Resinous composition for two liquid type water paint crosslinkable at normal temperature

A resinous composition for two-liquid type water paint crosslinkable at the normal temperature which has a long pot life and which is superior in properties such as hardness, gloss, solvent resistance and water resistance is disclosed. A resinous composition comprises: (A) a colloidal dispersion or emulsion obtained by copolymerizing a monomer mixture comprising a carbonyl group-containing unsaturated monomer, carboxyl group-containing unsaturated monomer and other unsaturated monomers to form a copolymer, neutralizing the copolymer with an alkali, dissolving or emulsifying it into water, and adjusting the pH to above 7; and (B) an easily water soluble dihydrazide compound having from 1 to 5 carbon atoms.

BACKGROUND OF THE INVENTION 
This invention relates to a resinous composition for two-liquid type water 
paint crosslinkable at normal temperatures, by which paint film having 
superior hardness, physical properties, gloss, solvent resistance, water 
resistance and the like can be formed. 
Disadvantages of the paint film obtained from an emulsion paint are that it 
shows tackiness at a high temperature state, and that its solvent 
resistance and initial water resistance before sufficient fusing of 
particles are poor. In order to improve these properties, it is generally 
known to introduce a carbonyl group and crosslink by adding dihydrazide as 
a crosslinking agent. As one method to utilize such emulsions, a process 
is disclosed in Japanese Laid-open Patent No. 4-372674/1992 wherein a 
carbonyl group is introduced into emulsion particles and the surfaces of 
the emulsion particles are controlled skillfully without contact with the 
crosslinking agent in the paint state, to obtain a one liquid type paint. 
Furthermore, an improved method is disclosed in Japanese Laid-open Patent 
No. 5-98071/1993 wherein a part of the emulsion is treated to be soluble 
and whereby contactability and water resistance are improved. 
However, in the processes to form a paint film by using the emulsion made 
by emulsion polymerization together with such surfactants to fuse 
particles, the properties of the paint film such as hardness, physical 
properties, gloss, solvent resistance and the like which are equivalent to 
those of a solvent type two-liquid resinous composition for urethane 
paints cannot be obtained. 
In order to obtain such properties, it is necessary to use resins such as a 
colloidal dispersion obtained by dispersing a polymer having a hydrophilic 
portion into water or a dispersive emulsion, wherein the main action of 
film formation is a crosslinking reaction. In such cases, there cannot be 
obtained one-liquid type paint by using the above mentioned particles 
because of non-clear particle states, and unavoidably becomes a two-liquid 
type paint. 
It was an object of this invention to obtain a resinous composition for 
paint crosslinkable at normal temperatures which exhibits the equal 
hardness, physical properties, gloss, a solvent resistance and water 
resistance equivalent to those of a solvent type two-liquid urethane paint 
even as an aqueous resinous composition. 
SUMMARY OF THE INVENTION 
Applicants have studied the crosslinking reaction between carbonyl group 
and dihydrazide in a disperse type aqueous resin for the purpose of 
forming a resinous composition for paint based on a resinous composition 
for a two-liquid type water paint having properties equal to the solvent 
type two-liquid paint. 
The first aspect of the present invention is a resinous composition for 
two-liquid type water paint crosslinkable at the normal temperature, which 
comprises (A) a colloidal dispersion or emulsion (referred simply to as 
"emulsion (A)" hereinafter) obtained by copolymerizing a monomer mixture 
comprising from 5 to 40% by weight of a carbonyl group-containing 
unsaturated monomer, from 1 to 20% by weight of a carboxyl 
group-containing unsaturated monomer and from 40% to 94% by weight of 
other unsaturated monomers to form a copolymer, neutralizing the copolymer 
with an alkali, dissolving or emulsifying it into water, and adjusting Ph 
value above 7, as well as (B) from 0.05 to 1.0 mole equivalent (based on 
the carbonyl group content contained in the said emulsion (A)) of readily 
water soluble dihydrazide compound (hereinafter referred to as 
"dihydrazide compound") having from 1 to 5 carbon atoms. 
The second aspect of the present invention is the resinous composition for 
two-liquid type water paint crosslinkable at the normal temperature 
according to the first aspect, wherein the copolymer to form particles of 
the emulsion (A) has a number average molecular weight of 500-150,000. 
The third aspect of the present invention is the resinous composition for 
two-liquid type water paint crosslinkable at normal temperatures according 
to the first aspect, wherein the emulsion (A) is an emulsion having pH of 
above 7. 
The fourth aspect of the present invention is the resinous composition for 
two-liquid type water paint crosslinkable at normal temperatures according 
to the first aspect, wherein the emulsion (A) is obtainable by 
copolymerizing a monomer mixture comprising from 5 to 40% by weight of a 
carbonyl group-containing unsaturated monomer, from 1 to 20% by weight of 
a carboxyl group-containing unsaturated monomer, from 5 to 40% by weight 
of a higher alkyl ester monomer of methacrylic acid having 9 to 30 carbons 
and from 5 to 89% by weight of other unsaturated monomers. 
The fifth aspect of the present invention is the resinous composition for 
two-liquid type water paint crosslinkable at normal temperatures according 
to any of the first to fourth aspects of the present invention, wherein 
the hydrazide compound (B) is one or two compounds selected from the group 
consisting of those expressed by the general formula (1) and (2) below: 
##STR1## 
(n=0 to 3), as well as malonic dihydrazide, maleic dihydrazide, itaconic 
dihydrazide and fumaric dihydrazide. 
The sixth aspect of the present invention is the resinous composition for 
two-liquid type water paint crosslinkable at normal temperatures according 
to the fifth aspect, wherein the hydrazide compound (B) is either (1) or 
(2) above.

PREFERRED EMBODIMENTS OF THE INVENTION 
The invention is based on the following three novel findings. 
(1) In order to obtain the objective of high properties, it is necessary to 
increase the crosslinking density and thus increase the amount of a 
crosslinking agent. As a result, the crosslinking reaction proceeds faster 
and pot life becomes too short, but the time of the pot life can be 
controlled by increasing Ph value upwardly. 
(2) By using adipic dihydrazide as is conventionally used in this field, 
the surface gloss is lost when dried in the case of large amounts of it 
being used. This tendency is strong particularly in a high pH range, but 
it can be solved by using a specific strong hydrophilic dihydrazide. 
(3) The dispersive type emulsion (A) used in the inversion may include long 
chain monomers of higher alkylesters of methacyclic acid having 9 to 30 
carbon atoms (hereinafter referred to as "long chain monomer"). By 
including the long chain monomer in the dispersive emulsion (A), water 
resistance and adhesion capability by means of entanglement of long chain 
monomer which is the hydrophobic component of the paint coating, even 
though the paint coating contains plenty of hydrophilic component. 
The emulsion (A) used in the invention is prepared by copolymerizing a 
mixture of a carbonyl group-containing unsaturated monomer, a carboxyl 
group-containing unsaturated monomer, the long chain monomer and other 
unsaturated monomers or the mixture excluding the long chain monomer by 
means of any known polymerization method such as solution polymerization, 
bulk polymerization and the like, to obtain a polymer, neutralizing the 
polymer with an alkali, and dissolving or dispersing it into water. 
The said emulsion (A) is different considerably in molecular weight of 
polymer which is to constitute the emulsion particles from the emulsion 
formed by an emulsion polymerization method using a surfactant. For 
example, the number average molecular weight is advantageously within a 
range of 500-150,000, preferably 1,000-80,000 in order to obtain a stable 
emulsion. 
On the other hand, the number average molecular weight prepared by an 
emulsion polymerization method is generally 150,000-1,000,000, and 
furthermore those having higher molecular weight are also included, 
wherein a part becomes a gel. 
As the carbonyl group-containing monomer used in synthesis of the emulsion 
according to the invention, there may be mentioned acrolein, diacetone 
acrylamide, diacetone methacrylamide, formyl styrol, vinyl alkyl ketones 
having 4-7 carbon atoms (such as vinyl methyl ketone, vinyl ethyl ketone, 
vinyl butyl ketone), diacetone acrylate, diacetone methacrylate, 
acetonitrile acrylate, 2-hydroxypropyl acrylate acetyl acetate, butane 
diol 1,4-acrylate acetyl acetate, acryl (or methacryl) oxyalkyl propenal, 
acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate and the like. 
Particularly preferable are diacetone acrylamide and diacetone 
methacrylamide which are easily controllable in their reaction rates by 
means of Ph. The used amount thereof is 5-40% by weight, preferably 7-30% 
by weight, more preferably 10-25% by weight. 
The carboxyl group-containing monomers are monomers generally used in the 
synthesis of water-soluble resins, and include for example acrylic acid, 
methacrylic acid, itaconic acid, maleic acid and the like. The used amount 
thereof is 1-20% by weight, preferably 2-10% by weight. 
Further, the long chain monomer of the present invention as a 
copolymerizing component is used to improve water resistance of the paint 
coating and adhesion capability of the coating on a metal surface adhered 
after the metal surface is dipped into water. As an example of the long 
chain monomer, methacrylic acid of higher alkyl ester having 9 to 30 
carbon atoms is mentioned. The long chain monomer contains an alkyl group 
having a long chain of carbon which is longer than C.sub.9. The 
hydrophobic side chains of the long chain monomer are entangled enough 
with each other to remarkably increase the water resistance of the paint 
coating. Further, the long chain monomer has a strong hydrophobic property 
which prevents copolymerization, and may not normally be introduced into 
an emulsion for emulsion polymerization in which a surfactant is used. 
However, in accordance with the present invention, the long chain monomer 
may be copolymerized by means of the solution polymerization, and the 
resultant copolymer may easily become an emulsion by means of 
neutralization by alkali and water dispersion. 
The long chain monomer may be an alkyl ester having C.sub.9 to C.sub.30 of 
methacrylic acid, preferably C.sub.12 to C.sub.26, further preferably 
C.sub.16 to C.sub.22. For example, nonyl methacrylate (C.sub.9), decyl 
(C.sub.10), undecyl (C.sub.11), dodecyl (lauryl) (C.sub.12), tridecyl 
(C.sub.13), hexadecyl (C.sub.16), heptadecyl (C.sub.17), octadecyl 
(stearyl) (C.sub.18), eicocyl (C.sub.20) or behenyl (C.sub.22). The 
contents of the long chain monomer is 5 to 40% by weight. 
The other monomers to be copolymerized with the above mentioned three 
monomers are not subjected to any limitation, and include, for example, 
styrene, acrylic or methacrylic esters with side-chains having 1 to 8 
carbon atoms, acrylonitrile, butadiene, vinyl toluene, methacrylonitrile, 
vinyl acetate, vinyl chloride, vinylidene chloride, olefins and the like. 
The used amount thereof is 5 to 89% by weight, preferably 20 to 80% by 
weight. 
The dihydrazide compound (B) used as a crosslinking agent according to the 
invention should have sufficient water-solubility. There may be mentioned, 
for example, carbodihydrazide expressed by the following chemical 
formulae: 
##STR2## 
(n=0 to 3). 
Furthermore, there may be mentioned malonic dihydrazide, maleic 
dihydrazide, itaconic dihydrazide, fumaric dihydrazide and the like. 
Preferably, n=0 or 1 in the above-mentioned formula, and carbodihydrazide 
is particularly preferable. The used amount thereof is 0.05 to 1 mole 
equivalent based on carbonyl group content (0.1 to 2 as functional group 
ratio), preferably 0.1 to 0.6 more preferably 0.15 to 0.5 mole equivalent. 
The neutralizing agent used in the invention is ammonia, a low molecular 
weight amine or an alkali metal. The pH value of the emulsion (A) is 
adjusted above 7, preferably 8 to 11. It is more preferably 8.5 to 10.5. 
If the amount of the crosslinking agent used in the invention is less than 
the above-mentioned range, the desired properties thereof is less 
effectively obtained, but even if too much, the effect is relatively 
small. If the Ph value is below 7, the reaction proceeds too fast to 
shorten the pot life. 
The invention has developed the resinous composition for two-liquid type 
water paint crosslinkable at the normal temperature, but crosslinking can 
be carried out more thoroughly by heating. During paint forming, pigments, 
extenders, thickeners, and other conventional additives are added. 
Furthermore, adhesives and the like may be applied. 
The invention is illustrated in more detail by the following examples. 
EXAMPLE 1 
150 parts by weight of ethylene glycol monobutyl ether was introduced into 
a 2 liter flask, heated to 110.degree. C., and substituted by nitrogen, 
and the following mixture was added dropwise for 1 hour: 
______________________________________ 
Acrylic acid 10 parts by weight 
Diacetone acrylamide 
30 parts by weight 
Butyl acrylate 50 parts by weight 
Styrene 30 parts by weight 
Methyl methacrylate 29 parts by weight 
Allyl methacrylate 1 part by weight 
Azobisisobutyronitrile 
3 parts by weight 
______________________________________ 
After the end of addition, it was kept at 110.degree. C. for 30 minutes, 
and then the following mixture was added dropwise for 1 hour: 
______________________________________ 
Diacetone acrylamide 
30 parts by weight 
Butyl acrylate 55 parts by weight 
Styrene 33 parts by weight 
Methyl methacrylate 
32 parts by weight 
Azobisisobutyronitrile 
1.5 parts by weight. 
______________________________________ 
One hour and one hour-and-half after the end of addition, 0.5 parts by 
weight of azobisisobutyronitrile was added, the mixture was kept 
110.degree. C. for further 2 hours, then cooled to 70.degree. C., and 14 
parts by weight of triethylamine was added, 500g of deionized water was 
added with stirring, to obtain an aqueous solution having high viscosity. 
The Ph value thereof was 8.6. The number average molecular weight 
calculated from the result of gel chromatography was 13,800. 
To 50 parts by weight of the solution, 10 parts by weight of deionized 
water and 0.8 parts by weight carbodihydrazide were added. The solution 
was shown in Table 1 respectively. After the retention period, the 
solution was coated on the treating plate, dried for 3 days, and 
thereafter the painting properties were tested. The results are shown in 
Table 1. 
TABLE 1 
______________________________________ 
Hours/Days after 
Properties of Three Days After Painting 
Adding Film 
Carbodihydrazide 
thickness 
Pencil Solvent 
Erichsen 
Mixing (.mu.m) Hardness Resistance 
Value Gloss 
______________________________________ 
Immediately after 
20 2H .largecircle. 
7 mm&lt; .largecircle. 
2 hours after 
19 2H .largecircle. 
7 mm&lt; .largecircle. 
6 hours after 
18 2H .largecircle. 
7 mm&lt; .largecircle. 
1 day after 
18 2H .largecircle. 
7 mm .largecircle..sup.- 
2 days after 
21 H .largecircle..sup.- 
5 mm .largecircle. 
(Thickened) 
______________________________________ 
Solvent resistance was obtained by rubbing with a cloth moistened with 
xylene for 10 times and observing the change. 
In the case that 1.6 parts by weight or 0.8 parts by weight of adipic 
dihydrazide was added, there was no gloss observed. 
"O" in table 1, as well as tables below, shows that satisfactory results 
have been obtained. 
EXAMPLE 2 
150 parts by weight of propylene glycol monoethyl ether was introduced into 
a 2 liter flask, heated to 110.degree. C., and substituted by nitrogen, 
and the following mixture was added dropwise for 2 hours: 
______________________________________ 
Acrylic acid 10 parts by weight 
Diacetone acrylamide 
60 parts by weight 
Butyl acrylate 105 parts by weight 
Styrene 65 parts by weight 
Methyl methacrylate 
60 parts by weight 
Azobisisobutyronitrile 
9 parts by weight. 
______________________________________ 
After the end of addition, it was kept at 110.degree. C. for 30 minutes, 
and 30 minutes and 1 hour after, 0.5 parts by weight of 
azobisisobutyronitrile was added respectively, kept at 110.degree. C. for 
2 hours, cooled, and then 14 parts by weight of triethylamine and 50 parts 
by weight of isopropanol were added, stirred thoroughly, and thereafter 
600g of deionized water was added dropwise. The aqueous solution was 
concentrated to solid content of 36% under a decreased pressure, to obtain 
an aqueous solution having pH of 8.8. The number average molecular weight 
calculated from the result of gel chromatography was 6,529. 
Test results of the painted film obtained by using 50 parts by weight of 
the solution and blending carbodihydrazide shown in Table 2 are also shown 
in Table 2. 
TABLE 2 
______________________________________ 
Water 
Carbodihydrazide 
Film thickness 
resistance Pencil 
(Parts by weight) 
(.mu.m) 2 hrs. submerged 
Gloss 
hardness 
______________________________________ 
0.8 20 .largecircle..sup.- 
.largecircle. 
2H 
0.6 21 .largecircle..sup. 
.largecircle. 
H-2H 
0.4 19 .largecircle..sup.- 
.largecircle. 
F 
______________________________________ 
Tests were carried out 2 days after painting. 
The results of Erichsen test were determined after 7 days, and for that 
wherein 0.6 parts by weight of carbohydrazide being added, the result was 
7mm. 
EXAMPLE 3 
150 parts by weight of propylene glycol monoethyl ether was introduced into 
a 2 liter flask, heated to 110.degree. C., and substituted by nitrogen, 
and the following mixture was added dropwise for 2 hours: 
______________________________________ 
Acrylic acid 10 parts by weight 
Diacetone acrylamide 
90 parts by weight 
Butyl acrylate 70 parts by weight 
Butyl methacrylate 
65 parts by weight 
Styrene 65 parts by weight 
Azobisisobutyronitrile 
9 parts by weight 
______________________________________ 
After the end of addition, it was kept at 110.degree. C., and 30 minutes 
and 1 hour after, 0.5 parts by weight of azobisisobutyronitrile was added 
respectively, kept at 110.degree. C. for 2 hours, cooled, and then 14 
parts by weight of triethylamine and 50 parts by weight of isopropanol 
were added, stirred thoroughly, and thereafter 450g of deionized water was 
added dropwise. The aqueous solution was concentrated to solid content of 
45.1% under a decreased pressure to obtain an aqueous solution having pH 
of 8.66. The number average molecular weight calculated from the result of 
gel chromatography was 7,274. 
To 40 parts by weight of the solution, 0.12 parts by weight of 
carbohydrazide was added, and after 40 minutes, the paint film coated on 
the treating plate expressed the following properties: 
______________________________________ 
Film thickness 25 .mu.m 
Water resistance (2 hours after submerged into water) 
.largecircle. 
Gloss .largecircle. 
Pencil hardness 2H 
Erichsen test value 5 mm 
______________________________________ 
EXAMPLE 4 
300 parts by weight of propylene glycol monoethyl ether was introduced into 
a 2 liter flask, heated to 110.degree. C., and substituted by nitrogen, 
and the following mixture was added dropwise for 2 hours: 
______________________________________ 
Acrylic acid 60 parts by weight 
Diacetone acrylamide 
60 parts by weight 
Butyl acrylate 90 parts by weight 
Methyl methacrylate 
90 parts by weight 
Azobisisobutyronitrile 
9 parts by weight. 
______________________________________ 
After the end addition, it was kept at 110.degree. C., and after 1 hour and 
2 hours, 1 part by weight of azobisisobutyronitrile was added 
respectively, kept at 110.degree. C. for 2 hours, cooled, and then 84 
parts by weight of triethylamine was added, and 300g of demineralized 
water was added, to obtain an aqueous solution having pH of 10.50. The 
number average molecular weight calculated from the result of gel 
chromatography was 15,050. 
1 part by weight of carbohydrazide was added to 50 parts by weight of the 
solution to form a product useful for 3 hours. Hardness of the paint film 
with paint thickness of 23 .mu.m was 2H after 7 days. 
COMATIVE EXAMPLE 
Polymerization was carried out analogously to Example 4, and after cooled, 
25 parts by weight of triethylamine was added with stirring, and then 300 
parts by weight of deionized water was added, to obtain an aqueous 
solution with pH of 6.12. The number average molecular weight calculated 
from the result of gel chromatography was 15,050. 
1 part by weight of carbodihydrazide was added to 50 parts by weight of the 
aqueous solution to form a product, which was gelled after 5 minutes. 
EXAMPLE 5 
270 parts by weight of propylene glycol monoetyl ether was introduced into 
a 5 liter separable flask, heated to 110.degree. C., and substituted by 
nitrogen, and the following mixture was added dropwise for 1.5 hours: 
______________________________________ 
Acrylic acid 31.5 parts by weight 
Diacetone acrylamide 270.0 parts by weight 
Styrene 180.0 parts by weight 
Stearyl methacrylate 270.0 parts by weight 
n-butyl methacrylate 343.5 parts by weight 
n-butyl acrylate 30.0 parts by weight 
i-butyl methacrylate 225.0 parts by weight 
PER-BUTYL-O 2.7 parts by weight 
(PER-BUTYL-O is a polymerization initializing 
agent provided by Nippon Oil and Fats Co., Ltd.) 
______________________________________ 
After the end of addition, PER-BUTYL-O was added dropwise again for 2 
hours. Further, it was kept heated for 4 hours, and then 54 parts by 
weight of triethylamine was added with stirring well to the resultant 
material above. Then 1575 parts by weight of water was added with 
stirring, to have the mixture emulsionized. The emulsion obtained through 
reduced-pressure distillation had 48.4% of solid content, 0.12 .mu.m of 
particle diameter, 46 poise of viscosity (measured by a B type viscosity 
meter at 20.degree. C. and 60 rpm, the same condition of which was used 
below) and 8.97 pH value. 
EXAMPLE 6 
An emulsion was obtained by the same method of example 5, with the monomers 
below: 
______________________________________ 
Acrylic acid 31.5 parts by weight 
Diacetone acrylamide 
270.0 parts by weight 
Styrene 270.0 parts by weight 
Stearyl methacrylate 
270.0 parts by weight 
n-butyl methacrylate 
508.5 parts by weight 
______________________________________ 
The emulsion obtained had 47.8% of solid content, 0.17 .mu.m of particle 
diameter, 33 poise of viscosity and 9.01 pH value. 
EXAMPLE 7 
An emulsion was obtained by the same method of example 5, using 2 liter 
flask in lieu of 5 liter one, in the one third scale. The monomers used 
are as follows: 
______________________________________ 
Acrylic acid 10.5 parts by weight 
Diacetone acrylamide 
90.0 parts by weight 
Styrene 60.0 parts by weight 
Stearyl methacrylate 
45.0 parts by weight 
n-butyl methacrylate 
94.5 parts by weight 
n-butyl acrylate 
75.0 parts by weight 
i-butyl methacrylate 
75.0 parts by weight 
______________________________________ 
The emulsion obtained had 46.7% of solid content, 0.08 .mu.m of particle 
diameter, 40 poise of viscosity and 9.01 pH value. 
EXAMPLE 8 
An emulsion was obtained by the same method of example 5, with the monomers 
below: 
______________________________________ 
Acrylic acid 31.5 parts by weight 
Diacetone acrylamide 270.0 parts by weight 
Styrene 180.0 parts by weight 
BLENMER SLMA 270.0 parts by weight 
(BLENMER SLMA is a synthesized lauryl 
methacrylate provided by Nippon Oil and Fats 
Co., Ltd.) 
Stearyl methacrylate 270.0 parts by weight 
n-butyl methacrylate 508.5 parts by weight 
n-butyl acrylate 30.0 parts by weight 
i-butyl methacrylate 225.0 parts by weight 
PER-BUTYL-O 2.7 parts by weight 
______________________________________ 
The emulsion obtained had 48.2% of solid content, 0.11 micro-meter of 
particle diameter, 48 poise of viscosity and 9.00 pH value. 
EXAMPLE 9 
An emulsion was obtained by the same method of example 5, with the monomers 
below: 
______________________________________ 
Acrylic acid 31.5 parts by weight 
Diacetone acrylamide 
270.0 parts by weight 
n-butyl methacrylate 
283.5 parts by weight 
n-butyl acrylate 
30.0 parts by weight 
Styrene 180.0 parts by weight 
i-butyl methacrylate 
225.0 parts by weight 
______________________________________ 
The emulsion obtained had 42.8% of solid content, 0.08 micro-meter of 
particle diameter, 35.9 poise of viscosity and 9.22 pH value. 
0.4 mole equivalent amount of carbohydrazide as to the amount of carbonyl 
group contained in each of the emulsions of examples 5 through 9 (0.8 mole 
equivalent amount of carbohydrazide as to the amount of functional group 
of the emulsion) was added to each of the emulsions of examples 5 through 
9, and viscosity of each of the emulsions was adjusted by adding water. 
The resultant emulsions were coated with a bar coater on a treatment panel 
for checking the coating properties. The results are shown in Table 3. 
TABLE 3 
______________________________________ 
Characteristics of Coating Seven Days After Painting 
Example 5 6 7 8 9 
______________________________________ 
Thickness of 
23 30 26 27 23 
Coating (.mu.m) 
Pencil 2H 2H 2H 2H 2H 
Hardness 
Anti- .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
solubility 
Erichsen 
7 mm&lt; 7 mm&lt; 7 mm&lt; 7 mm&lt; 7 mm&lt; 
Value (.mu.m) 
Gloss .largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
.largecircle. 
Water 1 Month 1 Month 1 Month 
1 Week 12 Hours 
Resistance 
OK OK OK OK OK 
(submerged 
into water) 
______________________________________ 
Note: Tests could not be achieved for those samples which were left aside 
for one day after hydrazide was added. 
Obviously from the examples, the resinous composition for paint obtained by 
adding an easily water soluble dihydrazide compound with 1-5 carbon atoms 
to a emulsion having pH adjusted above 7 with an alkali has long pot life, 
and provides paint film having superior properties such as hardness, 
gloss, solvent resistance, water resistance and the like.