary amino groups, acidic groups, or both tertiary amino and acidic groups which has been either partially or completely neutralized by an acidic or basic compound, an epoxy and hydrolyzable silyl groups-containing compound (B), and a composition further containing a hydrolyzable silyl and/or silanol groups-containing compound (F).

BACKGROUND OF THE INVENTION 
1. Technical Field 
The present invention relates to a useful new curable resin composition for 
use in water based paints. In particular, it relates to a curable resin 
composition, of particular use in paints, which has excellent weather 
resistant properties, and furthermore provides excellent curability, and 
gives excellent resistance against solvents, chemicals and water. The 
primary constituents of this curable resin composition include; a water 
based product obtained by dispersing or dissolving in water, a tertiary 
amino vinyl polymer, or vinyl polymer containing both tertiary amino and 
acidic functionalities which has been neutralised by an acidic compound, 
or alternatively, an acidic vinyl polymer, or vinyl polymer containing 
both tertiary amino and acidic functionalities which has been neutralised 
by a basic compound, and a compound containing both epoxy and hydrolysable 
silyl functionalities. 
2. Description of the Prior Art 
Due to recent worldwide demand for increased environmental conservation 
measures and improvements in workplace conditions, it is becoming 
necessary to move away from current organic solvent based paints, to 
paints which release less organic solvent into the atmosphere. In 
addition, from an energy conservation point of view, paint resins which 
will cross link at room temperature would be most attractive. 
In order to fulfil these requirements, aqueous emulsions of a copolymer 
formed from an unsaturated monomer of the ethylene family and a primary or 
secondary amino alkyl (meta) acrylate, with an epoxy silane coupling agent 
have been proposed (Japanese Patent Application, First Publication, No. 
Sho 61-28543), but the cured coating film from such compositions tends to 
be inferior in terms of its weather resistant properties. 
Furthermore, water based adhesive compositions formed by combining an epoxy 
silane coupling reagent, with a water based polymer formed by emulsion 
polymerisation of a vinyl monomer containing either carboxyl or tertiary 
amino functionalities (U.S. Pat. No. 4,077,932), or alternatively water 
based coating compositions for use with paper or textiles (Japanese Patent 
Application, First Publication, No. Hei 1-96270) have also been proposed, 
but the surface obtained from such compositions, in all cases, is 
inferior, either in terms of water and solvent resistance, or in terms of 
surface appearance. 
Moreover, alkali soluble adhesive compositions formed by combining a 
surface active agent and an epoxy silane coupling agent, with an aqueous 
solution of a carboxyl vinyl polymer, which is produced either by 
polymerisation of a single carboxyl vinyl monomer, or by copolymerisation 
of two or more different carboxyl vinyl monomers, have also been proposed 
(Japanese Patent Application, Unpublished, No. Hei 6-41504), but the 
surface formed from such compositions is inferior, particularly in terms 
of its resistance to water and alkalinity. The limitation then, of the 
aforementioned water based resins of vinyl polymers containing either 
emulsifiers or surface active reagents is that the resultant surfaces 
inevitably lack resistance to water and other solvents. 
SUMMARY OF THE INVENTION 
In view of the above probems, it is an object of the present invention to 
provide a novel, and highly practical curable resin composition for use in 
water based paints, which contains no, or very little, organic solvent 
when compared with current organic solvent based paints, and which yields 
a cured film which has excellent weather resistant properties, as well as 
resistance to solvents, chemicals and water. 
It is a further object of the invention to provide a novel, and highly 
practical curable resin composition for use in water based paints which 
will cross link at room temperature. 
Accordingly the present invention gives a curable resin composition for use 
in water based paints comprising; a water based product (A) obtained by 
dispersing or dissolving in water, a tertiary amino vinyl polymer (I) 
which has been either partially or completely neutralised by an acidic 
compound, and a compound (B) containing both epoxy and hydrolysable silyl 
groups, 
Moreover the present invention gives a curable resin composition for use in 
water based paints comprising; a water based product (C) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic functionalities to which has been added 
sufficient acidic compound so that the molar ratio of acidic 
functionalities in the added acidic compound to the tertiary amino 
functionalities in the vinyl polymer (II) is at least 0.1, and a compound 
(B) containing both epoxy and hydrolysable silyl functionalities. Herein 
the term molar ratio refers to an equivalence ratio, being the ratio of 
the equivalent numbers of the respective functionalities of compound (B) 
containing both epoxy and hydrolysable silyl groups. 
Furthermore the present invention gives a curable resin composition for use 
in water based paints comprising; a water based product (D) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic functionalities to which has been added 
sufficient basic compound so that the molar ratio of basic functionalities 
in the added basic compound to acidic functionalities in the vinyl polymer 
(II) is at least 0.1:1, and a compound (B) containing both epoxy and 
hydrolysable silyl groups. 
In addition the present inveintion gives a curable resin composition for 
use in water based paints comprising; a water based product (E) obtained 
by dispersing or dissolving in water, an acidic vinyl polymer (III) which 
has been partially, or completely, neutralised by a basic compound, and a 
compound (B) containing both epoxy and hydrolysable silyl groups. 
Again the present invention gives a curable resin composition for use in 
water based paints comprising; a water based product (A) obtained by 
dispersing or dissolving in water, a tertiary amino vinyl polymer (I) 
which has been either partially or completely neutralised by an acidic 
compound, a compound (B) containing both epoxy and hydrolysable silyl 
functionalities, and a compound (F) containing a hydrolysable silyl group 
and/or a silanol group, but excluding the compound (B). 
Again the present invention gives a curable resin composition for use in 
water based paints comprising; a water based product (C) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic groups to which has been added sufficient acidic 
compound so that the molar ratio of acidic groups in the added acidic 
compound to the tertiary amino groups in the vinyl polymer (II) is at 
least 0.1:1, a compound (B) containing both epoxy and hydrolysable silyl 
groups, and a compound (F) containing a hydrolysable silyl functionality 
and/or a silanol functionality, but excluding the compound (B). 
Furthermore the present invention gives a curable resin composition for use 
in water based paints comprising; a water based product (D) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic groups to which has been added sufficient basic 
compound so that the molar ratio of basic groups in the added basic 
compound to acidic groups in the vinyl polymer (II) is at least 0.1:1, a 
compound (B) containing both epoxy and hydrolysable silyl groups, and a 
compound (F) containing a hydrolysable silyl functionality and/or a 
silanol functionality, but excluding the compound (B). 
In addition the present invention gives a curable resin composition for use 
in water based paints comprising; a water based product (E) obtained by 
dispersing or dissolving in water, an acidic vinyl polymer (III) which has 
been partially or completely neutralised by a basic compound, a compound 
(B) containing both epoxy and hydrolysable silyl groups, and a compound 
(F) containing a hydrolysable silyl functionality and/or a silanol 
functionality, but excluding the compound (B). 
Again the present invention gives a curable resin composition for use in 
water based paints comprising; a water based product (A) obtained by 
dispersing or dissolving in water, a tertiary amino vinyl polymer (I) 
which has been either partially or completely neutralised by an acidic 
compound, a compound (B) containing both epoxy and hydrolysable silyl 
groups, and a curing catalyst (G). 
Moreover the present invention gives a curable resin composition for use in 
water based paints comprising; a water based product (C) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic groups to which has been added sufficient acidic 
compound so that the molar ratio of acidic groups in the added acidic 
compound to the tertiary amino groups in the vinyl polymer (II) is at 
least 0.1:1, a compound (B) containing both epoxy and hydrolysable silyl 
groups, and a curing catalyst (G). 
Furthermore the present invention gives a curable resin composition for use 
in water based paints comprising; a water based product (D) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic groups to which has been added sufficient basic 
compound so that the molar ratio of basic groups in the added basic 
compound to acidic groups in the vinyl polymer (II) is at least 0.1:1, a 
compound (B) containing both epoxy and hydrolysable silyl groups, and a 
curing catalyst (G). 
In addition the present inveintion gives a curable resin composition for 
use in water based paints comprising; a water based product (E) obtained 
by dispersing or dissolving in water, an acidic vinyl polymer (III) which 
has been partially or completely neutralised by a basic compound, a 
compound (B) containing both epoxy and hydrolysable silyl groups, and a 
curing catalyst (G). 
Again the present invention gives a curable resin composition for use in 
water based paints comprising; a water based product (A) obtained by 
dispersing or dissolving in water, a tertiary amino vinyl polymer (I) 
which has been either partially or completely neutralised by an acidic 
compound, a compound (B) containing both epoxy and hydrolysable silyl 
groups, a compound (F) containing a hydrolysable silyl functionality 
and/or a silanol functionality, but excluding the compound (B), and a 
curing catalyst (G). 
Again the present invention gives a curable resin composition for use in 
water based paints comprising; a water based product (C) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic groups to which has been added sufficient acidic 
compound so that the molar ratio of acidic groups in the added acidic 
compound to the tertiary amino groups in the vinyl polymer (II) is at 
least 0.1:1, a compound (B) containing both epoxy and hydrolysable silyl 
functionalities, a compound (F) containing a hydrolysable silyl 
functionality and/or a silanol functionality, but excluding the compound 
(B), and a curing catalyst (G). 
Furthermore the present invention gives a curable resin composition for use 
in water based paints comprising; a water based product (D) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic groups to which has been added sufficient basic 
compound so that the molar ratio of basic groups in the added basic 
compound to acidic groups in the vinyl polymer (II) is at least 0.1:1, a 
compound (B) containing both epoxy and hydrolysable silyl groups, a 
compound (F) containing a hydrolysable silyl functionality and/or a 
silanol functionality, but excluding the compound (B), and a curing 
catalyst (G). 
In addition the present invention gives a curable resin composition for use 
in water based paints comprising; a water based product (E) obtained by 
dispersing or dissolving in water, an acidic vinyl polymer (III) which has 
been partially or completely neutralised by a basic compound, a compound 
(B) containing both epoxy and hydrolysable silyl groups, a compound (F) 
containing a hydrolysable silyl functionality and/or a silanol 
functionality, but excluding the compound (B), and a curing catalyst (G). 
DETAILED DESCRIPTION OF THE INVENTION 
The composition formed by combining compounds which contain both epoxy and 
hydrolysable silyl groups, with specific aqueous solutions or dispersions 
of either a tertiary amino vinyl polymer, or a vinyl polymer containing 
both tertiary amino and acidic groups which has been neutralised by an 
acidic compound, or alternatively, an acidic vinyl polymer, or a vinyl 
polymer containing both tertiary amino and acidic groups which has been 
neutralised by a basic compound, contains little organic solvent, displays 
excellent curability, and also produces a coating film which is highly 
weather resistant and displays excellent resistance to solvents, 
chemicals, water and `yellowing` due to heat. 
It was predicted that water based products of acid or base neutralised 
resins, like those described in this invention, would, upon mixing with 
compounds containing epoxy and hydrolysable silyl groups react quickly, 
either by hydrolysis of the hydrolysable silyl functionality followed by a 
condensation reaction, resulting in consumption of the hydrolysable silyl 
functionality, or alternatively, by a ring opening reaction of the epoxy 
functionality, and that as a result, the curability of such mixtures would 
be inferior, and many of the properties of the resulting coating film 
would be affected. In actuality however, as detailed above, both the 
curability and coating film were of an excellent standard. 
That is to say the present invention is a curable resin composition for use 
in water based paints made from, a water based product (A) obtained by 
dispersing or dissolving in water, a tertiary amino vinyl polymer (I) 
which has been either partially or completely neutralised by an acidic 
compound, and a compound (B) containing both epoxy and hydrolysable silyl 
groups, 
Moreover the present invention is a curable resin composition for use in 
water based paints made from, a water based product (C), obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic groups to which has been added sufficient acidic 
compound so that the molar ratio (also referred to hereunder as the molar 
ratio of the acidic groups in the added acidic compound/tertiary amino 
groups in the vinyl polymer) of acidic groups in the added acidic compound 
to the tertiary amino groups in the vinyl polymer (II) is at least 0.1:1, 
and a compound (B), containing both epoxy and hydrolysable silyl groups. 
Furthermore the present invention is a curable resin composition for use in 
water based paints made from; a water based product (D) obtained by 
dispersing or dissolving in water, a vinyl polymer (II) containing both 
tertiary amino and acidic groups to which has been added sufficient basic 
compound so that the molar ratio of basic groups in the added basic 
compound to acidic groups in the vinyl polymer (II) is at least 0.1:1, and 
a compound (B), containing both epoxy and hydrolysable silyl groups. 
Additionally the present invention is a curable resin composition for use 
in water based paints made from a water based product (E) obtained by 
dispersing or dissolving in water, an acidic vinyl polymer (III) which has 
been partially, or completely, neutralised by a basic compound, and a 
compound (B) containing both epoxy and hydrolysable silyl groups. 
Furthermore, this novel and highly practical curable resin composition for 
use in water based paints gives a coating film which has excellent weather 
resistant, solvent resistant, chemical resistant and water resistant 
properties, and compared to current organic solvent based paints contains 
less or no organic solvent. 
In the production of the curable resin composition for use in water based 
paints described in this invention, a vinyl polymer is used as the 
required base constituent of the resin, that is, the required film forming 
constituent. Representative examples of this vinyl polymer include acrylic 
polymers, aromatic vinyl polymers, vinyl ester polymers and fluoro olefin 
polymers. 
Furthermore, of these various vinyl polymers, acrylic polymers and fluoro 
olefin polymers are particularly suitable. 
Of these various vinyl polymers we will firstly explain the aforementioned 
water based product (A), obtained by dispersing or dissolving in water, a 
tertiary amino vinyl polymer (I) which has been either partially or 
completely neutralised by an acidic compound. 
The aforementioned tertiary amino vinyl polymer (I) can be easily produced 
by standard methods. For example, (1) a method involving copolymerising a 
tertiary amino vinyl monomer with other co-polymerisable vinyl monomer, or 
(2) a method as is described in Japanese Patent, First Publication No. Sho 
59-56243, involving dehydrative imidisation processing following the 
addition reaction of a compound containing both tetiary amino and primary 
amino groups to a vinyl polymer containing an acid anhydride 
functionality. 
There are various suitable production methods, but of these, method (1) 
above is the most simple and convenient to carry out, and is thus most 
suitable. 
Particularly suitable examples of the tertiary amino vinyl monomer 
{hereafter abbreviated as (a-1)} used to produce the tertiary amino vinyl 
polymer (I) described in production method (1) above include the various 
(meta) acrylic acid ester monomers such as 2-dimethylamino ethyl (meta) 
acrylate, 2-diethylamino ethyl (meta) acrylate, 3-dimethylamino propyl 
(meta) acrylate, 3-diethylamino propyl (meta) acrylate, N-(2-(meta) 
acryloyl oxyethyl) piperidine, N-(2-(meta) acryloyl oxyethyl) pyrrolidine 
and N-(2-(meta) acryloyl oxyethyl) morpholine; the various aromatic 
monomers such as 4-(N,N-dimethylamino) styrene, 4-(N,N-diethylamino) 
styrene and 4vinyl pyridine; the various acrylamide monomers such as 
N-(2-dimethylamino ethyl) (meta) acrylamide, and N-(3-dimethylamino 
propyl) (meta) acrylamide; and the various vinyl ether monomers such as 
2-dimethylamino ethyl vinyl ether, 2-diethylamino ethyl vinyl ether, 
3-dimethylamino propyl vinyl ether, 3-diethylamino propyl vinyl ether, 
4dimethylamino butyl vinyl ether, and 6-dimethylamino hexyl vinyl ether. 
Particularly representative examples of the other vinyl monomer {hereafter 
abbreviated as (a-2)} to be copolymerised with the tertiary amino vinyl 
monomer (a-1) mentioned above include, the various meta acrylic acid 
esters such as methyl (meta) acrylate, ethyl (meta) acrylate, n-propyl 
(meta) acrylate, iso-propyl (meta) acrylate, n-butyl (meta) acrylate, 
iso-butyl (meta) acrylate, tert-butyl (meta) acrylate, 2-ethylhexyl (meta) 
acrylate, lauryl (meta) acrylate, cyclohexyl (meta) acrylate, benzyl 
(meta) acrylate, 2-hydroxyethyl (meta) acrylate, 2-hydroxypropyl (meta) 
acrylate, 2-hydroxybutyl (meta) acrylate, and 4-hydroxybutyl (meta) 
acrylate; the various unsaturated di-acidic alkyl esters such as dimethyl 
maleate, dimethyl fumarate, dibutyl fumarate and dimethyl itaconate; the 
various vinyl monomers containing a carboxylic acid amide functionality 
such as N,N-dimethyl (meta) acrylamide, N-alkoxymethyl (meta) acrylamides, 
diacetone (meta) acrylamide, and N-methylol (meta) acrylamide; the various 
crotonic acid esters such as methyl crotonate, ethyl crotonate, and 
n-butyl crotonate; the various vinyl esters such as vinyl acetate, vinyl 
benzoate, and Veova (a branched chain mono carboxyl vinyl ester produced 
by Shell Corporation, Holland); the various vinyl monomers containing 
nitrile functionality such as acrylonitrile; the various (per)fluoroalkyl 
vinyl monomers such as fluoroalkyl (meta) acrylates, perfluoroalkyl (meta) 
acrylates, perfluoro cyclohexyl (meta) acrylate, di-perfluoro cyclohexyl 
fumarate, and N-isopropyl perfluorooctane sulfonamide ethyl (meta) 
acrylate; the various vinyl monomers containing polysiloxane functionality 
such as CH.sub.2 .dbd.CHCOO(CH.sub.2).sub.3 [Si(CH.sub.3).sub.2 O].sub.n 
Si(CH.sub.3).sub.3, CH.sub.2 .dbd.C(CH.sub.3) COOC.sub.6 H.sub.4 
[Si(CH.sub.3).sub.2 O].sub.n Si(CH.sub.3).sub.3, 
CH2.dbd.C(CH.sub.3)COO(CH.sub.2).sub.3 [Si(CH.sub.3).sub.2 O].sub.n 
Si(CH.sub.3).sub.3, CH.sub.2 .dbd.C(CH.sub.3)COO(CH.sub.2).sub.3 
[Si(CH.sub.3)(C.sub.6 H.sub.5)O].sub.n Si(CH.sub.3).sub.3 and CH.sub.2 
.dbd.C (CH.sub.3)COO(CH.sub.2).sub.3 [Si(C.sub.6 H.sub.5).sub.2 O].sub.n 
Si(CH.sub.3).sub.3 (Note that n should be zero, or any integer between 1 
and 130); the various halogenised olefins such as vinyl chloride, 
vinylidine chloride, vinyl fluoride, vinylidine fluoride, tetrafluoro 
ethylene, hexafluoro propylene, and chloro trifluoro ethylene; the various 
aromatic vinyl monomers such as styrene, .alpha.-methyl styrene, 
p-tert-butyl styrene, and vinyl toluene; and the various vinyl ethers such 
as ethyl vinyl ether, n-propyl vinyl ether, iso-butyl vinyl ether, 
2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, cyclopentyl vinyl ether, 
2-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxybutyl 
vinyl ether, 6-hydroxyhexyl vinyl ether. 
Furthermore, monomers containing a polyether segment such as polyethylene 
glycol mono (meta) acrylate, mono alkoxy polyethylene glycol (meta) 
acrylate, polypropylene glycol mono (meta) acrylate, polytetramethylene 
glycol mono (meta) acrylate, mono alkoxy polypropylene glycol (meta) 
acrylates, and mono alkoxy polypropylene glycol (meta) acrylates may also 
be used with no loss in the weather resistant or water resistant 
properties of the final product. 
In order to produce the vinyl polymer (I) any of the aforementioned 
monomers can be polymerised by any of the standard methods, but radical 
polymerisation in solution is the simplest and most convenient method, and 
is thus particularly recommended. 
Particular suitable solvents to use for this reaction include, the various 
hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and 
octane; the various alcohol solvents such as methanol, ethanol, 
iso-propanol, n-butanol, iso-butanol, sec-butanol, ethylene glycol 
monomethyl ether, ethylene glycol mono ethyl ether, ethylene glycol mono 
iso-propyl ether, and ethylene glycol monobutyl ether, the various esters 
such as methyl acetate, ethyl acetate, n-butyl acetate, and amyl acetate; 
and the various ketone solvents such as acetone, methyl ethyl ketone, 
methyl iso-butyl ketone, and cyclohexanone. All of these solvents may be 
used separately or in mixtures of 2 or more solvents. Water may also be 
added. 
Polymerisation can be carried out by normal methods, using the selected 
solvent and any well known radical polymerisation initiators such as azo 
or peroxide compounds. Furthermore, if required, chain transfer reagents 
such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercapto 
ethanol, thioglycolic acid octyl, 3-mercapto propionic acid, and 
.alpha.-methyl styrene dimer may be used as molecular weight regulating 
reagents. 
A tertiary amino vinyl polymer (I) produced in this way should contain 
between about 0.03 and 2.5 moles of tertiary amino groups per 1000 grams 
of solid material, with between 0.05 and 1.5 moles being preferable, and 
between 0.05 and 0.5 moles being most suitable. Furthermore, the average 
molecular weight for the polymer (I) should generally be in the range 
500-100,000, and preferably in the range 1000-30,000. 
Moreover, in cases where hydroxyl functionality is introduced into the 
tertiary amino vinyl polymer (I), by for example using a monomer 
containing a hydroxyl group as a comonomer, then the curability of this 
invention's final composition, which will contain the water based product 
(A) formed from this polymer (I) as the constituent necessary for the 
formation of the coating film, can be improved one step, producing a 
coating film which has even better external appearance, even better 
resistance to solvents, and an even greater level of hardness. 
In those instances where hydroxyl functionality is introduced into the 
tertiary amino vinyl polymer (I), then 1000 grams of solid material should 
contain between 0.04 and 2 moles, and preferably between 0.08 and 1.2 
moles of hydroxyl groups. 
By adding an acidic compound to the tertiary amino vinyl polymer (I) formed 
by the method mentioned above, the tertiary amino groups in the polymer 
are partially, or completely neutralised, and a polymer which is soluble, 
or dispersible in water is generated. 
Particularly representative acidic compounds which can be used in this 
instance include carboxylic acids with between 1 and 10 carbon atoms such 
as formic acid, acetic acid, propionic acid, butyric acid, 2-methyl 
butyric acid, iso-valeric acid, trimethyl acetic acid, glycolic acid and 
lactic acid; mono- or dialkyl esters of phosphoric acid such as phosphoric 
acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid 
mono-iso-propyl ester, phosphoric acid di-iso-propyl ester, phosphoric 
acid mono-2-ethylhexyl ester, and phosphoric acid di-2-ethylhexyl ester, 
organic sulfonic acids such as methanesulfonic acid, propanesulfonic acid, 
benzenesulfonic acid, dodecyl benzenesulfonic acid; and various inorganic 
acids such as hydrochloric acid, sulphuric acid, nitric acid and 
phosphoric acid. Among the above acidic compounds however, the carboxylic 
acids are the most suitable. 
The quantity of acidic compound to be added to the polymer, should be at 
least enough to generate dispersibility in the vinyl polymer (I) outlined 
above, and the molar ratio of the number of acidic groups in the added 
acidic compound to the number of amino groups in the polymer, in other 
words the equivalence ratio: acidic groups in acid/tertiary amino groups 
in polymer (I), should be 0.1:1 or greater, but in order not to lose the 
properties of the coating film generated, a ratio of between 0.1:1 and 3:1 
is preferred, and a ratio of between 0.1:1 and 2:1 is most suitable. 
The previously mentioned water based product (A), can be generated from the 
thus produced neutralised vinyl polymer (I), using various standard 
methods. For example, water can be simply added to the neutralised 
material, or alternatively, the material added to water to produce the 
water based product. 
Furthermore, the water based product (A) can be produced, as required, with 
either partial, or complete removal of the organic solvent used in the 
production of the vinyl polymer (I), by removing the solvent under 
temperature, or under reduced pressure. 
Next, we will explain the previously mentioned water based product (C), 
obtained by dispersing or dissolving in water, a vinyl polymer (II) 
containing both tertiary amino and acidic groups to which has been added 
sufficient acidic compound so that the molar ratio of acidic groups in the 
added acidic compound to tertiary amino groups in the vinyl polymer is at 
least 0.1. 
This vinyl polymer (II) containing both tertiary amino and acidic groups 
can be produced by various standard means. For example, (3) a mixture of 
monomers containing a tertiary amino vinyl monomer and an acidic vinyl 
monomer can be polymerised, (4) as presented in Japanese Patent, First 
Publication, No. Sho 59-56243, a vinyl polymer containing a carboxylic 
acid anhydride functionality can be reacted with a compound which contains 
a tertiary amino functionality and a functionality with an active 
hydrogen, (5) a vinyl polymer containing hydroxyl and tertiary amino 
groups can be reacted with a dicarboxylic acid anhydride, or (6) a mixture 
of monomers containing a tertiary amino vinyl monomer, and a vinyl monomer 
containing a blocked acid functionality such as a trialkyl silyl ester 
functionality, a hemiacetyl ester functionality, or a tert-butyl ester 
functionality, which can easily be converted to a free acid functionality 
by the action of acid, heat or water, can be polymerised, producing a 
vinyl polymer with tertiary amino and blocked acid groups, which can then 
have the blocked acid groups converted to free acid groups. Among the 
methods outlined, method (3) is particularly recommended, because it is 
the most simple and convenient. 
The tetiary amino vinyl monomer required to produce the vinyl polymer (II) 
containing both tertiary amino and acidic groups by method (3) above, can 
be any of the various tertiary amino vinyl monomers (a-1) mentioned 
previously as possible precursors to the tertiary amino vinyl polymer (I). 
Furthermore, particularly suitable acidic vinyl monomers {hereafter 
abbreviated as (a-3)} for the production of this vinyl polymer (II) 
include (meta) acrylic acid, crotonic acid, maleic acid, itaconic acid, 
half esters of maleic acid and alkyl alcohols containing between 1 and 10 
carbon atoms, half esters of itaconic acid and alkyl alcohols containing 
between 1 and 10 carbon atoms, fumaric acid, or half esters of fumaric 
acid and alkyl alcohols containing between 1 and 10 carbon atoms, 
citraconic acid, 4-vinyl benzoic acid, cinnamic acid, succinic acid mono 
2-(meta) acrylol oxyethyl ester, phthalic acid 2-(meta) acryloyl oxyethyl 
ester, the various mono vinyl esters of multi carboxylic acids such as 
malonic acid, adipic acid and sebacic acid; the various vinyl monomers 
containing phosphoric acid functionality such as mono{2-(meta) acryloyl 
oxyethyl} acid phosphate; and the various vinyl monomers containing 
sulfonic acid functionality such as p-vinyl benzenesulfonic acid, 2-(meta) 
acryloyl oxyethanesulfonic acid, 3-(meta) acryloyl oxypropanesulfonic 
acid, and 2-acrylylamido-2-methylpropanesulfonic acid 
Among these, the use of monomers containing carboxylic acid functionality 
is desirable, and (meta) acrylic acid is particularly suitable. 
Furthermore, other copolymerisable vinyl monomers which can be used in the 
production of the vinyl polymer (II) include the various vinyl monomers 
(a-2) previously mentioned in the discussion regarding production of vinyl 
polymer (I). 
The use of solvents and initiators in the production of the vinyl polymer 
(II) from the various aforementioned monomers, follows the same pattern as 
is described for production of vinyl polymer (I). 
A vinyl polymer (II) containing both tertiary amino and acidic groups 
produced in this way should contain between about 0.03 and 2.5 moles of 
tertiary amino groups per 1000 grams of solid material, with between 0.05 
and 1.5 moles being preferable, and between 0.05 and 0.5 moles being most 
suitable. 
Furthermore, it should contain between about 0.07 and 5.0 moles of acidic 
groups, with between 0.07 and 2.0 moles being preferable, and between 0.1 
and 0.7 moles being most suitable. Moreover, the average molecular weight 
for the polymer (II) should generally be in the range 500-100,000, and 
preferably in the range 1000-30,000. 
Furthermore, in cases where hydroxyl functionality is introduced into the 
vinyl polymer (II) containing both tertiary amino and acidic groups, by 
for example using a monomer containing a hydroxyl group as a comonomer, 
then the curability of this invention's final composition, which will 
contain the water based product (C) formed from this polymer (II) as the 
constituent necessary for the formation of the coating film, can be 
improved one step, producing a coating film which has even better external 
appearance, even better resistance to solvents, and an even greater level 
of hardness. 
In those instances where hydroxyl functionality is introduced into the 
vinyl polymer (II) containing both tertiary amino and acidic groups, then 
1000 grams of solid material should contain between 0.04 and 2 moles, and 
preferably between 0.08 and 1.2 moles of hydroxyl groups. 
By adding an acidic compound to the vinyl polymer (II) containing both 
tertiary amino and acidic groups formed by the method mentioned above, the 
tertiary amino groups in the polymer are partially, or completely 
neutralised, and a polymer which is soluble, or dispersible in water is 
generated. 
The acidic compound used in this step can be any of the acidic compounds 
mentioned previously as being suitable in the production of the water 
based product (A), but of these, carboxylic acids are the most suitable. 
The quantity of acidic compound to be added to the polymer, should be 
sufficient to ensure that the molar ratio of acidic groups in the added 
acidic compound to tertiary amino groups in the vinyl polymer (II) is at 
least 0.1:1. A ratio of between 0.1:1 and 3:1 is preferred, and a ratio of 
between 0.1 and 2 is most suitable. 
The previously mentioned water based product (C), can be generated from the 
thus produced neutralised vinyl polymer (II) produced by this method, by 
the same methods outlined above for producing the water based product (A) 
from the neutralised vinyl polymer (I). 
Next, we will explain the previously mentioned water based product (D), 
obtained by dispersing or dissolving in water, a vinyl polymer (II) 
containing both tertiary amino and acidic functionalities to which has 
been added sufficient basic compound so that the molar ratio of basic 
functionalities in the added basic compound to acidic functionalities in 
the vinyl polymer (II) is at least 0.1:1. 
Firstly, the vinyl polymer (II) containing both tertiary amino and acidic 
functionalities can be produced by the method already described in the 
discussion concerning the production of water based product (C). 
Furthermore, in cases where hydroxyl functionality is introduced into the 
vinyl polymer (II) containing both tertiary amino and acidic groups, by 
for example using a monomer containing a hydroxyl group as a comonomer, 
then the curability of this invention's final composition, which will 
contain the water based product (D) formed from this polymer (II), can be 
improved one step, producing a coating film which has even better external 
appearance, even better resistance to solvents, and an even greater level 
of hardness. In those instances where hydroxyl functionality is introduced 
into the vinyl polymer (II) containing both tertiary amino and acidic 
groups, then 1000 grams of solid material should contain between 0.04 and 
2 moles, and preferably between 0.08 and 1.2 moles of hydroxyl groups. 
By adding a basic compound to the vinyl polymer (II) containing both 
tertiary amino and acidic groups formed by the method mentioned above, the 
acidic groups in the polymer are partially, or completely neutralised, and 
a polymer which is soluble, or dispersible in water is generated. 
Particularly representative examples of basic compounds which can be used 
in this instance include the various organic amines such as methyl amine, 
dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl 
amine, n-butyl amine, tri-n-butyl amine, 2-amino-2-methyl propanol, 
2-amino ethanol, and 2-dimethylamino ethanol; the various inorganic basic 
compounds beginning with ammonia, and including sodium hydroxide and 
potassium hydroxide; and quaternary ammonium hydroxides such as 
tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethyl 
benzyl ammonium hydroxide. 
Among the basic compounds listed, ammonia or the various organic amines are 
particularly suitable. 
The quantity of basic compound to be added to the polymer, should be 
sufficient to ensure that the molar ratio of basic groups in the added 
basic compound to acidic groups in the vinyl polymer (II) is at least 
0.1:1. A ratio of between 0.1:1 and 3:1 is preferred, and a ratio of 
between 0.1:1 and 2:1 is most suitable. 
In order to prepare the water based product (D) from the thus formed 
mixture of vinyl polymer (II) and basic compound, the same methods 
outlined above for producing the water based product (A) from the 
neutralised vinyl polymer (I) can be used. 
Next, we will explain the previously mentioned water based product (E), 
obtained by dispersing or dissolving in water, an acidic vinyl polymer 
(III) which has been partially or completely neutralised by a basic 
compound. 
This acidic vinyl polymer (III) can be produced by various standard means. 
For example, (7) an acidic vinyl monomer can be copolymerised with other 
co-polymerisable vinyl monomer, (8) a vinyl monomer having hyroxy group 
can be reacted with a dicarboxylic acid anhydride, or (9) as was described 
previously, a vinyl monomer with a blocked acidic functionality can be 
copolymerised with other suitable vinyl polymer, and the blocked acidic 
functionality then converted to a free acid functionality. 
Of these methods, method (7) is recommended as it is the simplest and most 
convenient. 
The acidic vinyl monomer required to produce the acidic vinyl polymer (III) 
by method (7) above, can of course be any of the various acidic vinyl 
monomers (a-3) mentioned previously as suitable monomers for the 
production of the vinyl polymer (II) containing both tertiary amino and 
acidic groups. 
Of these, monomers containing carboxylic acid functionality are 
particularly suitable. 
Furthermore, other copolymerisable vinyl monomers which can be used in the 
production of the vinyl polymer (III) include, of course, the various 
vinyl monomers (a-2) previously mentioned in the discussion regarding 
production of vinyl polymer (I). 
Similar solvents, initiators and procedure used in the production of the 
vinyl polymer (III) are selected, respectively from the representatives 
mentioned earlier in this invention for production of vinyl polymer (I). 
A vinyl polymer (III) produced in this way should contain between about 
0.07 and 5.0 moles of acidic groups per 1000 grams of solid material, with 
between 0.3 and 2.0 moles being preferable. Furthermore, the average 
molecular weight for the vinyl polymer (III) should generally be in the 
range 500-100,000, and preferably in the range 1000-30,000. 
Moreover, in cases where hydroxyl functionality is introduced into the 
acidic vinyl polymer (III), by for example using a monomer containing a 
hydroxyl group as a comonomer, then the curability of this invention's 
final composition, which will contain the water based product (F) formed 
from this polymer (III) as the constituent necessary for the formation of 
the coating film, can be improved one step, producing a coating film which 
has even better external appearance, even better resistance to solvents, 
and an even greater level of hardness. 
In those instances where hydroxyl functionality is introduced into the 
acidic vinyl polymer (III), then 1000 grams of solid material should 
contain between 0.04 and 2 moles, and preferably between 0.08 and 1.2 
moles of hydroxyl groups. 
By adding a basic compound to the acidic vinyl polymer (III) prepared by 
the method mentioned above, the acidic groups in the polymer (III) are 
partially, or completely neutralised, and then a polymer which is soluble 
or dispersible in water is generated. 
The basic compound used in this step can, of course, be any of the 
compounds mentioned previously as being suitable in the production of the 
water based product (D), but among them, ammonia and organic amines are 
suitable. 
The quantity of basic compound to be added to the polymer, should be 
sufficient to ensure that the molar ratio of basic groups in the added 
basic compound to acidic groups in the vinyl polymer (III) is at least 
0.1:1. A ratio of between 0.1:1 and 3:1 is preferred, and a ratio of 
between 0.1:1 and 2:1 is most suitable. 
In order to prepare the water based product (E) from the thus formed 
mixture of vinyl polymer (III) and basic compound, the similar way 
outlined above for producing the water based product (A) from the 
neutralised vinyl polymer (I) may be used. 
Representative examples of the previously mentioned compound (B), which 
contains both epoxy and hydrolysable silyl groups in the one molecule, 
include vinyl polymers with both these types of reactive functionality, 
silane coupling reagent which contains epoxy functionality, and silicone 
resins with both types of reactive functionality. 
Hydrolysable silyl functionality here, refers to groups of atoms which 
contain a silicon atom which is bonded to, for example, a halogen atom, or 
an alkoxy, substituted alkoxy, phenoxy, isopropenyloxy, acyloxy or 
iminooxy functionality, and which are easily hydrolysable to form a 
silanol functionality. Particularly representative examples include the 
alkoxy silyl, phenoxy silyl, halo silyl, isopropenyloxy silyl, acyloxy 
silyl, and iminooxy silyl groups. 
Any of the standard methods can be used to produce the vinyl polymers 
containing these two reactive groups, but the recommended methods include; 
(i) a solution radical copolymerisation of a vinyl monomer containing a 
hydrolysable silyl functionality such as .gamma.-(meta) acryloyl oxy 
propyl trimethoxy silane, .gamma.-(meta) acryloyl oxy propyl methyl 
dimethoxy silane, .gamma.-(meta) acryloyl oxy propyl triisopropenyloxy 
silane, .gamma.-(meta) acryloyl oxy propyl triiminooxy silane, vinyl 
trimethoxy silane, vinyl triethoxy silane, vinyl (tris-.beta.-methoxy 
ethoxy) silane, vinyl triacetoxy silane, or vinyl trichloro silane, with a 
vinyl monomer containing an epoxy functionality such as glycidyl (meta) 
acrylate, (.beta.-methyl) glycidyl (meta) acrylate, 3,4-epoxy cyclohexyl 
(meta) acrylate, aryl glycidyl ether, 3,4-epoxy vinyl cyclohexane, 
di(.beta.-methyl) glycidyl maleate, or (.beta.-methyl) glycidyl fumarate, 
where, if necessary, solution radical copolymerisation with the various 
aforementioned vinyl monomers (a-2) may also be employed, or 
alternatively, (ii) a solution radical (co)polymerisation of a mixture of 
monomers which must include one of the various epoxy vinyl monomers 
mentioned above, in the presence of one of various chain transfer agents 
which include a hydrolysable silyl functionality, such as .gamma.-mercapto 
propyl trimethoxy silane, .gamma.-mercapto propyl triethoxy silane, 
.gamma.-mercapto propyl methyldimethoxy silane, .gamma.-mercapto propyl 
triisopropenyloxy silane, .gamma.-mercapto propyl triiminooxy silane. 
Alternatively a combination of the two methods, (i) and (ii) may be used. 
Particularly representative examples of the epoxy silane coupling reagent 
mentioned above include various epoxy silane compounds such as 
.gamma.-glycidoxy propyl trimethoxy silane, .gamma.-glycidoxy propyl 
triethoxy silane, .gamma.-glycidoxy propyl methyl dimethoxy silane, 
.gamma.-glycidoxy propyl methyl diethoxy silane, .beta.-(3,4-epoxy 
cyclohexyl) ethyl trimethoxy silane, .beta.-(3,4-epoxy cyclohexyl) ethyl 
methyl diethoxy silane, .gamma.-glycidoxy propyl triisopropenyloxy silane, 
.gamma.-glycidoxy propyl triiminooxy silane; the addition products of 
various isocyanato silane compounds, such as .gamma.-isocyanato propyl 
triisopropenyloxy silane or .gamma.-isocyanato propyl trimethoxy silane 
with glycidol; the addition products of various amino silane compounds, 
such as .gamma.-aminopropyl trimethoxy silane with diepoxy compounds; or 
compounds which contain two or more hydrolysable silyl groups and two or 
more epoxy groups in a molecule, formed by a partial hydrolysis 
condensation of the various epoxy silane compounds mentioned above. 
Particularly representative examples of the aforementioned silicone resins 
which contain both epoxy and hydrolysable silyl groups are the cyclic 
tetra siloxanes, an example of which is shown below. 
##STR1## 
(Note, the Gly in this diagram represents a 3-glycidoxy propyl 
functionality) 
In the production of the particular curable resin composition for use in 
water based paint, detailed in this invention, which contains the 
aforementioned water based product (A) and compound (B) containing both 
epoxy and hydrolysable silyl groups, as the base resin constituents, the 
two constituents (A) and (B) should be mixed together in a proportion that 
will yield to typical values for the molar ratio of the number of moles of 
tertiary amino groups in the water based product (A), to the number of 
moles of epoxy groups in compound (B) {hereafter also described as the 
molar ratio [tertiary amino groups in water based product (A)/epoxy groups 
in compound (B)]} of between about 0.1:1 and 5.0:1, with a ratio of 
between 0.3:1 and 3.0:1 being preferable, and a ratio of between 0.5:1 and 
2.0:1 being most suitable. 
Furthermore, in the production of the particular curable resin composition 
for use in water based paint, detailed in this invention, which contains 
either of the aforementioned water based products (C) or (D) and compound 
(B), containing both epoxy and hydrolysable silyl groups as the necessary 
base resin constituents, the two constituents (C) and (B), or 
alternatively (D) and (B) should be mixed together in a proportion that 
will yield typical values for the molar ratio [functionalities (namely, 
tertiary amino+acidic functionalities) in water based product (C) or 
(D)/epoxy functionalities in compound (B)] of between about 0.1:1 and 
5.0:1, with a ratio of between 0.3:1 and 3.0:1 being preferable, and a 
ratio of between 0.5:1 and 2.0:1 being most suitable. 
In the production of the particular composition, detailed in this 
invention, which contains the water based product (E) and compound (B) 
containing both epoxy and hydrolysable silyl functionalities as the 
necessary base resin constituents, the two constituents (E) and (B) should 
be mixed together in a proportion that will yield to typical values for 
the molar ratio [acidic functionalities in water based product (E)/epoxy 
functionalities in compound (B)] of between about 0.1:1 and 5.0:1, with a 
ratio of between 0.3:1 and 3.0:1 being preferable, and a ratio of between 
0.5:1 and 2.0:1 being most suitable. 
According to another aspect of this invention, addition of a compound (F), 
which contains a hydrolysable silyl functionality and/or a silanol 
functionality, but excludes the compound (B) which contain both epoxy and 
silyl functionalities, the weather resistance of the cured coating film 
obtained is improved, as is the hardness of the surface. 
Particularly representative examples of this compound (F), containing a 
hydrolysable silyl functionality and/or a silanol functionality are 
silicate compounds such as methyl silicate, ethyl silicate, isopropyl 
silicate, and n-butyl silicate; various trifunctional silane compounds 
such as methyl trimethoxy silane, phenyl trimethoxy silane, methyl 
triethoxy silane, phenyl triethoxy silane, and isobutyl trimethoxy silane; 
various difunctional silane compounds such as dimethyl dimethoxy silane, 
dimethyl diethoxy silane, diethyl diethoxy silane, diphenyl dimethoxy 
silane; low molecular weight silanol compounds obtained by virtually 
complete hydrolysis of the trifunctional and difunctional silane compounds 
mentioned above, or of the various halo silanes such as methyl trichloro 
silane, phenyl trichloro silane, ethyl trichloro silane, dimethyl dichloro 
silane, and diphenyl dichloro silane; linear or cyclic polysiloxanes 
containing silanol functionality, obtained by carrying out a dehydration 
condensation on the silanol compounds mentioned above; and linear or 
cyclic polysiloxanes containing alkoxysilyl functionality, obtained by 
carrying out a partial hydrolysis condensation on at least one of the 
compounds from the group of aforementioned difunctional and trifunctional 
silane compounds and silicate compounds. 
Concerning the amount of aforementioned compound (F), containing 
hydrolysable silyl and/or silanol functionality, which should be further 
added to each of the resin compositions comprising compound (B) containing 
both epoxy and hydrolysable silyl functionalities, and the various water 
based products (A), (C), (D) or (E), to provide the curable resin 
compositions for use in water based paint described in this invention, 
then for each 100 parts, by weight, of the solid component of the resins 
from water based products (A), (C), (D) or (E), between 0.5 and 200 parts, 
by weight, of the compound (F) should be added, with between 1 and 100 
parts being preferable. 
Furthermore, if necessary, a curing catalyst (G) may be added to the 
curable resin compositions for use in water based paint described in this 
invention. Addition of such a catalyst results in an improvement in the 
curability of the compositions. 
Representative examples of this catalyst (G) include various basic 
compounds such as lithium hydroxide, sodium hydroxide, potassium 
hydroxide, and sodium methylate; various metallic compounds such as 
tetraisopropyl titanate, tetra n-butyl titanate, tin octylate, lead 
octylate, cobalt octylate, zinc octylate and calcium octylate, zinc 
naphthenate and cobalt naphthenate, di n-butyl tin diacetate, di n-butyl 
tin dioctoate, di n-butyl tin dilaurate and di n-butyl tin maleate; and 
various acidic compounds such as p-toluenesulfonic acid, trichloroacetic 
acid, monoalkyl phosphoric acids, dialkyl phosphoric acids, monoalkyl 
phosphorous acids and dialkyl phosphorous acids. 
Furthermore, if required, various additives may be added to the curable 
resin compositions for use in water based paint, described in this 
invention. Such additives include various coalescing agents such as 
isopropyl alcohol, sec-butanol, n-butanol, 2-ethyl hexanol, 2-propoxy 
ethanol, 2-n-butoxy ethanol, 2-n-propoxy propanol, 3-n-propoxy propanol, 
2-n-butoxy propanol, 3-n-butoxy propanol, 2-n-butoxy ethyl acetate, 
diethylene glycol monobutyl ether, N-methyl pyrrolidone, 
2,2,4-trimethyl-1,3-pentanediol monobutarate, dibutyl phthalate ester and 
butyl benzyl phthalate ester, anti-foaming reagents, organic pigments, 
inorganic pigments, plasticizers, antioxidants, UV absorber, 
photostabilising reagents, levelling reagents, anti-streaking reagents, 
dispersing reagents and thickening reagents. 
When using the curable resin compositions for use in water based paints 
described in this invention, and outlined above, a so called two component 
system is used with the constituent compound (B) containing both epoxy and 
hydrolysable silyl functionalities, being mixed with the other 
constituents immediately before use. The mixture should then be used 
within one day (24 hours), with use inside of 12 hours being preferable. 
Particular care needs to be taken in this respect, as if left for more 
than one day, the room temperature curability of the composition decreases 
markedly. 
The curable compositions for use in water based paints described in this 
invention can be used, with conventional methods, to paint various 
surfaces, and then either dried at ambient temperature for between 1 and 
10 days, force dried at between 40 and 100.degree. C. for between 1 and 60 
minutes, or bake dried at between 100 and 180.degree. C. for between 1 and 
60 minutes. This process emits very little organic solvent into the 
atmosphere and provides a coating film that has excellent weather 
resistant and curability properties, and excellent resistance to solvents, 
chemicals and water. 
The curable resin compositions for use in water based paints described in 
this invention then, are novel and yet highly practical, contain no, or 
very little, organic solvent when compared with current organic solvent 
based paints, and yield a cured surface which has excellent weather 
resistant and curability properties as well as excellent resistance to 
solvents, chemicals and water. 
Consequently, these curable resin compositions for use in water based 
paints, which yield such excellent cured surfaces, are suitable for a wide 
range of uses, including the painting of new vehicles, the repair of 
vehicles, woods, building, the painting of roof tiles, building materials, 
glass and various goods manufactured from plastics, and further, in the 
painting of a variety of metallic materials such as aluminium, stainless 
steel, chrome plating, corrugated iron and tinned sheet iron.

EXAMPLES 
Next, we will attempt to explain the invention in more concrete terms, by 
giving reference, working and comparative examples. Note, however that 
this in no way implies that the invention is limited to the examples 
illustrated. Unless specified otherwise, reference in these examples to 
`parts` or `percentages` refers to relative weights. 
Reference Example 1 
example of the production of a tertiary amino vinyl polymer (I) 
660 parts of ethylene glycol monoisopropyl ether was placed in a reaction 
vessel fitted with a stirrer, a thermometer, a reflux condenser and a 
nitrogen gas inlet, and the temperature raised to 80.degree. C., under 
nitrogen gas atmosphere. 
Next, a mixture of 100 parts styrene, 250 parts methyl methacrylate, 480 
parts n-butyl methacrylate, 70 parts ethyl acrylate, 100 parts dimethyl 
aminoethyl methacrylate, 8 parts of azobis isobuturonitrile, and 5 parts 
tert-butyl peroxy octoate (TBPO) was dripped in slowly over a period of 4 
hours. 
On completion of this addition, the temperature was maintained for a 
further 10 hours. The product thus obtained was a solution of the targeted 
tertiary amino vinyl polymer (I) (average molecular weight 9,500) with a 
non volatile component of 60%. Hereafter this polymer is abbreviated as 
polymer (I-1). 
Reference Example 2 
example of the production of the water based product (A) 
1.0 part of an 88% water solution of formic acid was added, at room 
temperature, to 100 parts of the polymer (I-1) obtained in reference 
example 1, and the mixture stirred. In this instance a 50% neutralisation 
rate was obtained. 
Next, a further 49 parts of water were added, and stirring continued until 
a uniform mixture was obtained. The product thus obtained was the targeted 
water based product, and had a non volatile component of 40%. Hereafter 
this product is abbreviated as water based product (A-1). 
Reference Example 3 
example of the production of the water based product (A) 
2 parts of an 88% water solution of formic acid was added, at room 
temperature, to 100 parts of the polymer (I-1) obtained in reference 
example 1, and the mixture stirred In this instance a 100% neutralisation 
rate was obtained. 
Next, a further 98 parts of water were added, and stirring continued until 
a uniform mixture was obtained. The product thus obtained was the targeted 
water based product, and had a non volatile component of 30%. Hereafter 
this product is abbreviated as water based product (A-2). 
Reference Example 4 
example of the production of a tertiary amino vinyl polymer (I) 
Following the standard method, the polymerisation reaction was carried out 
with a mixture of 100 parts styrene, 700 parts n-butyl methacrylate, 100 
parts ethyl acrylate, 50 parts 2-hydroxy ethyl acrylate and 50 parts 
dimethyl aminoethyl methacrylate as the monomers, as well as 8 parts 
azobis isobuturonitrile, and 5 parts tert-butyl peroxy octoate (TBPO), 
present as polymerisation initiators. This mixture of solvent, monomers, 
and polymerisation initiators was dripped in slowly over a period of 4 
hours. 
After the completion of this addition, the temperature was maintained for a 
further 10 hours. The product thus obtained was a solution of the targeted 
tertiary amino vinyl polymer (I) (average molecular weight 9,000) with a 
non volatile component of 60%. Hereafter this polymer is abbreviated as 
polymer (I-2). 
Reference Example 5 
example of the production of the water based product (A) 
1.0 part of an 88% water solution of formic acid was added, at room 
temperature, to 100 parts of the polymer (I-2) obtained in reference 
example 4, and the mixture stirred. In this instance a 100% neutralisation 
rate was obtained. 
Next, a further 49 parts of water were added, and stirring continued until 
a uniform mixture was obtained. The product thus obtained was the targeted 
water based product, and had a non volatile component of 40%. Hereafter 
this product is abbreviated as water based product (A-3). 
Reference Example 6 
example of the production of a tertiary amino vinyl polymer (I) 
Following the standard method, the polymerisation reaction was carried out 
using a mixture of 660 parts isopropyl alcohol as solvent, 100 parts 
styrene, 700 parts n-butyl methacrylate, 100 parts ethyl acrylate, and 100 
parts dimethyl aminoethyl methacrylate as the monomers, as well as 8 parts 
azobis isobuturonitrile, and 5 parts tert-butyl peroxy octoate (TBPO), 
present as polymerisation initiators. This mixture of solvent, monomers, 
and polymerisation initiators was dripped in slowly over a period of 4 
hours. 
After the completion of this addition, the temperature was maintained for a 
further 10 hours. The product thus obtained was a solution of the targeted 
tertiary amino vinyl polymer (I) (average molecular weight 9,000) with a 
non volatile component of 60%. Hereafter this polymer is abbreviated as 
polymer (I-3). 
Reference Example 7 
example of the production of the water based product (A) 
1.1 parts of acetic acid was added, at room temperature, to 100 parts of 
the polymer (I-3) obtained in reference example 6, and the mixture 
stirred. In this instance a 50% neutralisation rate was obtained. 
Next, a further 90 parts of water were added, and stirring continued until 
a uniform mixture was obtained. After this the mixture was heated to 
30.degree. C. to 40.degree. C. and the isopropyl alcohol removed under 
reduced pressure. The product thus obtained was the targeted water based 
product, and had a non volatile component of 40%. Hereafter this product 
is abbreviated as water based product (A-4). 
Reference Example 8 
example of the production of a vinyl polymer (II) containing both tertiary 
amino and acidic functionalities 
Using a mixture of 100 parts styrene, 250 parts methyl methacrylate, 440 
parts n-butyl methacrylate, 150 parts ethyl acrylate, 40 parts dimethyl 
aminoethyl methacrylate, and 20 parts acrylic acid as the monomers, as 
well as 10 parts TBPO as the polymerisation initiator, and otherwise 
carrying out the reaction in an identical manner to that described in 
reference example 1 above, a solution of the targeted vinyl polymer (II) 
containing both tertiary amino and acidic functionalities (average 
molecular weight 8,000) with a non volatile component of 60% was obtained. 
Hereafter this polymer is abbreviated as polymer (II-1). 
Reference Example 9 
example of the production of the water based product (C) 
0.8 parts of an 88% water solution of formic acid was added, at room 
temperature, to 100 parts of the polymer (II-1) obtained in reference 
example 8, and the mixture stirred. 
Next, a further 49.2 parts of water were added, and stirring continued 
until a uniform mixture was obtained. The product thus obtained was the 
targeted water based product, and had a non volatile component of 40%. 
Hereafter this product is abbreviated as water based product (C-1). 
Reference Example 10 
example of the production of the water based product (D) 
1.7 parts of triethyl amine were added, at room temperature, to 100 parts 
of the polymer (II-1) obtained in reference example 8, and the mixture 
stirred. 48.7 parts of water were then added and stirring continued until 
a uniform dispersion was obtained. The product thus obtained was the 
targeted water based product, and had a non volatile component of 40%. 
Hereafter this product is abbreviated as water based product (D-1). 
Reference Example 11 
example of the production of a vinyl polymer (II) containing both tertiary 
amino and acidic functionalities 
Using a mixture of 100 parts styrene, 250 parts methyl methacrylate, 340 
parts n-butyl methacrylate, 150 parts ethyl acrylate, 100 parts 
2-hydroxyethyl acrylate, 40 parts dimethyl aminoethyl methacrylate, and 20 
parts acrylic acid as the monomers, as well as 10 parts TBPO as the 
polymerisation initiator, and otherwise carrying out the reaction in an 
identical manner to that described in reference example 1 above, a 
solution of the targeted vinyl polymer (II) containing both tertiary amino 
and acidic functionalities (average molecular weight 8,000) with a non 
volatile component of 60% was obtained Hereafter this polymer is 
abbreviated as polymer (II-2). 
Reference Example 12 
example of the production of the water based product (D) 
1.7 parts of triethyl amine were added, at room temperature, to 100 parts 
of the polymer (II-2) obtained in reference example 11, and the mixture 
stirred 48.7 parts of water were then added and stirring continued until a 
uniform dispersion was obtained The product thus obtained was the targeted 
water based product, and had a non volatile component of 40%. Hereafter 
this product is abbreviated as water based product (D-2). 
Reference Example 13 
example of the production of a vinyl polymer (II) containing both tertiary 
amino and acidic functionalities 
Using a mixture of 666 parts isopropyl alcohol as solvent, 100 parts 
styrene, 690 parts n-butyl methacrylate, 127 parts ethyl acrylate, 33 
parts dimethyl aminoethyl methacrylate, and 50 parts acrylic acid as the 
monomer mixture, and 10 parts TBPO as the polymerisation initiator, and 
otherwise carrying out the reaction in an identical manner to that 
described in reference example 1 above, a solution of the targeted vinyl 
polymer (II) containing both tertiary amino and acidic functionalities 
(average molecular weight 8,000) with a non volatile component of 60% was 
obtained. Hereafter this polymer is abbreviated as polymer (II-3). 
Reference Example 14 
example of the production of the water based product (D) 
2.5 parts of triethyl amine were added to 100 parts of the polymer (II-3) 
obtained in reference example 13, and the mixture stirred. 69 parts of 
water were then added and stirring continued until a uniform dispersion 
was obtained. 
Next, the mixture was heated to between 30 and 40.degree. C. and the 
isopropyl alcohol, used as the polymerisation solvent, removed under 
reduced pressure. The product thus obtained was the targeted water based 
product, and had a non volatile component of 32%. Hereafter this product 
is abbreviated as water based product (D-3). 
Reference Example 15 
example of the production of a vinyl polymer (III) containing acidic 
functionalities 
Using a mixture of 666 parts butyl alcohol as solvent, 200 parts styrene, 
500 parts n-butyl methacrylate, 200 parts ethyl acrylate, and 100 parts 
acrylic acid as the monomer mixture, and 10 parts TBPO as the 
polymerisation initiator, and otherwise carrying out the reaction in an 
identical manner to that described in reference example 1 above, a 
solution of the targeted vinyl polymer (III) containing acidic 
functionalities (average molecular weight 8,000) with a non volatile 
component of 60% was obtained. Hereafter this polymer is abbreviated as 
polymer (III-1). 
Reference Example 16 
example of the production of the water based product (E) 
1.8 parts of N,N dimethyl octyl amine were added to 100 parts of the 
polymer (III-1) obtained in reference example 15, and the mixture stirred. 
96 parts of water were then added and stirring continued until a uniform 
dispersion was obtained. The product thus obtained was the targeted water 
based product, and had a non volatile component of 30%. Hereafter this 
product is abbreviated as water based product (E-1). 
Reference Example 17 
example of the production of an acidic vinyl polymer (III) 
Using a mixture of 666 parts ethylene glycol mono isopropenyl ether as 
solvent, 150 parts styrene, 500 parts n-butyl methacrylate, 150 parts 
ethyl acrylate, 100 parts 2-hydroxyethyl acrylate, and 100 parts acrylic 
acid as the monomer mixture, and 10 parts TBPO as the polymerisation 
initiator, and otherwise carrying out the reaction in an identical manner 
to that described in reference example 1 above, a solution of the targeted 
acidic vinyl polymer (III) (average molecular weight 8,000) with a non 
volatile component of 60% was obtained Hereafter this polymer is 
abbreviated as polymer (III-2). 
Reference Example 18 
example of the production of the water based product (E) 
1.8 parts of N,N dimethyl octyl amine were added to 100 parts of the 
polymer (III-2) obtained in reference example 17, and the mixture stirred. 
96 parts of water were then added and stirring continued until a uniform 
dispersion was obtained. The product thus obtained was the targeted water 
based product, and had a non volatile component of 30%. Hereafter this 
product is abbreviated as water based product (E-2). 
Reference Example 19 
example of the production of a compound containing both epoxy and 
hydrolysable silyl functionalities (B) 
800 parts of toluene was placed in a similar reaction vessel to that 
described in reference example 1, and the temperature raised to 
120.degree. C. under a stream of nitrogen. 
Next, a mixture of 416 parts lauryl methacrylate, 284 parts glycidyl 
methacrylate, 300 parts .gamma.-methacryloyl oxy propyl trimethoxy silane 
and 40 parts TBPO was dripped in slowly over a period of 6 hours. 
After the completion of this addition, the temperature was maintained for a 
further 10 hours. The product thus obtained was a solution of the targeted 
polymer, containing both epoxy and methoxy silyl functionalities (epoxy 
equivalence 1000) with a non volatile component of 50%. Hereafter this 
compound is abbreviated as compound (B-1). 
Reference Example 20 
example of the production of a vinyl polymer containing both primary amino 
and acidic functionalities 
Using a mixture of 100 parts styrene, 250 parts methyl methacrylate, 425 
parts n-butyl methacrylate, 120 parts ethyl acrylate, 55 parts methacrylic 
acid and 50 parts acrylic acid as the monomer mixture, n-butyl acetate as 
the solvent, and 10 parts TBPO as the polymerisation initiator, and 
otherwise carrying out the reaction in an identical manner to that 
described in reference example 1 above, a solution of the vinyl polymer to 
be used for comparative purposes was obtained. The non volatile component 
of the solution was 60%. 
Next, the temperature was lowered to 40.degree. C.,36.3 parts of propylene 
imine added, and the mixture allowed to react for 6 hours. At this point 
the acid value of the solid constituent of the resin had fallen to 37.4. 
42 parts of triethyl amine were then added at room temperature and the 
mixture stirred. Next, 755 parts of water were added and stirring 
continued until a uniform dispersion was obtained. The product thus 
obtained was the water based product to be used for comparative purposes, 
and had a non volatile component of 40%. Hereafter this product is 
referred to as the comparative resin. 
Working examples 1-12 and comparative examples 1 and 2 
White paints made of the various resin compositions for use in water based 
paints were produced by mixing the various constituents in the ratios 
shown in Table 1. 
Next, using a 6mil applicator, each of the paints was applied to a zinc 
phosphate treated steel sheet; a steel sheet which had already been 
painted with a primer, constituted of an oil free alkyd resin and melamine 
resin, and then bake dried (ie, a prepainted sheet); a slate sheet; and a 
polypropylene sheet, and then left to dry at ambient temperature for 7 
days to produce a fully cured coating film. 
The coating film applied to the polypropylene sheet was separated from the 
sheet and its gelling coefficient was measured, while the coating film 
applied to the prepainted steel sheet was submitted to the exposure test, 
for a period of two years, in the suburbs of Miyazaki city, after which 
time its weather resistance and resistance to pollution was evaluated. A 
summary of these results is also shown in Table 1. 
TABLE 1 (1-1) 
______________________________________ 
* Working Working 
Working 
Working 
example 1 
example 2 
example 3 
example 4 
______________________________________ 
Water based product 
100 
(A-1) 
Water based product 100 
(A-2) 
Water based product 100 
(A-3) 
Water based product 100 
(A-4) 
[R-930] 24.2 18.5 22.6 23.8 
UV absorber 0.8 0.6 0.8 0.8 
.gamma.-GPTMS 
7.2 6.3 3.0 6.0 
DBTDL 0.04 0.03 0.04 0.03 
TSL 20.0 20.0 
Paint name CC01 CC02 CC03 CC04 
______________________________________ 
*PAINT COMPOSITION 
[Table 1: footnotes 
[R930] . . . abbreviation for [TIPAQUE R930] [brand name for titanium 
oxide produced by Ishihara Sanngyo Kaisya Co., Ltd. 
UV absorber . . . a 1:1 mixture, by weight, of [TINUBIN 765] and [TINUBIN 
384] (both brand names, produced by Cibageigy Ltd., Switzerland) 
GPTMS . . . abbreviation for glycidoxy propyl trimethoxy silane 
DBTDL . . . abbreviation for dibutyl tin dilaurate 
TSL . . . abbreviation for a blend, in a molar ratio of 2:1, of the 2 
silicate compounds [TSL8178; phenyltriethoxy silane] and [TSL8122; 
dimethyldiethoxy silane] [produced by Toshiba Silicone Co., Ltd. 
TABLE 1 (1-2) 
______________________________________ 
* Working Working 
Working 
Working 
example 1 
example 2 
example 3 
example 4 
______________________________________ 
Paint Name CC01 CC02 CC03 CC04 
Gelling coefficient 
94 92 96 94 
(%) 
Initial Gloss (20.degree. ) 
80 80 87 78 
Pencil hardness 
2B HB H 2B 
Gloss retention 
66 76 77 62 
coefficient (%) 
Solvent resistance 
o o O o 
Resistance to acidity 
GOOD 
Resistance to 
GOOD 
alkalinity 
Water resistance 
GOOD 
Wet adhesion 100 90 100 100 
Resistance to 
0.4 0.2 0.1 0.4 
yellowing under 
heat (.DELTA.b) 
______________________________________ 
*COATING FILM PROPERTIES 
[Table 1: footnotes 
Gelling coefficient (%) . . . This percentage is calculated as 100 times 
the ratio of the weight of the paint film, having been separated from the 
material and then soaked in acetone for 24 hours, to the weight of film 
prior to soaking in acetone. 
Pencil hardness . . . This refers to the hardness of [Mitsubishi Uni] 
pencil [brand name, produced by Mitsubishi Pencils Co., Ltd.] required to 
scratch the coating film. 
Gloss retention coefficient (%) . . . This percentage value is calculated 
by the formula below. The higher this value, the greater the weather 
resistant properties of the coating film. 
Gloss retention coefficient (%) = G.sub.1 /G.sub.0 .times. 100 
[Note, in this formula G.sub.1 refers to the 60.degree. gloss value (the 
percentage of 60.degree. incident light reflected) after 2 years exposure 
to the elements, and G.sub.0 refers to the initial 60.degree. gloss value 
Solvent resistance . . . A piece of felt soaked in methyl ethyl ketone wa 
placed on a sample of the paint film and weighted down with a 500 g 
weight. The felt was then rubbed back and forth over the paint surface 10 
times and the external appearance of the coating film evaluated by eye. 
The evaluation standards used are as follows. 
O no change 
o slight scratches visible 
.DELTA. marked loss in surface Gloss 
X dissolution and loss of coating film 
Resistance to acidity . . . A 5% water solution of sulfuric acid was 
dripped on to the film for a period of 24 hours, and the film then washed 
with water, and its external appearance evaluated by eye. 
Resistance to alkalinity . . . A 5% water solution of sodium hydroxide wa 
dripped on to the film for a period of 24 hours, and the film then washed 
with water, and its external appearance evaluated by eye. 
Water resistance . . . A sample of the paint film was soaked in warm wate 
at 40.degree. C. for a period of one week and the external appearance of 
the film then evaluated by eye. 
Wet adhesion . . . Following soaking in warm water at 40.degree. C. for a 
period of one week, a cross cut pattern, consisting of 11 horizontal and 
11 vertical cuts at regular intervals, was made on the film's surface and 
a stripping test carried out using cellophane tape. 
Resistance to yellowing under heat . . . A paint film, cured for 7 days a 
room temperature, was placed on a sheet of white material and over baked 
at 80.degree. C. for a period of one hour, at which point the yellowing o 
the film was measured. The value [b] refers to the difference in the 
measured value and that of the white material. 
TABLE 1 (2-1) 
______________________________________ 
* Working Working 
Working 
Working 
example 5 
example 6 
example 7 
example 8 
______________________________________ 
Water based product 
100 
(C-1) 
Water based product 100 
(D-1) 
Water based product 100 
(D-2) 
Water based product 100 
(D-3) 
[R-930] 24.4 24.6 24.6 19.4 
UV absorber 0.8 0.8 0.8 0.64 
.gamma.-GPTMS 
7.6 7.6 7.6 5.8 
DBTDL 0.04 
TSL 10.0 10.0 10.0 
N-MP 2.0 2.0 2.0 2.0 
Paint name CC05 CC06 CC07 CC08 
______________________________________ 
*PAINT COMPOSITION 
[Table 1: footnotes 
NMP . . . abbreviation for Nmethyl pyrrolidone. 
TABLE 1 (2-2) 
______________________________________ 
* Working Working 
Working 
Working 
example 5 
example 6 
example 7 
example 8 
______________________________________ 
Paint Name CC05 CC06 CC07 CC08 
Gelling coefficient 
89 90 96 88 
(%) 
Initial Gloss (2.degree. ) 
80 78 88 83 
Pencil hardness 
2B B H 2B 
Gloss retention 
58 73 78 71 
coefficient (%) 
Solvent resistance 
o o O o 
Resistance to acidity 
GOOD 
Resistance to 
GOOD 
alkalinity 
Water resistance 
GOOD 
Wet adhesion 98 100 100 85 
Resistance to 
0.1 0.1 0.1 0.1 
yellowing under 
heat (.DELTA.b) 
______________________________________ 
*COATING FILM PROPERTIES 
TABLE 1 (3-1) 
______________________________________ 
* Working 
Working 
Working 
Working example 
example 
example 
example 9 
10 11 12 
______________________________________ 
Water based product 
100 100 
(A-1) 
Water based product 100 
(A-2) 
Water based product 100 
(A-3) 
[R-930] 28.2 23.8 19.6 19.6 
UV absorber 1.0 0.8 0.6 0.6 
.gamma.-GPTMS 6.0 
.gamma.-GPMDMS 8.0 8.0 
Polymer (B-1) 
25.0 
DBTDL 0.04 
SH-6018 2.0 2.0 2.0 2.0 
Paint name CC09 CC10 CC11 CC12 
______________________________________ 
*PAINT COMPOSITION 
[Table 1: footnotes 
GPMDMS . . . Abbreviation for glycidoxy propyl methyl dimethoxy silane. 
[SH6018] . . . Abbreviation for [Toray Silicone SH6018] a silicone resin 
containing hydroxyl groups produced by Toray Silicone Co., Ltd. 
TABLE 1 (3-2) 
______________________________________ 
* Working 
Working 
Working 
Working example 
example 
example 
example 9 
10 11 12 
______________________________________ 
Paint Name CC09 CC10 CC11 CC12 
Gelling coefficient 
95 92 94 96 
(%) 
Initial Gloss (20.degree. ) 
72 80 80 87 
Pencil hardness 
4B 2B F 2H 
Gloss retention 
63 74 58 69 
coefficient (%) 
Solvent resistance 
o O o O 
Resistance to acidity 
GOOD 
Resistance to 
GOOD 
alkalinity 
Water resistance 
GOOD 
Wet adhesion 100 100 80 70 
Resistance to 
0.3 0.3 0.1 0.1 
yellowing under 
heat (.DELTA.b) 
______________________________________ 
*COATING FILM PROPERTIES 
TABLE 1 (4-1) 
______________________________________ 
* Comparative 
Comparative 
example 1 example 2 
______________________________________ 
Polymer (I-1) 100 
Comparative resin 100 
Titanium Oxide R-930 
26.2 35.7 
UV absorber 0.8 1.2 
.gamma.-GPTMS 12.4 9.0 
DBTDL 0.04 0.06 
N-MP 2.0 
Solvent mixture 43 
Paint name CC'01 CC'02 
______________________________________ 
*PAINT COMPOSITION 
[Table 1: footnotes 
Solvent mixture . . . This is a 70/30 mixture by weight, of toluene and 
nbutyl acetate. 
TABLE 1 (4-2) 
______________________________________ 
* Comparative 
Comparative 
example 1 example 2 
______________________________________ 
Paint Name CC'01 CC'02 
Gelling coefficient (%) 
80 95 
Pencil hardness 2B B 
Gloss retention coefficient (%) 
20 66 
Solvent resistance X .DELTA. 
Resistance to acidity 
GO OD 
Resistance to alkalinity 
GO OD 
Water resistance GO OD 
Wet adhesion 0 100 
Resistance to yellowing under heat (.DELTA.b) 
0.2 3 
______________________________________ 
*COATING FILM PROPERTIES