United States Patent (19) 11) 4,340,519

Kotera et al. 45 Jul. 20, 1982

54). POLYESTER RESEN AQUEOUS 57) ABSTRACT
OSPERSION
An aqueous dispersion of polyester resin which com
75 Inventors: Nobukazu Kotera, Kyoto; Yutaka prises
Mizumura, Shiga; Hideo Miyake, (A) a crystalline polyester having a melting point of
Otsu, all of Japan 70° to 200° C. and containing 0.5 to 10% by mole of
an aromatic dicarboxylic acid having a metal sulfo
73 Assignee: Toyo Boseki Kabushiki Kaisha, nate group as the polycarboxylic acid component,
Osaka, Japan (B) a non-crystalline polyester having a softening
(21) Appl. No.: 217,629 point of 40 to 200° C. and containing 0.5 to 10%
by mole of an aromatic dicarboxylic acid having a
22 Filed: Dec. 18, 1980 metal sulfonate group as the polycarboxylic acid
component,
30 Foreign Application Priority Data (C) a water-soluble organic compound having a boil
Dec. 21, 1979 JP Japan ................................ 54-167002 ing point of 60' to 200 C., and
(D) water, said components (A), (B), (C) and (D)
51) Int. Cl. ....................... C08L 67/02; C08L 81/08 being incorporated in the following weight ratio:
52 U.S. Cl. ........................... 523/414; 260/DIG. 38;
428/458; 428/480; 525/444; 524/376; 524/385; A/B=0-95/100-5 (1)
524/389; 524/539
58 Field of Search .................. 260/29.2 E, 29.2 TN, A+B/C/D=10-70/2-40/20–88 (2)
260/29.2 EP, 29.4 R; 525/444; 528/295
56 References Cited 0.02s C/C+Ds0.66. (3)
U.S. PATENT DOCUMENTS
3,546,008 12/1970 Shields et al. .................... 117/138.8 The aqueous dispersion of this invention has excellent
4,022,740 5/1977 Morie et al. .... ... 260/29.2 E dispersibility in water and can give a coating layer hav
4,104,262 8/1978 Schade ........................... 260/29.2 E ing excellent water resistance and weatherability and
hence is useful for preparation of various laminated
FOREIGN PATENT DOCUMENTS products, coating compositions, aqueous printing ink,
47-40873 10/1972 Japan. aqueous binder for coating and surface treating agent
for giving drip-proof.
Primary Examiner-Theodore E. Pertilla
Attorney, Agent, or Firm-Jones, Tullar & Cooper 10 Claims, No Drawings
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4,340,519
2
Under the circumstances, the present inventors have
POLYESTER RESIN AQUEOUS DISPERSION intensively studied on the production of an improved
polyester resin aqueous dispersion without decreasing
The present invention relates to a polyester resin the water resistance and weatherability. As a result, it
aqueous dispersion, more particularly an aqueous dis has been found that an aqueous dispersion comprising
persion of a polyester resin having a fine particle size one or two kinds of specific polyester containing a
which can give a coating film having excellent water metal sulfonate group, a water-soluble organic com
resistance and excellent weatherability. pound and water satisfies the desired properties.
Hitherto, a large amount of various organic solvents An object of the present invention is to provide an
have widely been used in various fields such as paints, 10 improved aqueous dispersion of polyester resin which
ink, coating compositions, adhesives, treating agents for can give a coating film having excellent water resis
textile or paper products, or the like. Recently, how tance and weatherability. Another object of the inven
ever, it becomes very difficult to use a large amount of tion is to provide an improved polyester resin satisfying
organic solvents in view of saving oil resources and both of the water dispersibility and also the water resis
preventing of environmental pollution. Accordingly, it 15 tance and weatherability. A further object of the inven
has been proposed to prepare the above-mentioned tion is to provide use of the polyester resin aqueous
compositions in the form of non-organic solvent, such dispersion for various utilities such as coating composi
as (1) high solid type, (2) non-aqueous dispersion type,
(3) aqueous dispersion type, (4) emulsion type, and (5) tions, laminated products, aqueous printing ink, aqueous
non-solvent type. Among them, the aqueous dispersion 20 binder for coating, and surface treating agent for giving
type compositions are most useful because of easy han drip-proof. These and other objects and advantages of
dling. the present invention will be apparent to persons skilled
On the other hand, the conventional resins used for in the art by the following description.
these compositions are mostly hydrophobic, and hence, The aqueous dispersion of polyester resin of the pres
it is problem how to disperse them into water or to 25 ent invention comprises
make them compatible with water. Moreover, it is also (A) a crystalline polyester having a melting point of
problem that the resin aqueous dispersion can give a 70 to 200 C. and containing 0.5 to 10% by mole of an
coating film having excellent water resistance and ex aromatic dicarboxylic acid having a metal sulfonate
cellent weatherability. These problems are common in group as the polycarboxylic acid component,
all resins including polyester resins. 30 (B) a non-crystalline (i.e. amorphous) polyester hav
There have already been proposed some methods for ing a softening point of 40 to 200 C. and containing 0.5
dispersing polyester resins into water or for making to 10% by mole of an aromatic dicarboxylic acid having
them compatible with water, for example by copoly a metal sulfonate group as the polycarboxylic acid com
merizing them with hydrophilic monomers, such as a ponent,
compound having a metal sulfonate group, an aliphatic 35 (C) a water-soluble organic compound having a boil
dicarboxylic acid, or a mixture thereof. However, these ing point of 60 to 200° C., and
hydrophilic monomers should be used in a large amount (D) water, said components (A), (B), (C) and (D)
in order to give the polyester resins sufficient water-dis being incorporated in the following weight ratio:
persibility or water-compatibility, and further, the re
Sulting aqueous dispersion of polyester resins gives A/B=0-95/100-5 (1)
merely a coating film having inferior water resistance
and weatherability and inferior adhesion properties. A-B/C/D=10-70/2-40/20-88 (2)
For instance, it is disclosed in Japanese Patent Publi 0.02s C/C+DS0.66. (3)
cation No. 40873/1972 that in order to sufficiently dis
perse the resins into water, 8% by mole or more (based 45 By incorporating (A) a crystalline polyester resin
on the total acid components) of a compound having a
metal sulfonate group and 20% by mole or more (based containing a metal sulfonate group, (B) a non-crystalline
on the total glycol components) of polyethylene glycol polyester resin containing a metal sulfonate group, (C) a
are required. It will readily be understood that such water-soluble organic compound having a boiling point
polyester resins show inferior water resistance and 50 of 60 to 200 C., and (D) water in the specified weight
weatherability. That is, when a resin has sufficient dis ratio, there can be obtained an aqueous dispersion hav
persibility into water, it results in inferior water resis ing both of hydrophilic properties, and high adhesion
tance of the coating film prepared by coating the resin and water resistance. The aqueous dispersion thus ob
aqueous dispersion, followed by drying. In this case, tained has a particle size of 1p, or less and is very stable.
when the formed coating film is contacted with water, 55 The crystalline and non-crystalline polyester resins
it shows decreased adhesion and color change. Accord contain 0.5 to 10% by mole of aromatic dicarboxylic
ingly, such a resin can not be used for preparation of acid having a metal sulfonate group as the polycarbox
paints, inks, coating compositions, adhesives, or the like. ylic acid component. Preferably, the crystalline and
Besides, when a large amount of polyethylene glycol is non-crystalline polyester resins have a molecular
used, the resulting resin shows significantly decreased 60 weight of 2,500 to 30,000 and comprise polycarboxylic
water resistance and weatherability. acid components consisting of 40 to 99.5% by mole of
It is also well known that when a large amount of an an aromatic dicarboxylic acid having no metal sulfonate
aliphatic dicarboxylic acid is copolymerized, the result group, 59.5 to 0% by mole of an aliphatic or alicyclic
ing polyester resin shows decreased properties such as dicarboxylic acid having 4 to 36 carbon atoms and 0.5 to
inferior mechanical properties. 65 10% by mole of an aromatic dicarboxylic acid having a
Thus, the practically useful resin should satisfy both metal sulfonate group, and polyol components consist
of the inconsistent properties, i.e. hydrophilic properties ing of 20 to 100% by mole of an aliphatic glycol having
and water resistance and weatherability. 2 to 8 carbon atoms and/or an alicyclic glycol having 6
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4,340,519
4.
to 12 carbon atoms and 80 to 0% by mole of bisphenol selected from terephthalic acid and isophthalic acid as
Aethylene oxide (or propylene oxide) adduct. the polycarboxylic acid component and 85 to 100% by
Suitable examples of the aromatic dicarboxylic acid mole of a polyl selected from ethylene glycol and bu
having no metal sulfonate group are terephthalic acid, tanediol as the polyol component. Besides, suitable non
isophthalic acid, orthophthalic acid, 2,6-naphthalene crystalline polyester comprises 10 to 80% by mole of
dicarboxylic acid, or the like. These aromatic dicarbox terephthalic acid as the polycarboxylic acid component
ylic acid having no metal sulfonate group is preferably and 20 to 80% by mole of a polyol selected from ethyl
incorporated in an amount of 40 to 99.5% by mole ene glycol and butanediol as the polyol component.
based on the total polycarboxylic acid components. Suitable examples of the aromatic dicarboxylic acid
When the content of the aromatic dicarboxylic acid 10 having a metal sulfonate group are metal salts on sulfo
having no metal sulfonate group is less than 40% by aromatic dicarboxylic acids, such as sulfoterephthalic
mole, the polyester resin thus obtained has disadvanta acid, 5-sulfo-isophthalic acid, 4-sulfophthalic acid, 4
geously inferior mechanical strength and inferior water sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfo
resistance, and on the other hand, when the content is phenoxy)isophthalic acid, or the like. The metal salts
over 99.5% by mole, the polyester resin is hardly dis 15 include salts of the metals such as lithium (Li), sodium
persible into the aqueous system. (Na), potassium (K), magnesium (Mg), calcium (Ca),
Suitable examples of the aliphatic or alicyclic dicar copper (Cu), iron (Fe), or the like. Particularly suitable
boxylic acid are succinic acid, adipic acid, azelaic acid, compound is 5-sodium sulfo-isophthalic acid. The aro
sebacic acid, dodecanedionic acid, dimer acid tetrahy matic dicarboxylic acids having a metal sulfonate group
drophthalic acid, hexahydrophthalic acid, hexahy 20 are incorporated in an amount of 0.5 to 10% by mole,
droisophthalic acid, hexahydroterephthalic acid, or the
like. Particularly, adipic acid, sebacic acid and azelaic preferably 1.0 to 6% by mole, based on the total poly
carboxylic acid components. When the aromatic dicar
acid are suitable. The aliphatic and/or alicyclic dicar boxylic acid having a metal sulfonate group is entirely
boxylic acids are preferably incorporated in an amount
of 59.5 to 0% by mole based on the total polycarboxylic 25 not incorporated, the polyester resin obtained shows
acid components. When the amount of the aliphatic remarkably inferior dispersibility into water. With in
and/or alicyclic dicarboxylic acid is more than 59.5% crease of the amount of aromatic dicarboxylic acid
by mole, the polyester resin obtained shows decreased having a metal sulfonate group, the polyester resin ob
water resistance and mechanical strength of the coating tained shows better dispersibility into water. However,
film prepared therefrom, and shows tackiness. Option 30 when the amounts of the aromatic dicarboxylic acid
ally, p-hyroxybenzoic acid, p-(2-hydroxyethoxy)ben having a metal sulfonate group is over 10% by mole, the
zoic acid, or hydroxypivalic acid, y-butyrolactone, polyester resin gives a coating film having remarkably
e-caprolactone, or the like may be incorporated as the inferior water resistance, while the dispersibility into
polycarboxylic acid component. Moreover, tri- or more water is excellent.
polyvalent polycarboxylic acid such as trimellitic acid, 35 The crystalline polyester resin used in the present
pyromellitic acid may optionally be incorporated in an invention has a melting point of 70 to 200 C., prefera
amount of not more than 10% by mole, usually 0.01 to bly 90 to 180° C. When the crystalline polyester resin
10% by mole based on the total polycarboxylic acid has a melting point of lower than 70° C., the polyester
components. resin aqueous dispersion give a coating film having
Suitable examples of the aliphatic glycol having 2 to 40 inferior water resistance, and on the other hand, when
8 carbon atoms are ethylene glycol, propylene glycol, the melting point is higher than 200° C., the polyester
1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5- resin shows less dispersibility into water. Besides, the
pentanediol, 1,6-hexanediol, or the like. Suitable exam crystalline polyester resin should have a heat of fusion
ples of the alicyclic glycol having 6 to 12 carbon atoms of 50 cal or more, preferably 100 to 1,500 cal, per poly
are 1,4-cyclohexanedimethanol, or the like. These ali 45 mer unit. When it has a heat of fusion of less than 50 cal
phatic glycol having 2 to 8 carbon atoms and alicyclic per polymer unit. The polyester resin shows inferior
glycol having 6 to 12 carbon atoms are incorporated in water resistance, particularly inferior resistance to hot
an amount of 90 to 100% by mole based on the total Water.
polyol components. Optionally, tri- or more polyvalent The non-crystalline polyester resin used in the pres
polyols such as trimethylolpropane, trimethylolethane, 50 ent invention has a softening point of 40 to 200° C.,
glycerine, pentaerythritol, or the like may be incorpo preferably 60' to 180° C. When the softening point of
rated in an amount of not more than 10% by mole, the non-crystalline polyester resin is lower than 40 C.,
usually 0.01 to 10% by mole, based on the total polyol the polyester resin aqueous dispersion give a coating
components. Moreover, polypropylene glycol or poly film having inferior water resistance and having unfa
tetramethylene glycol having a molecular weight of 500 55 vorable tackiness, and on the other hand, when the
to 5,000 may optionally be incorporated in an amount of softening point is higher than 200° C., the polyester
not more than 40% by weight, usually 0.01 to 40% by resin shown inferior dispersibility into water.
weight, based on the total polyol components. Besides a The crystalline and non-crystalline polyester resins
polyalkylene glycol, particularly a polyethylene glycol have a molecular weight of 2,500 to 30,000, preferably
having a molecular weight of 106 to 10,000 may option 60 3,000 to 20,000. When the polyester resins have a mo
ally be incorporated in an amount of not more than 10% lecular weight of smaller than 2,500, the polyester resin
by weight, preferably 0.01 to 5% by weight, based on aqueous dispersion shows inferior water resistance and
the total polyol components. When the polyalkylene inferior adhesion properties, and also inferior mechani
glycol, particularly polyethylene glycol is incorporated cal properties, especially inferior flexibility, and on the
in an amount of more than 10% by weight, the polyester 65 other hand, when the molecular weight is larger than
resin shows extremely decreased water resistance and 30,000, the polyester resins shows inferior dispersibility
weatherability. Suitable crystalline polyester comprises into water, and further it is difficult to incorporate the
50 to 99.5% by mole of an aromatic dicarboxylic acid resins into the aqueous dispersion in a large amount
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4,340,519
because the aqueous dispersion thereof shows too high 0.02s C/C-DS0,66. (3)
viscosity.
The polyester resins can be produced by any conven The aqueous dispersion of the present invention con
tional methods. The polyester resins may optionally be tains the non-crystalline polyester resin (B) alone or
used after being mixed with an amino resin, an epoxy both of the crystalline polyester resin (A) and the non
compound, an isocyanate compound or the like in the crystalline polyester resin (B), but the crystalline poly
molten state or in the form of a solution in a water-solu ester resin (A) is preferably contained in an amount of
ble organic compound, or may be used in the form of a 1% by weight or more based on the weight of the total
partial reaction product with the above-mentioned polyester resins because the aqueous dispersion can give
amino resin, epoxy compound, isocyanate compound or 10 a coating film having greater water resistance, particu
the like. larly resistance to hot water. On the other hand, when
The water-soluble organic compound used in the the crystalline polyester resin (A) is contained in an
present invention is used for increasing the hydrophilic amount of larger than 95% by weight, the polyester
properties of the polyester resins and thereby promot resins show inferior dispersibility into water.
ing the dispersibility thereof into water. That is, when 15 When the polyester resins (A) and (B) are incorpo
the polyester resins, a small amount of the water-soluble rated in an amount of less than 10% by weight or more
organic compound and water are mixed, there can be than 70% by weight based on the total weight of the
obtained the desired aqueous dispersion. aqueous dispersion, the aqueous dispersion shows unfa
The water-soluble organic compounds have a solubil vorably too low or too high viscosity, respectively.
ity of 20 g or more/1 liter of water at 20° C. and include 20 When the water-soluble organic compound (C) is
aliphatic and alicyclic alcohols, ethers, esters, ketones, incorporated in an amount of less than 2% by weight
or the like. Suitable examples of the water-soluble or based on the total weight of the aqueous dispersion, it
ganic compounds are monovalent alcohols such as results in less dispersibility of the polyester resins and
methanol, ethanol, n-propanol, isopropanol, n-butanol, there can not be obtained the desired stable aqueous
isobutanol, sec-butanol, tert-butanol; glycols such as 25 dispersion having a particle size of less than 1. On the
ethylene glycol, propylene glycol; glycol derivatives other hand, when the water-soluble organic compound
such as methyl cellosolve, ethyl cellosolve, n-butyl is incorporated in an amount of more than 40% by
cellosolve, 3-methyl-3-methoxybutanol, n-butyl cello weight, the aqueous dispersion shows unfavorably infe
solve acetate; ethers such as dioxane, tetrahydrofuran; rior drying properties, Particularly preferable amount of
esters such as ethyl acetate; ketones such as methyl 30 the water-soluble organic compound (C) is in the range
ethyl ketone, cyclohexanone, cyclooctanone, cy of 2.5 to 30% by weight based on the total weight of the
clodecanone, isophorone; or the like. Particularly suit , aqueous dispersion.
able examples are n-butyl cellosolve, ethyl cellosolve, The aqueous dispersion of the present invention can
isopropanol, or the like. These water-soluble organic 35 be used for various purposes as it stands, but may be
compounds may be used alone or in a mixture of two or used after being mixed with one or more crosslinking
more kinds thereof. The water-soluble organic com agents such as amino resins, epoxy compounds and
pounds have a boiling point of 60 to 200° C. When the isocyanate compounds.
organic compounds have a boiling point of lower than Suitable examples of the amino resins are formalde
60° C., it is very difficult to keep a temperature neces 40 hyde adduct of urea, melamine or benzoguanamine, and
sary for uniformly dispersing or dissolving the polyester alkylated product thereof with an alcohol having 1 to 6
resins in the water-soluble organic compound, and on carbon atoms, which may optionally be used together
the other hand, when the boiling point is higher than with formaline to give preferable effect.
200 C., the aqueous dispersion is hardly dried when Suitable examples of the epoxy compounds are poly
coated, and further the aqueous dispersions shows less 45 glycidyl esters and ethers, such as diglycidyl ether of
storage stability as well as inferior drying properties bisphenol A or its oligomer, diglycidyl ether of hydro
genated bisphenol A or its oligomer, diglycidyl or
when an amide or sulfonate compound is used as a thophthalate,
water-soluble compound. diglycidyl isophthalate, diglycidyl tere
The aqueous dispersion of the present invention is phthalate, p-hydroxybenzoic acid glycidyl ester ether,
prepared by previously mixing a crystalline polyester diglycidyl tetrahydrophthalate, diglycidyl hexahy
resin (A), a non-crystalline polyester resin (B) and a 50 drophthalate, diglycidyl succinate, diglycidyl adipate,
water-soluble organic compound (C) at 50 to 200 C. diglycidyl sebacate, ethylene glycol diglycidyl ether,
and adding thereto water (D), or by adding a mixture of propylene glycol diglycidyl ether, 1,4-butanediol di
the components (A), (B) and (C) to water (D), followed glycidyl ether, 1,6-hexanediol diglycidyl ether, and
by agitating the mixture at 40 to 120° C. Alternatively, other polyalkylene glycol diglycidyl ethers, triglycidyl
the aqueous dispersion may be prepared by adding the 55 trimellitate, triglycidyl isocyanurate, 1,4-diglycidyloxy
benzene, diglycidyldimethylhydantoin, diglycidyle
polyester resins (A) and (B) into a mixture of a water thyleneurea,
soluble organic compound (C) and water (D), followed diglycidylpropyleneurea, glycerol poly
by agitating the mixture at 40' to 100° C. In any meth glycidyl ether, trimethylolethane polyglycidyl ether,
ods, the components: a crystalline polyester resin (A), a 60 trimethylolpropene polyglycidyl ether, pentaerythritol
non-crystalline polyester resin (B), a water-soluble or polyglycidyl ether, polyglycidyl ether of glycelol alkyl
ganic compound (C) and water (D) should be incorpo ene oxide adduct, or the like.
rated in the following weight ratio in order to obtain the The isocyanate compounds include aromatic, ali
desired properties of the aqueous dispersion: phatic and araliphatic diisocyanates, tri- or more poly
valent polyisocyanates, which may be low molecular
A/B=0-95/100-5 (1) 65 compounds or high molecular compounds. Suitable
examples of the isocyanate compounds are tetramethyl
A-B/C/D=10-70/2-40/20-88 (2) ene diisocyanate, hexamethylene diisocyanate, toluene
diisocyanate, diphenylmethane diisocyanate, hydroge
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4,340,519
8
nated diphenylmethane diisocyanate, xylylene diisocya nated products. That is, the polyester resin aqueous
nate, hydrogenated xylylene diisocyanate, trimer of dispersion is coated onto the surface of various metallic
isophorone diisocyanate, or compounds having termi products (e.g. various products of iron, aluminum, tin,
nal isocyanate group which are obtained by reacting an lead, zinc or the like, more particularly cold-rolled steel
excess amount of the above-mentioned isocyanate com plate, zinc phosphate-treated steel plate, galvanized
pounds with low molecular active hydrogen com sheet, tinplate, aluminum plate, etc.), various plastic
pounds such as ethylene glycol, propylene glycol, tri products (e.g. films or sheets of polyesters such as poly
methylolpropane, glycerine, sorbitol, ethylenediamine, ethylene terephthalate or polybutylene terephthalate,
monoethanolamine, diethanolamine, or triethanol or polyvinyl chloride), or various fiber products (e.g.
amine; or high molecular active hydrogen compounds 10 woven, knitted or non-woven products of synthetic
such as various polyether polyols, polyester polyols, or fibers such as polyamide, polyester or natural fibers
polyamides. such as cotton, wool), and thereon a non-solvent type
The isocyanate compounds may be blocked isocya polyester resin is coated or a polyester film is laminated,
nate compounds which are prepared by subjecting the by which there is produced a laminated product having
above-mentioned isocyanate compounds to an addition 5 excellent durability, adhesion and water resistance
reaction with a blocking agent. Suitable examples of the which is useful as outdoor building materials such as
blocking agent are phenols such as phenol, thiophenol, pipe, fence, coated steel plate, or hot-melt adhesives.
methylthiophenol, ethylphenol, cresol, xylenol, resorci The polyester resin aqueous dispersion can be coated
nol, nitrophenol, chlorophenol; oximes such as acetox onto the various products with conventional means
ime, methyl ethyl ketoxime, cyclohexanone oxime; pri 20 such as roll coater, bar coater, spray coater in a thick
mary alcohols such as methanol, ethanol, propanol, ness of 0.5 to 20 u, preferably 1 to 10 u. The coating of
butanol; halogeno-alcohols such as ethylene chlorohy the non-solvent type polyester resin or the laminating of
drin, 1,3-dichloro-2-propanol; tertiary alcohols such as a polyester film onto the products coated with the aque
tert-butanol, tert-pentanol, tert-butanethiol; lactams ous dispersion can be carried out by conventional meth
such as e-caprolactam, 8-valerolactam, y-butyrolactam, 25 ods such as extrusion lamination, powder coating, film
(8-propiolactam; aromatic amines; imides; active methy lamination, or the like in a thickness of 5 to 300 u, pref
lene compounds such as acetylacetone, acetoacetic acid erably 20 to 150 u.
esters, ethyl malonate, mercaptanes; imines; ureas; dial The polyester resin aqueous dispersion of the present
lyl compounds; sodium bisulfite, or the like. invention is also useful for the preparation of an aqueous
A curing agent or a crosslinking promoting agent 30 printing ink by mixing with pigments. Suitable examples
may be incorporated together with the crosslinking of the pigments are white pigments (e.g. titanium oxide,
agent. Zinc white, white lead), black pigments (e.g. carbon
The crosslinking agent may be incorporated into the black, lamp black, graphite), gray pigments (e.g. zinc
aqueous dispersion in various manners in accordance powder, lead suboxide, slate dust), red pigments (e.g.
with the kinds of the agents, for example, by admixing 35 cadmium red, cadmium-mercury red, red ocher), yell
to the crystalline polyester resin (A) or the non-crystal low pigments (e.g. cadmium yellow, zinc yellow,
line polyester resin (B), adding directly to the aqueous chrome yellow, titanium yellow), green pigments (e.g.
dispersion, or dissolving previously in the water-soluble viridian, chrome oxide green, cobalt green, chrome
organic compound (C) or a mixture of the water-soluble green), blue pigments (e.g. ultramarine blue, iron blue,
organic compound (C) and water (D). 40 cobalt blue), violet pigments (e.g. manganese violet,
The polyester resin aqueous dispersion of the present cobalt violet), iron oxide pigments (e.g. mars yellow,
invention can be used for various utilities, such as adhe iron oxide black), extender pigments (e.g. calcium car
sives, inks, particularly aqueous printing ink, coating bonate, barium sulfate, alumina, talc, clay), azo type
composition, aqueous binder for coating, treating agent organic pigments (e.g. permanent red 4R, Hansa yellow
for textile or paper products, particularly surface treat 45 G, Hansa yellow 10G, brilliant carmine 3B, brilliant
ing agent for giving drip-proof, or the like, and can give carmine 6B), phthalocyanine organic pigments (e.g.
these products excellent water resistance and excellent phthalocyanine green, first sky blue), metallic powder
weatherability. pigments (e.g. silver pigments, copper pigment, gold
For example, the aqueous dispersion of the present pigment), glass powder, glass flake, glass bead, or the
invention can be used as paints, particularly easily peel 50 like. The pigments are incorporated in the weight ratio
able paint which is used for coating onto the surface of of 50-2:50-98 (pigments : polyester resin contained in
metals, steel plates, plastic articles or the like in order to the aqueous dispersion). The aqueous printing ink may
prevent the products from soil or scratch during storage optionally be incorporated with conventional lubricat
thereof and can easily be peeled off when the products ing agents and defoaming agents, such as acrylic addi
are used. For this purpose, the aqueous dispersion may 55 tives (e.g. Modaflow, made by Monsanto Co., or Poly
be used as it stands, but may be used after being admixed flow S, made by Kyoeisha Yushi), silicone additives
with other resin aqueous dispersions or emulsions, pig (e.g. Bysilone OL, made by Bayer, YF-3818, XF-3913,
ments and other various additives. Other resin aqueous TSA-720, made by Toshiba Silicone). The aqueous
dispersions or emulsions include aqueous dispersions or printing ink thus obtained shows excellent adhesion to
emulsions of acrylic resin, urethane resin, ethylene 60 various plastic films (e.g. polyester film, polyvinyl chlo
vinyl acetate resin, rubber latex or the like. Pigments ride film), papers, metals (e.g. aluminum, copper, iron),
include inorganic pigments such as titanium oxide, sili fiber woven products, or the like and shows also excel
cone oxide, magnesium oxide, zinc oxide, talc; or other lent water resistance, anti-blocking properties and flexi
coloring agents. Other additives include fluoric, silicone bility.
or acrylic flowability improvers, antioxidants, antifun 65 The polyester resin aqueous dispersion of the present
gal agents, or the like. invention is also useful as an aqueous binder for coating
The polyester resin aqueous dispersion of the present in case of being incorporated with amino resins as men
invention is useful for the preparation of various lami tioned above. The aqueous binder for coating may also
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10
be incorporated with curing agents (e.g. acids such as (4) Viscosity: It was measured with a B type viscome
p-toluenesulfonic acid, dinonylnaphthalenedisulfonic ter at 20 C.
acid, hydrochloric acid), modifying agents (e.g. acrylic (5) Adhesion: It was measured by the method as dis
resin dispersion, epoxy resin dispersion, urethane resin closed in ASTM D-3359.
dispersion, aqueous polyisocyanate blocked with so (6) Tackiness of surface of the coating film: it was
dium hyposulfite etc.), organic or inorganic pigments, evaluated by finger touch.
additives for paints (e.g. acrylic additives, silicone addi (7) Solvent resistance: The coating film prepared
tives, fluorine additives), or the like. The aqueous from the aqueous dispersion was rubbed with a
binder for coating has excellent adhesion to metals and gauze impregnated with xylene until the substrate
also excellent water resistance, particularly resistance 10 appeared, and the time of rubbing was calculated.
against boiling water, and excellent anticorrosion, and is (8) Erichsen value: It was measured by the method as
useful for coating of cans and further as precoating, disclosed in JIS Z-2247.
wire coating, or baking coating. (9) Water resistance: It was measured by the method
The polyester resin aqueous dispersion of the present as disclosed in JIS 5400. .
invention is further useful as a surface treating agent for 15 (10) Gloss: It was measured with a glossmeter (Type
giving drip-proof to various products such as plastic VG 107, made by Nippon Denshoku Kogyo K.K.).
products (e.g. films, sheets or other articles of polyeth (11) Weatherability (degree of retention of surface
ylene terephthalate, polycarbonate or polyvinyl chlo gloss): After irradiating the coating film for 100 or
ride), glass products, metallic products, or the like. The 300 hours with Sunshine Weather-Ometer (made
surface treating agents for giving drip-proof may pref 20 by Atlas), the gloss was measured.
erably be incorporated with a nonionic surfactant, such The weatherability was also evaluated by measuring
as polyethylene glycol or its monocarboxylic acid ester, the change of appearance and adhesion after expos
monoalkyl ether, monoalkylphenyl ether, sorbitan ester ing the coating film outdoor for three months.
or polyethylenesorbitan ester, which have preferably an (12) Anticorrosion: It was measured by the method as
HLB of not less than 10, more preferably 13 to 30. The 25 disclosed in JIS Z-2371.
surface treating agent may also be incorporated with a (13) Anti-blocking properties: It was evaluated by
water-soluble resin, for example, polyvinyl alcohol or finger touch.
its derivatives such as saponified polyvinyl acetate, or a (14) Resistance against boiling water: After dipping
saponified product of a copolymer of vinyl monocar the coating film in boiling water for one hour, the
boxylate and vinyl monomer (e.g. ethylene, propylene, 30 degree of retention of surface gloss was measured.
styrene, vinyl chloride, acrylonitrile, acrylic acid, meth (15) Drip-proof: The inside wall of a stainless steel
acrylic acid, maleic acid, itaconic acid, or alkyl ester or vessel was treated with a surface treating agent for
hydroxyalkyl ester of these acids), wherein the saponifi giving drip-proof, and water was added to the
cation degree is preferably 40 to 100%, or an acetal vessel, which was heated at 50 C., and then, there
product of polyvinyl alcohol having an acetal degree of 35 was observed the formation of moisture condensa
not more than 20%. The surface treating agent may tion on the treated wall.
further be incorporated with other conventional addi Besides, the water resistance of the products treated
tives such as curing agents, curing promoters, weather with the surface treating agent for giving drip-proof
ing agents, lubricating agents, pigments, and further was evaluated by measuring the drip-proof, transpar
aqueous resins such as acrylic emulsion, acrylic disper ency and adhesion after washing the treated products
sion, polyvinyl acetate emulsion, polyvinyl chloride with flowing water for one hour.
emulsion, self-emulsifiable polyurethane, or the like. PREPARATION 1
The plastic products and glass products treated with the
surface treating agent show excellent transparency, Dimethyl terephthalate (95 parts), dimethyl iso
drip-proof and durability and are suitable as materials 45 phthalate (5 parts), ethylene glycol (71 parts), neopentyl
for horticultural house, materials for window, lens, or glycol (110 parts), zinc acetate (0.1 part) and antimony
the like. .. .
trioxide (0.1 part) were charged into a reactor and were
The present invention is illustrated by the following subjected to an ester exchange reaction at 140 to 220
Preparations and Examples, but is not limited thereto. C. for 3 hours. To the reaction mixture was added 5
In the Preparations and Example, "part' means part 50 sodium sulfo-isophthalic acid (6.0 parts), followed by
by weight unless specified otherwise, and various prop subjecting the mixture to an esterification reaction at
erties were measured in the following manner. 220 to 260° C. for one hour and further to a polycon
(1) Molecular weight: It was measured with a molec densation reaction under reduced pressure (10-0.2
ular weight measuring apparatus (115 type, made mmHg) at 240 to 270° C. for 2 hours to give a polyester
by Hitachi, Ltd.). 55 resin (B-1) having a molecular weight of 19,500 and a
(2) Softening point and melting point of crystals: softening point of 160 C.
They were measured with a wholly automatic In the same manner as described above except that
melting point apparatus (Model FP-1, made by the starting materials as shown in Table 1 were used,
Mettler Co.). there were obtained various polyester resins (B-2 to
(3) Particle size of the aqueous dispersion: It was 60 B-8), properties of which are shown in Table 1.
measured with a grindometer and a light micro
scope.
TABLE 1
Polyester resin of the Polyester resin of
Components (% by mole") , , present invention reference
and properties B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8
Poly- Terephthalic acid 49 30 47 30 50 - 80 68
 1.
4,340,519
12
TABLE 1-continued
Polyester resin of the Polyester resin of
Components (% by mole") present invention reference
and properties B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8
carboxylic Isophthalic acid 49 30 47 30 50 88 19 2O
acid 5-Sodium sulfo
component isophthalic acid 2 1.5 3 5 --- 12 2
Adipic acid - 38.5 m 30 --- -- O
Trinellitic acid
anhydride - - 3 5 - - - m

Polyol Neopentylglycol 60 35 58 35 60 - - 60
component Ethylene glycol 40 65 42 65 40 - 00 40
Diethylene glycol -- - -- -- - 100 --
Properties Softening point (C.) 60 110 30 92 157 - 230-k 68
Molecular weight 9500 7000 3900 5200 18300 20100 21000 550
*% by mole in polyester (measured by NMR)
**Melting point of crystal

PREPARATION 2 ins (B-10 to B-13), properties of which are shown in

Table 2.
TABLE 2
Polyester resins of Polyesters resins
Components (% by mole) the present invention of reference
and properties A-l A-2 A-3 B-9 B-10 B-11 B-12 B-13
Dicarboxylic acid
component:
Terephthalic acid 49 45
Isophthalic acid 48 50
5-Sodium sulfo
isophthalic acid
Adipic acid
Trimellitic acid
anhydride
Glycol component:
Ethylene glycol
Neopentylglycol
1,4-Butanediol 52
1,6-Hexanedioi 45
Diethylene glycof
Polytetramethylene
glycol (MW = 1000)
Properties:
Softening point (C.) 152 130 05 148
Melting point ("C.) 116 1 28 110
Heat of fusion
(cal/unit) 270 320 260 O O ()
Molecular weight 18000 16000 15000 7000 12000 15000 1500 2000

Dimethyl terephthalate (475 parts), dimethyl iso

phthalate (466 parts), dimethyl 5-sodium sulfo-isophtha 45 PREPARATION 3
late (45 parts), ethylene glycol (443 parts), neopentyl
glycol (400 parts), zinc acetate (0.44 part), sodium ace In the same manner as described in Preparation 2
tate (0.05 part) and antimony trioxide (0.43 part) were except that the starting materials as shown in Table 3
charged in a reactor and were subjected to an ester were used, there were obtained polyester resins (B-15 to
exchange reaction at 140 to 220 C. for 4 hours. The 50 B-18), properties of which are shown in Table 3.
pressure of the reaction system was gradually reduced TABLE 3
until 5 mmHg in one hour with raising the temperature Polyester
until 260° C. Finally, at 260° C. and under 0.1-0.3 Resin of
mmHg, the mixture was subjected to a polycondensa Components the present Polyester resin
tion reaction for one hour to give a non-crystalline 55 and(% by mole) invention of reference
polyester resin (B-9) having a molecular weight of 7,000 properties B-15 B-16 B.17 B-18
and a softening point of 152 C. As a result of NMR acid Polycarboxylic
analysis, the polyester resin (B-9) was composed of component:
terephthalic acid: 49% by mole, isophthalic acid: 48% Terephthalic acid 43 50 48 30
by mole, 5-sodium sulfo-isophthalic acid: 3% by mole, 60 Isophthalic acid 50 50 48 5
ethylene glycol: 52% by mole, and neopentyl glycol: 5-Sodium Sulfo Sebacic acid --- - - 50

48% by mole. Besides, the heat of fusion of the polyes

ter resin (B-9) was measured with a differential scanning isophthalic
Glycol
acid 7 - 4 s

calorimeter, but no endothermic peak was observed. component:

In the same manner as described above except that 65 Ethylene glycol - 45 50 50
the starting materials as shown in Table 2 were used, Neopentylglycol -
1,4-Butandediol
55 50 50
35 -- -- -

there were obtained various crystalline polyester resins Polytetra

(A-1 to A-4) and various non-crystalline polyester res methylene
 13
4,340,519
14
TABLE 3-continued TABLE 4
Polyester Non-solvent type
Resin of Components (% by mole) polyester resin
Components the present Polyester resin and properties P-1 P-2 P-3
(% by mole) invention of reference
and properties B-5 B-16 B-17 B-18 Polycarboxylic acid
component:
glycol Terephthalic acid 100 85 95
(MW = 1000) -- --- --- - Isophthalic acid 15
1,6-Hexanediol - - - Adipic acid
10 Trimellitic acid
DA-350 65 mem m --
Properties: anhydride
Molecular Glycol component:
weight 18000 16000 2000 25000 Ethylene glycol 68 100 65
Softening Lower than 1,4-Butandediol -

point (C.) 175 60 68 room temp. Neopentyl glycol 32 -

35
Melting Polytetramethylene
point (C) - -- u- -- 15 glycol (MW = 1000)
"DA-350: An adduct of ethylene oxide (2.5 mole) to bisphenol A (1 mole) (made by Properties:
Nihon Yushi) Melting point (C) - 216
Softening point (C) 175 82
Molecular weight 20000 18000 2800
PREPARATION 4 20
Dimethyl terephthalate (970 parts), ethylene glycol PREPARATION 5
(546 parts), neopentyl glycol (229 parts), zinc acetate
(0.44 part) and antimony trioxide (0.43 part) were Dimethyl terephthalate (95 parts), dimethyl iso
charged into a reactor and were subjected to an ester phthalate (95 parts), ethylene glycol (71 parts) neopen
exchange reaction at 140 to 220 C. for 3 hours. The 25 tylglycol (110 parts), zinc acetate (0.1 part) and anti
pressure of the reactor was reduced until 5 mmHg at mony trioxide (0.1 part) were charged into a reactor
220 to 260 C. in 30 minutes, and thereafter, the mix and were subjected to an ester exchange reaction at
ture was subjected to a polycondensation reaction at 140 to 220 C. for 3 hours. After adding thereto 5
265 C. and under 0.1 to 0.3 mmHg for 90 minutes to sodium sulfo-isophthalic acid (6.0 parts), the mixture
give a faint yellow, transparent polyester resin (P-1) 30 was subjected to an esterification reaction at 220 to
having a molecular weight of 20,000 and a softening 260 C. for one hour and further subjected to a polycon
point of 175° C. As a result of NMR analysis, the poly densation reaction at 240' to 270° C. under reduced
ester resin (P-1) was composed of terephthalic acid: pressure (10 to 0.2 mmHg) for 2 hours to give a polyes
100% by mole, ethylene glycol: 68% by mole and neo ter resin (B-19) having a moleculare weight of 19,500
pentylglycol: 32% by mole. 35 and a softening point of 160° C.
In the same manner as described above except that In the same manner as described above except that
the starting materials as shown in Table 4 were used, the starting materials as shown in Table 5 were used,
there were obtained polyester resins (P-2 and P-3), there were obtained polyester resins (B-20 to B-23),
properties of which are shown in Table 4. properties of which are shown in Table 5.
TABLE 5
Polyester resins of Polyesters resins
Components (% by mole) the present invention of reference
and properties B-19 B-20 B-21 B-22 B-23
Polycarboxylic acid
component:
Terephthalic acid 49 49 43 50 -
Isophthalic acid 49 48 20 50 88
5-Sodium sulfo
isophthalic acid 2 3 2 - 2
Adipic acid - - 30 - ---

Trinellitic acid
anhydride - - 5 - -

Glycol component:
Ethylene glycol 40 48 - 40 ---
Neopentyl glycol 60 --- 45 60 -
DA-350 r- 52 - - ---

Cyclohexanedi
methanol --- - 55 - -

Diethylene glycol -- -- -- - 100

Properties:
Softening point
(°C) 160 178 74 157 -m-
Molecular weight 19500 16000 3100 8300 20100

PREPARATION 6
65 In the same manner as described in Preparation 1
except that the starting materials as shown in Table 6
were used, there were obtained polyester resins (B-24 to
B-28), properties of which are shown in Table 6.
 4,340,519
5 16
TABLE 6
Polyester resins of Polyesters resins of
Components (% by mole) the present invention reference
and properties B-24 B-25 B-26 B-27 B-28
Acid component
Terephthalic acid 40 45 50 48 40
Isophthalic acid 40 45 50 40 30
5-Sodium sulfo
isophthalic acid 5 O - 2 30
Adipic acid 5 - -- - -
Glycol component:
Ethylene glycol 40 30 53 - 51
Neopentylglycol 20 ---- 47 - 49
1,6-Hexanediol - 40 -- - -
DA-350 40 30 -- - -
Diethylene glycol - --- - 00 -
Properties:
Molecular weight 5000 6000 5000 15000 12000
Melting point (C) 145 138 54 32 51

PREPARATION 7 20 PREPARATION 8
In the same manner as described in Preparation 1 In the same manner as described in Preparation 1
except that the starting materials as shown in Table 7 except that the starting materials as shown in Table 8
were used, there were obtained polyesters resins (B-29 were used, there were obtained polyester resins (B-37 to
to B-36), properties of which are shown in Table 7. B-42), properties of which are shown in Table 8.
TABLE 7
Polyester resins of
Starting materials (% by - the present invention - - - Polyester resins of reference -
mole) and properties B-29 B-30 B-31 B-32 B-33 B-34 B-35 B-36
Acid component:
Terephthalic acid 54 35 48 49 - 50 33 5
Isophthalic acid 43 31 48 48 90 50 42 2
Adipic acid - 30 - - - -- 70
Trimellitic acid - - 2 l - --- -- m
5-Sodium sulfo
isophthalic acid s 4. 2 2 10 m 5
Glycol component:
Ethylene glycol 45 - - 38 - 46 45 50
Neopentyl glycol 55 42 - - - 54 55 50
1,6-Hexanediol - - 56 62 m m
1,4-Cyclohexan
dimethanol - 58 - - - - m -

DA-350 - - 44 - --- --- -- --

Diethylene glycol - - - r- 00 re- -- -

Properties:
Molecular weight 15000 2000 5500 7000 6000 5000 2000 5000
Softening point (°C) 157 10 35 132 106 56 61 55

TABLE 8
Polyester resins of Polyesters resins of
Components (% by mole) the present invention reference
and properties B-37 B-38 B-39 B-40 B-4 B-42
Dicarboxylic acid
component:
Terephthalic acid 54 70 35 55 40 2
Isophthalic acid 43 25 32 5 38 s
5-Sodium sulfo
isophthalic acid 3 s 3. --- 2 l
Adipic acid - - 30 -- -- ---
Glycol component:
Ethylene glycol 45 50 50 46 85
Neopentyl glycol 55 39.5 - 54 ---- AS
1,4-Cyclohexane
dimethanol -- - -- - ---

Polyethylene
glycol (MW = 4000) - ).5 m-- m --
Diethylene glycol -- - - -- 100 m
DA-350 - - 50 -- m -

Properties:
Molecular weight 5000 7000 14000 4000 500 700
Softening point (C.) 57 S6 75 53 02 :35
 17
4,340,519
18
EXAMPLE 1. EXAMPLES 2 to 5
Polyester resin (B-1) (300 parts) and n-butyl cello In the same manner as described in Example 1 except
solve (140 parts) were charged into a vessel and were that the starting materials as shown in Table 9 were
agitated at 150 to 170° C. for about 3 hours to give a used, there were prepared some aqueous dispersions
homogeneous, viscous mixture. To the mixture was (X-2 to X-5), properties of which are shown in Table 10.
gradually added with vigorous agitation water (560 The aqueous dispersions (X-2 and X-5) were coated
parts) over a period of about one hour to give a faint onto a polyethylene terephthalate film (thickness: 125p)
bluish white aqueous dispersion (X-1). The aqueous in the same manner as in Example 1. The properties of
dispersion had a particle size of less than lu. When this 10 the resulting coating layers as well as those of Example
aqueous dispersion was allowed to stand at -5° C. for 1 are shown in Table 11.
20 days, no change of appearance and viscosity was
observed, and the aqueous dispersion showed excellent REFERENCE EXAMPLES 1 to 5
storage stability. In the same manner as described in Example 1 except
The aqueous dispersion (X-1) was coated onto a poly 15 that the starting materials as shown in Table 9 were
ethylene terephthalate film (thickness: 125p) with a bar used, there were prepared some aqueous dispersions
coater #20 in a thickness of 10u (in dry state) and then (X-6 to X-10), properties of which are shown in Table
dried at 100° C. for 20 minutes. The resulting coating 10.
layer had very excellent adhesion, and even when it was The aqueous dispersions (X-7 to X-9) were coated
dipped in water, it showed excellent water resistance 20 onto a polyethylene terephthalate film (thickness: 125u)
without showing any blushing. in the same manner as described in Example 1. The
properties of the resulting coating layers are also shown
in Table 11.
TABLE 9
Starting materials Example No. w Reference Example No.
(part) 2 3 4. 5 1 2 3 4 5
Aqueous dispersion X-1 X-2 X-3 X-4 X-5 X-6 X-7 X-8 X-9 X-10
Polyester resin (B-1) (B-2) (B-3) (B-4) (B-2) (B-5) (B-6) (B-7) (B-1) (B-8)
300 300 400 400 200 300 300 300 100 200
n-Butyl cellosolve 140 140 80 90 60 40 - 140 - -
Ethyl cellosolve M --- - 50 40 - - - -
Ethanol - - 20 - -- - - -- - -

Surfactant - - -- -- - m --- 4.

Water 560 560 500 560 700 560 700 560 900 700
"Surfactant: Noniolite AL-20 (made by Kyoeisha Yushi)

TABLE 10
Properties of aqueous Example No. Reference Example No.
dispersions 1 2 3 4. 5 1 2 3 4. 5
Aqueous dispersion X-1 X-2 X-3 X-4 X-5 X-6 X-7 X-8 X-9 X-10
Disper- State of O O O O O X O A A O
sibility dispersion"
Particle < <1 <1 <1 <1 - <10 <2000 <2000 <1
size(u)
Storage Change of No No No No No - Frozen Sepa- Frozen Frozen
stability appearance change change change change change rated sepa- sepa
(-5. C., rated rated
20 days) Change of No No No No No - Aqueous- al -
particle change change change change change disper
size sion
Change of <100 <100 < 100 <100 < 100 - could - - -
viscosity not be
(cps) recoV
ered
*O: Excellent dispersibility (faint bluish white aqueous dispersion),
A: Inferior dispersibility (white turbid dispersion was obtained, but it had wide range of particle distribution),
X: Entirely not dispersed (separated)
'They were evaluated after being allowed to stand at 25" C. for 24 hours.

TABLE 11
Properties of coating Example No. Reference Example No.
layer 1 2 5 2 3 4.
Aqueous dispersion X-1 X-2 X-5 X-7 X-8 X-9
Appearance Excellent Excellent Excellent Excellent Bad dis- Bad,
continuous uneven
layer thickness
Adhesion 100/100 100/100 100/100 100/100 Impos- 94/100
Water After Adhe- 100/100 100/100 100/100 45/100 sible 93/100
resist- dipping sion to No
ance" (25 C., Appear. No No No Blush- 82S No
3 days) ance change change change ing change
After Adhe- 100/100 100/100 100/100 Dis- 93/100
 4,340,519
19 20
TABLE 1 1-continued
Properties of coating Example No. Reference Example No.
layer. l 2 5 2 3 4.
dipping sion solved
(60° C., Appear- No No No Out No
2 hours) ance change change change change
"When it was coated and dired, it crystallized and no continuous layer was formed.
"It was evaluated after being dipped in water, followed by wiping up water.

TABLE 1.3
Reference
Example No. Example No.
Properties 9 10 8
EXAMPLES 6 to 8 15 Erichsen value (mm) >7 >7 >7 5
Adhesion 100/100 100/100 100/100 00/100
To the aqueous dispersion (X-1, X-3 Ot X-5) (each 100 Weatherability 72 78 18 46
parts) were added to a melamine resin (Sumimal M-50, (degree of retention (chalk
made by Sumitomo Chemical Co.) (10 parts) and a 50% of gloss, 9%) ing)
by weight solution (0.5 part) of a silicone compound 0 Wats E. For 97 98 45 40
(XF-3913, made by Toshiba Silicone Co.) in ethanol, 'E'
and the mixture was agitated well to give a homogene-
E,
(50° C., Adhesion 100/100 00/100 55/100 34/100
ous varish. The resulting varnish was coated onto a 150 hrs.)
polyethylene terephthalate film (thickness 100u) with a
bar coater #26 in a thickness of 10u (in dry state) and 25
baked at 100° C. for 30 minutes to give a hardened EXAMPLE 11
coating layer, properties of which are shown in Table In the same manner as described in Preparation 1,
12.
there was produced a polyester resin (B-43) which was
REFERENCE EXAMPLES 6 and 7 composed of terephthalic acid: 68% by mole, iso
In the same manner as described in the above Exam 30 phthalic acid: 20% by mole, 5-sodium sulfoisophthalic
ples 6 to 8 except that the aqueous dispersions (X-7 and acid: 3% by mole, ethylene glycol: 40% by mole and
X-10) were used, hardened coating layers were formed neopentyl glycol: 60% by mole, and had a softening
on a polyethylene terephthalate film (thickness: 125u). point of 135° C. and a molecular weight of 16,000.
The properties thereof are also shown in Table 12. In the same manner as described in Example 1 except
35 that the polyester resin (B-43) was used instead of the
TABLE 12 polyester resin (B-1), there was prepared and aqueous
Solvent dispersion (X-11), and the aqueous dispersion (X-11)
Example
Tacki
ness of
Resis Water resistance was coated onto a polyethylene terephthalate film
tance (25 C., days) (thickness: 125u) to form a coating layer. The proper
No. Adhesion surface (times) Adhesion Appearance 40 ties of the aqueous dispersion and coating layer are
Ex. 6 100/100 No >50 100/100 No change shown in Table 14.
Ex... 7 100/100 No 100/100
Ex. 8 100/100 No 100/100 TABLE 14
Ref.
Ex. 6
Properties of aqueous dispersion and coating layer Example 11
100/100 Yes 35 60/100 Blushing
Ref.
Ex. 7 45 Aqueous dispersion
Proper- Disper- State of dispersion"
X-1
d
100/100 No >50 40/100 Blushing
ties of sibili- Particle size (u) k
aqueous ty
disper- Storage Change of appearance No change
EXAMPLES 9 and 10 sion stabi- Change of particle size No change
lity Change of viscosity (cps) < 100
To the aqueous dipersion (X-1 or X-3) (each 100 50 (-5° C.
parts) were added a melamine resin (Suminal M-50, 20 days)
made by Sumitomo Chemical) (10 parts), a 50% by Proper- Appearance Excellent
ties of Adhesion 100/100
weight solution (0.5 part) of a silicone compound (XF coating Water After Adhesion 00/100
3913, made by Toshiba Silicone) in ethanol and titanium layer resis- dipping Appearance No change
oxide (10 parts), and the mixture was mixed with agita 55 ance (25° C.
tion and then kneaded with a three-roll mill to give a 3 days)
white composition. The resulting composition was After Adhesion 100/100
dipping Appearance No change
coated onto a soft steel panel with a bar coater #26 in a (60° C.
thickness of 10 (in dry state) and baked at 150° C. for 10 2 hrs.)
minutes. The properties of the resulting coating layer 60 *O: Excellent dispersibility (faint bluish white aqueous dispersion)
are shown in Table 13.
REFERENCE EXAMPLES 8 and 9 EXAMPLE 12
In the same manner as described in Examples 9 and 10 In the same manner as described in Example 7 except
except that the aqueous dispersions (X-7 and X-10) were 65 that the aqueous dispersion (X-11) was used instead of
instead of aqueous dispersion (X-1), there was formed a the aqueous dispersion (X-1), there were prepared a
coating layer, properties of which are also shown in coating composition and a coating layer. The properties
Table 13. of the coating layer are shown in Table 15.
 21
4,340,519
22
TABLE 1.5 one month, no change of appearance was observed, and
Properties of coating layer Example 12 the aqueous dispersion showed excellent storage stabil
ity.
Erichsen value (mm) >7 The aqueous dispersion (X-12) was coated onto a
Adhesion 100/100 5
Weatherability (degree of 70 polyethylene terephthalate film (thickness: 125u) with a
retention of gloss, 9%) bar coater #20 in a thickness of 100in dry state and
Water Degree of retention 95 then dried at 100° C. for 20 minutes. The resulting coat
resistance of gloss (%) ing layer had very excellent adhesion, and even when it
(50° C., Adhesion 100/100
150 hrs) was dipped in water for 7 days, and further even when
10 it was dipped in a hot water of 60° C. for one day, it
showed excellent water resistance without showing any
EXAMPLE 13 blushing.
The crystalline polyester resin (A-1) (120 parts, the EXAMPLES 14 to 16 AND REFERENCE
non-crystalline polyester (B-9) (180 parts) and n-butyl 15 EXAMPLES 10 to 16
cellosolve (140 parts) were charged into a vessel and the In the same manner as described in Example 13 ex
mixture was agitated at 150 to 170° C. for about 3 hours cept that the starting materials as shown in Table 16
to give a homogeneous viscous mixture. To the mixture were used, there were prepared aqueous dispersions
was gradually added with vigorous agitation water (560
parts (over a period of about one hour to give a faint 20 (X-13 to X-22), and further coating layers therefrom.
The properties of the aqueous dispersions and coating
bluish white aqueous dispersion (X-1). The aqueous layers are shown in Table 17 and Table 18, respectively.
dispersion had a particle size of less than 1. When this
TABLE 16
Example
Starting materials No, Reference Example No.
(part) 14 15 16 10 11 12 13 14 15 16
Aqueous dispersion X-13 X-14 X-15 X-16 X-17 X-18 X-19 X-20 X-21 X-22
Crystalline polyester A- A-2 A-3 A-1 A-1 A- A-1 A-1 A-1 A-1
resin 60 180 150 120 120 300 80 80 150 150
Non-crystalline poly- B-10 B-10 B-9 B-11 B-12 -- B-9 B-9 B-13 B-9
ester resin 140 120 150 180 180 120 120 150 150
n-Butyl cellosolve -- - 40 140 140 140 - --- 140 -
Ethyl cellosolve - 100 - - - - - - m
Dioxane 80 40 - m- - - - - m

Isopropanol 80 -- - -- - - - -

Surfactant* - - - - - - - 4 - --
Water 640 560 560 560 560 560 560 800 S60 700
*Noniolite AL-20, made by Kyoeisha Yushi Kagaku Kogyo K.K.

TABLE 17
Properties of aqueous Example No. Reference Example No.
dispersion 14 , 15 16 10 11 12 13 14 15 16
Aqueous dispersion X-13 X-14 X-15 X-16 X-17 X-18 X-19 X-20 X-21 X-22
Dispers- State of O O O O O X X O X X
ibility dispersion'
Particle <1 <1 <l <1 <1 > 100 100 <1 > 100 s 100
size (u) -
Storage Change of No No No No No Sepa- Sepa- Frozen, Sepa- Sepa
stabil- appearance change change change change change rated rated sepa- rated rated
ity rated
(-5. C., Change of No No No No No --- - - -- ---
1 month) particle" change change change change change
*O: Excellent dispersibility (faint bluish white aqueous dispersion), A: Inferior dispersibility (white turbiddispersion was obtained, but it had
wide range of particle distribution), X: Entirely not dispersed (separated)
"It was evaluated after being allowed to stand at 25 C. for 24 hours.
aqueous dispersion was allowed to stand at -5 C. for
TABLE 18
- Example No. --Reference Example No
Properties of coating layer 14 15 16 10 11 12 13 14 15 16
Aqueous dispersion X-13 X-14 X-15 X-16 X.17 X-18 X-19 X-20 X-21 X-22
Appearance Excel- Excel- Excel- Excel- Excel- Bad Bad Bad Bad ' Bad
lent lent lent lent lent
Adhesion 100/100 100/100 100/100 100/100 100/100 Impos- Impos- 92/100 Impos- Impos
Water After Adhesion 100/100 100/100 100/100 75/100 80/100 sible sible 90/00 sible sible
resist- dipping Appear- No No No Blush- Blush- tO to No to to
3Ce (25 C., ance change change change ing ing meas- meas- change meas- meas
7 days) ure ure ure ure
After Adhesion 100/100 100/100 100/100 0/100 25/100 86/100
dipping Appear- No No No Blush- Blush- Slight
(60 C, ance change change change ing ing ly
1 day) blush
 23
4,340,519
24
TABLE 18-continued
Example No. Reference Example No.
Properties of coating layer 14 5 16 10 2 13 14 5 16
ing

EXAMPLE 17 agitated for about one hour to give a homogeneous faint

bluish white aqueous dispersion CX-24).
The crystalline polyester resin (A-1) (150 parts), the 10 The aqueous dispersion (X-24 ) was coated into a
non-crystalline polyester resin (B-9) (150 parts), and steel panel coated with a melamine alkyd resin (Amilac
n-butyl cellosolve (140 parts) were charged into a vessel red, made by Kansai Paint Co.) with a cup gun in a
and were agitated at 150 to 170° C. for about 3 hours to thickness of 30 u, and dried at 100° C. for 10 minutes.
give a homogeneous viscous mixture. To the mixture When this product was subjected to a peel strength
was gradually added with vigorous agitation water (560 15 test at 180, it showed a peel strength of 60 g/cm and
parts) over a period of about one hour to give a homo could easily be peeled off with hand. When this test
geneous, faint bluish white aqueous dispersion. To this piece was dipped in hot water of 40° C. for 300 hours,
aqueous dispersion was added a methylated melanine the peelable paint composition did not show any disso
resin (Sumimal M-50 W, made by Sumitomo Chemical lution, Swelling, cracking and peeling, and when it was
Co.) (45 parts), and the mixture was agitated by give a 20 subjected to peel strength test, it showed a peel strength
homogeneous aqueous dispersion (X-23). This aqueous of 50 g/cm and could easily be peeled off with hand.
dispersion had a particle size of less than lu, and when Moreover, after this sample was irradiated with a sun
it was allowed to stand at -5° C. for one month, no shine weather-ometer for 100 hours and further exposed
change of appearance was observed, and the aqueous outdoor for 3 months, it was tested likewise. As the
dispersion showed excellent storage stability. 25 result, there was observed no deterioration such as
The aqueous dispersion (X-23) was coated onto a softening or cracking, and the peel strengths in each test
polyethylene terephthalate film (thickness: 125p) with a were 36 g/cm and 50 g/cm, respectively.
bar coater in a thickness of 10u (in dry state) and the Besides, the melamine alkyd paint which was coated
coating layer was hardened at 100° C. for 30 minutes to the steel panel had an initial gloss of 94, and the gloss
and then dried. The coating layer thus formed had an 30 thereof was still 94 even after subjected to tests for
excellent adhesion as 100/100, and excellent water resis water resistance and weatherability, which means that
tance. That is, even when it was dipped in water for 7 this peelable paint composition of the example does not
days and further even when it was dipped in hot water show any bad effect on the coating layer of the mala
of 60° C. for one day, it did not show any blushing. mine alkid paint but rather shows protective effect.
EXAMPLES 18 TO 21 AND REFERENCE 35 When the peelable paint composition was not coated,
EXAMPLE 17 TO 21 the melamine alked paint-coated steel panel showed a
gloss of 94 after being subjected to water resistance, a
The aqueous dispersions prepared in Example 13 to gloss of 92 after irradiation with a sunshine weatherom
15 and 17 and Reference Examples 10 to 14 were each eter, and a gloss of 92 after being exposed outdoor.
coated onto a suede cloth of 100% polyester with a bar In the same manner as described above, various aque
coater #20 and then dried at room temperaure for 24 40 ous dispersions were prepared by using polyester resins
hours. The coated cloths were piled up by facing each as shown in Table 20, and the aqueous dispersions were
coated surface and bonded at 150° C., under pressure of tested. The results are shown in Table 21.
300 g/cm2 for 10 minutes. The adhesion (peal strength) TABLE 20
of the bonded cloths was measured with an Instrone Ref
eference
type peel strength tester (made by Shimazu Seisakusho), Aqueous dispersion and Example Example No.
Besides, the bonded cloths were dipped in hot water of - thereof - 22 Examp23 No. 24 --
60°O C. for one day, and the adhesion (peal strength) was dispersibility 22
X
also measured, and the retention thereof was calculated. So insion : g B-1s
The results are shown in Table 19. (part) 300 300 50 300
TABLE 19
Example No. . . . . Reference Example No. --
Properties 18 19 20 21 17 8 9 20 2.
Aqueous dispersion X-12 X-13 X-14 X-23 X-16 X-17 X-18 X-19 X-20
Initial 1.2 0.87 0.94 1.6 1.1 0.22 Impos- Impos- 0.88
Adhesion (kg/cm) sible sible
Adhesion (kg/cm) to to
after dipping COat Coat
at 60° C. for 1.0 0,74 0.80 1.4 0.64 0.08 0.47
1 day
Retention (%) 83 85 85 88 58 36 53

EXAMPLE 22 P.
The polyester resin (B-15) (300 parts was mixed into 65 -Buty tly (part) O 70 . -
n-butyl cellosolve (70 parts), and the mixture was added Ele (part) o to o too
with vigorous agitation into a mixture of isopropanol Water (part) 560 560 560 -
(70 parts) and water (506 parts), and the mixture was Dispersibility Excel. Bad Excei- Excel
 25
4,340,519
26
TABLE 20-continued dried at 100 C. for 5 minutes and then cured at 240 C.
Reference
for one minute.
Aqueous dispersion and Example Example No. Onto the coating layer thus formed was coated poly
dispersibility thereof 22 22 23 24 ester resin (P-1) which was previously mixed with 20%
lent lent lent by weight of titanium oxide with an extruder at 220 C.
in a thickness of 70p to give a coated steel panel. Prop
erties of this coated steel panel were tested. As a result,
TABLE 21 it showed excellent mechanical strength, water resis
Properties of peelable Example Reference Example No. 10 tance and anticorrosion, as shown in Table 22.
paint composition 22 22 23 24 EXAMPLE 25
Aqueous dispersion X-24 X-25 X-26 -
Initial gloss (%) of 94 94. 94 In the same manner as described in Example 23, the
melamine alkyd paint polyester resin (B-21) (300 parts) was dissolved in n
Initial peel strength 60 Hardly Hardly 130 butyl cellosolve (70 parts) and butyl acetate (30 parts),
(g/cm) coated peeled 15
and thereto was gradually added water (600 parts) to
Water Change of No Crack- No
resist- appearance change ing change give an aqueous dispersion (X-29).
2C8 Peel strength 50 Hardly 105 To the aqueous dispersion (X-29) was added a water
(g/cm) peeled soluble melamine resin (Sumimal M-50W) (40 parts).
Sun- Change of No Crack- No
shine appearance change ing change 20 The resulting homogeneous mixture was coated onto a
weath- Peel strength 36 Hardly 90 cold-rolled steel panel (thickness: 0.8 mm) with a bar
er-
oneter
(g/cm)
Gloss of coating 92
peeled
- 82
coater in a thickness of 6p, dried at 100° C. for 5 minutes
and then cured at 240 C. for one minute.
layer (%) Onto the coating layer thus formed was coated a
Ex- Change of No Crack- No
posed appearance change ing change 25 powder coating composition which was prepared by
outdoor Peel strength 50 Hardly 95 mixing the polyester resin (P-3) (1000 parts), a crosslink
(g/cm) peeled ing agent (U-I, made by Bayer) (220 parts), titanium
Gloss of coating 92 - 84
layer (%) oxide (400 parts), polyflow (made by Kyoeisha Yushi
It was difficult to completely peel the coating layer, since apart of the coating layer Kagaku Kogyo) (5 parts) and dibutyl tin dilaurate (3
was broken by peeling thereof. 30 parts) and pulverizing the mixture. The coating was
carried out with an electrostatic coating machine in a
EXAMPLE 23
thickness of 50 and then the coating layer was cured at
180 C. for 20 minutes to give a coated steel panel.
The polyester resin (B-19) (300 parts) and n-butyl Properties of this coated steel panel were tested. As a
cellosolve (140 parts) were charged into a vessel and 35 result, it showed excellent mechanical strength, water
agitated at 150 to 170° C. for about 3 hours to give a resistance and anticorrosion, as shown in Table 22.
homogeneous viscous mixture. To the mixture was
gradually added with vigorous agitation water (560 REFERENCE EXAMPLE 25
parts) over a period of about one hour to give a faint Without coating any aqueous dispersion, the polyes
bluish white aqueous dispersion (X-27). 40 ter resin (P-2) was coated onto a cold-rolled steel panel
To the aqueous dispersion (X-27) was added a water (thickness: 0.8 mm) treated with zinc phosphate with an
soluble melamine resin (Sumimal M-50W, made by extruder at 240° C. in a thickness of 50 to give a coated
Sumitomo Chemical Co.) (35 parts), and the mixture steel panel. Properties of this coated steel panel were
was mixed well to give a homogeneous aqueous disper tested. As a result, it did not show sufficient adhesion
sion. This dispersion was coated onto a cold-rolled steel 45 and it was inferior in the anticorrosion, too.
panel (thickness: 0.8 mm) treated with zinc phosphate
with a roll coater in a thickness of 10, dried at 100 C. REFERENCE EXAMPLE 26
for 5 minutes and then cured at 240 C. for one minute. In the same manner as described in Example 23, the
Onto this layer thus formed was coated the polyester polyester resin (B-22) (300 parts) was dissolved in n
resin (P-1) at 240 C. with an extruder in a thickness of 50 butyl cellosolve (140 parts), and thereto was gradually
50p to give a coated steel panel. Properties of this added water (560 parts). However, the polyester resin
coated steel panel were tested. As a result, it showed coagulated and there could not be obtained any stable
excellent mechanical strength, water resistance and aqueous dispersion, and the mixture could not be coated
anticorrosion, as shown in Table 22. onto a steel panel.
55
EXAMPLE 24 REFERENCE EXAMPLE 27
In the same manner as described in Example 23, the In the same manner as described in Example 23, the
polyester resin (B-20) (300 parts) was dissolved in n polyester resin (B-23) (300 parts) was dissolved in hot
butyl cellosolve (80 parts) and cyclohexanone (60 water of 70 to 90° C. (700 parts), and the mixture was
parts), and thereto was gradually added water (560 60 agitated for about 3 hours to give a homogeneous aque
parts) to give an aqueous dispersion (X-28). ous dispersion (X-30).
To the aqueous dispersion (X-28) were added a To the aqueous dispersion (X-30) was added a water
water-soluble melamine resin (Sumimal M-50W) (45 soluble melamine resin (Sumimal M-50 W) (35 parts),
parts) and a homogeneous dispersion (100 parts) of and the resulting homogeneous mixture was coated
titanium oxide (50% by weight as solid component) in 65 onto a cold-rolled steel panel (thickness; 0.8 mm)
ethylene glycol. The resulting homogeneous mixture treated with zinc phosphate with a roll coater in a thick
was coated onto a cold-rolled steel panel (thickness: 0.8 ness of 10, dried at 100° C. for 5 minutes, and then
mm) treated with zinc phosphate in a thickness of 10, cured at 240 C. for one minute.
 4,340,519
27 28
Onto the coating layer thus formed was coated the
polyester resin (P-2) with an extruder at 240° C. in a EXAMPLE 28
thickness of 50p to give a coated steel panel. Properties The polyester resin (B-29) (300 parts) and n-butyl
of this coated steel panel were tested. As a result, it cellosolve (140 patts) were charged into a vessel and
showed insufficient water resistance and anticorrosion, 5 were agitated at 150 to 170° C. for about 3 hours to
as shown in Table 22. give a viscous mixture. To the mixture was gradually
TABLE 22
Properties of - Example No- Reference Example No.
coating layer 23 24 25 25 36 27 r
Apperance Excel- Excel- Excel- Good Excel
lent lent lent Impos- lent
Adhesion OO/100 100/100 100/100 0/100 sible 100/100
Erichsen value 7.< 7.< 7.< 7.< to 7(
(mm) coat
Water resistance 100/100 00/100 100/100 O/100 O/100
Anticorrosion* 1> ld 1> 4.5 3.2
(mm)
*It was evaluated after being kept at 50 C. for 300 hours.
**It was evaluated in account of the width corroded after being dipped in water at 40 C. for 500 hours.

added with vigorous agitation water (560 parts) over a

period of about one hour to give a homogeneous, faint
bluish white aqueous dispersion. To this aqueous disper
EXAMPLES 26 AND 27 AND REFERENCE sion (100 parts) was added an amino resin (Sumimal
EXAMPLES 28 TO 30 M-50W, made by Sumitomo Chemical Co., in the form
- (B-24 to B-28) were each added ' of
The polyester resins of aa 80%
80% by
by weight lution) (20
weight aqueous solution) (20 parts) to gi
to give
to a mixture of water and isopropanol (and n-butyl an aqueous binder for C9ating which contained the
cellosolve or tert-butyl cellosolve in Examples 26 and polyester resin (B-29): 25% by weight, the amino resin:
27) in an amount as shown in Table 23, and the mixture 13% by Weight, a Water compartible organic Com
was mixed at 70 to 75° C. for 3 hours to give aqueous 30 pound: 12% by weight, and water: 50% by weight.
binders for printing ink, which had a particle size of less The aqueous binder was allowed to stand at 0°C. and
than 1. After these binders were kept at 0° C. for one 40C for one month, but any change of appearance was
month, the state of dispersion was observed. The results
are shown in Table 23.
notToobserved -
the aqueous binder (100 parts) were added a ho
The binders (aqueous dispersion) thus formed (100 s togenous dispersion of titanium oxide in ethylene
parts), titanium oxide (15 parts) and a 50% by weight glycol (solid content: 50% by weight) (40 parts) and a
solution (0.5 part) of a silicone compound (XF-3913, 50% by Weight solution (0.5 part) of a painting additive
made by Toshiba Silicone Co.) were mixed with a ball (XF-3913, made by Toshiba Silicone Co.) in ethanol,
mill to give a white aqueous ink. This ink was coated and the mixture was mixed well to give an aqueous
onto a polyethylene terephthalate film (thickness: 125u) to conting composition
with a bar coater #20 in the thickness of 7u and dried at The aqueous coating composition was coated onto a
70° C. for 2 minutes. The properties of the coating layer cold-rolled steel panel treated with zinc phosphate with
were measured. The results are shown in Table 23. a bar coater #36 in a thickness of 20, dried at 150° C.
for 2 minutes and baked at 250 C. for 2 minutes. The
- ABE- coating layer thus formed had excellent gloss and
Components Example No. Reference Example No. smoothness and further had a pencil hardness: 2H, Er
(% by weight) 26 27 28 29 30 ichsen value: more than 7 mm, and adhesion: 100/100,
Polyester 35 - - - - an adhesion after testing the water resistance for 300
resin B-24 hours: 100/100, a width corroded after testing anticor
E. -- 35 - - rosion for 300 hours: 2.5mm, and a degree of retention
Polyester - -- 30 - - of gloss after testing boiling water resistance: 95%.
it is - - - 30 - EXAMPLES 29 to 31 AND REFERENCE
resin B-27 EXAMPLES 31 TO 33
Eis - --- -- --- 30 In the same manner as described in Example 28,
Isopropanol 10 8 14 14 4. various aqueous binders were prepared by using the
n-Butyl 3 - - - starting materials as shown in Table 24. Properties of
sely - 4 - - - the aqueous binders are shown in Table 24.
E. By using these aqueous binders there were prepared
Water 52 53 56 56 56 aqueous coating compositions which were coated onto
Dispers- Excel. Excel. Bad Excel. Excel. 99 a cold-rolled steel panel likewise to form coating layers.
ibility
Gloss lent
86 lent
85 -- lent
82 lent
78 2 show n in Table
Properties of the coating layers are al 25.
Anti- Excel- Excel- - Bad Bad
blocking lent lent TABLE 24
Adhesion 100/100 100/100 - 100/100 25/100
Water No No - Losing Losing 65 Reference
resistance" change change gloss gloss Components - Example No. - Example No.
*After being dipped in water at 30 C. for one day; the appearance was observed. (% by weight) 28 29 30 31 31 32 33
Polyester resin B-29 B-30 B-31 B-32 B-33 B-34 B-35
 29
4,340,519 30
TABLE 24-continued period of about one hour to give a homogeneous, faint
Refeference bluish white aqueous dispersion.
Components Example No. Example No. To the aqueous dispersion (1,000 parts) were added a
(% by weight) - tape
29 30 - 31 - a No-32
33 10% by weight aqueous solution (300 parts) of a non
25 30 40 5 ionic surfactant (Nissan Nonione E-230, made by Nihon
Ami O Sin 13 15 10 3512 25
13 25
13 25
13 Yushi) and a 10% by weight aqueous solution (150
Organic compounds parts) of polyvinyl alcohol (GL-05, made by Nihon
compatible with Gosei) to obtain
w aw treatinggag
agent for g1V1ng
giving drip-proof.
drip-p
St. ceilosolve
n-Butyl losol 12 4 5 6 12 12 12 When this treating agent was allowed to stand at 40”
t-Butyl cellosolve ' ' ' ' ' ' ', 10 C. for 2 months, any change of appearance was ob
Cyclohexanone - - 5 - - - - served.
Isopropanol - - - 4 - - - This treating agent was coated onto aa polyetny
gagent polyethylene
al f
E. or
E.x- E.
Ex- Ex- Ex
fn- E. 50
Ex- Ex-
terephthalate film (thickness: 25u) with a bar coater
#18 in a thickness of 2p (in dry state), and dried at 105
1spersion in cel- cel- cel- cel- fer- cel- cel
water
Storage at O' C.
in ent ent in for lent in 15 excellent
Ex- Ex- Ex- Ex- - Ex- Ex-
C. for 5 minutes. The coating layer thus formed had
drip-proof properties and had an adhesion:
bill-
ity ii. it. it. i
e e it. f
en 100/100, adhesion after washing with water for one
el e c
at 40 C. Ex- Ex- Ex- Ex- - Ex- Ex- hour: 100/ 100, and further no change of transparency
cel- ce- cel- cel- cel- cel- and drip-proof properties was observed.
lent lent lent lent lent lent 20
EXAMPLES 33 AND 34 AND REFERENCE
EXAMPLES 34 TO 36
TABLE 25 In the same manner as described in Example 32, vari
Reference ous treating agents for giving drip-proof were prepared
Properties of - 28 Example
coating layer 29 30
No. 31 31
Example
32
No. 22 25 by using the starting materials as shown in Table 26.
The treating agents were coated onto a polyethylene
Smoothness Ex- Ex- Ex- Ex- Ex- Good terephthalate film to form a coating layer, likewise. The
cel- cel-
lent lent cel- cel-
lent lent cel-
lent properties of the coating layer are shown in Table 27.
Pencil hardness 2H H H F Hardly 2H 2B
coated 30 TABLE 26
Gloss 92 86 87 87 74 65 Ref
Erichsen value >7 >7 >7 >7 >7 >7 eference
(mm) Components Example No. Example No.
Adhesion 100/ 100/ 100/ 100/ 100/ 100/ (part by weight) 32 33 34 34 35 36
100 100 00 100 100 100 '
Adhesion after 100/ 100/ 100/ 100/ ?o, 35 Polyester resin : ; ; ; ; ;
testing of water 100 100 100 100 100 100 Nonionic surfactant:
resistance
Anticorrosion
(mm)
2.5 3.0 1.5 3.0 5.0 a 10 NaNini. -1.J.-r
so to
--- m ..
- as
- -
as
m

Degree of 90 85 88 85 4S 20 SEGanic 15 - 10 - -
retention of 40 compounds: 3.
E. foil. n-Butyl cellosolve 50 50 60 60 - m
in Site Isopropanol -- --- - - 50
St. Water 155 1110 1055 740 950 975
State of dispersion Ex- Ex- Ex- In- Ex- Ex
in water cel- cel- cel- fer- cel- cel
45 lent lent lent ior lent lent
EXAMPLE 32 Stability (40 C, 2 months) Ex- Ex- Ex- - Ex- Ex
cel- cel- cel- cel- cel
The polyester resin (B-37) (200 parts) and n-butyl lent lent lent lent lent
cellosolve (50 parts) were charged into a vessel and
TABLE 27
Properties of Example No. Reference Example No.
coating layer 32 33 34 35 36
Clouding" (%) 1. 1 1 1 2
Dip-proof properties Excellent Excellent Excellent Excellent Excellent
Adhesion 100/100 100/100 100/100 100/100 70/100
After Drip-proof
washing properties Excellent Excellent Excellent. Dissolved Peeled
with Adhesion 100/100 100/100 100/100
flowing Clouding (%) 1 1 1
water
for
1 hour
"Clouding, less than 10% = excellent transparency
10% or more = inferior transparency
65
were agitated at 150 to 170° C. for about 3 hours to EXAMPLE 35
give a viscous mixture. To the mixture was gradually A woven fabric of 100% polyester spun was padded
added with vigorous agitation water (750 parts) over a with the aqueous dispersion (X-1) and was squeezed at
 4,340,519
3. 32
a squeezing degree of 70%, and thereafter, the resultant carbon atoms and 80 to 0% by mole of bisphenol A
was dried at 120° C. for 5 minutes, soaped with a neutral ethylene oxide or propylene oxide adduct,
detergent (0.2 g/liter) at 60° C. for 5 minutes, washed (C) a water-soluble organic compound having a boil
with water for 5 minutes, and dried with press. The thus ing point of 60° to 200° C., and
treated woven fabric had properties as shown in Table 5 (D) water, said components (A), (B), (C), and (D)
28. being incorporated in the following weight ratio:
EXAMPLE 36
A/B=0-95/100-5 (1)
The aqueous dispersion (X-1) (100 parts) and Sumitex
M-3 (made by Sumitomo Chemical Co.) (4 parts) were 10 A-B/C/D=10-70/2-40/20-88 (2)
mixed with agitation to give a treating agent.
In the same manner as described in Example 35 ex 0.02s C/C+Ds0.66. (3)
cept that the treating agent as obtained above was used
instead of the aqueous dispersion (X-1), a woven fabric 2. An aqueous dispersion according to claim 1, which
was treated wherein the fabric was dried at 100 C. for 15 comprises
2 minutes and subjected to heat-treatment at 160C. for (B) a non-crystalline polyester having a molecular
2 minutes. The properties of the fabric are also shown in weight of 2,500 and 30,000 and a softening point of
Table 28. 60 to 180 C. and comprising polycarboxylic acid
REFERENCE EXAMPLE 37
components consisting of 40 to 99.5% by mole of
20 an aromatic dicarboxylic acid having no metal
Sumitex M-3 (100 parts), Sumitex AC-C (10 parts) sulfonate group, 59.5 to 0% by mole of an aliphatic
and water (100 parts) were mixed with agitation to give or alicyclic dicarboxylic acid having 4 to 36 carbon
a treating agent. atoms and 0.3 to 10% by mole of an aromatic dicar
In the same manner as described in Example 35 ex boxylic acid having a metal sulfonate group, and
cept that the treating agent as obtained above was used 25 polyol components consisting of 20 to 100% by
instead of the aqueous dispersion (X-1), a woven fabric mole of an aliphatic glycol having 2 to 8 carbon
was treated. The properties of the fabric are also shown atoms and/or an alicyclic glycol having 6 to 12
in Table 28. carbon atoms and 80 to 0% by mole of bisphenol A
TABLE 28 ethylene oxide or propylene oxide adduct,
Properties of the Example No. Reference Example No. 30 (C) a water-soluble organic compound having a boil
treated fabric 35 36 37 ing point of 60' to 200 C., and
Hardness" (mm) 58 67 70 (D) water, said components (B), (C) and (D) being
Retention of hardness' incorporated in the following weight ratio:
after washing for
5 times (%) 75 80 45 35 B-C-D=100 (1)
"It was measured by cantilever method.
"Degree of retention of hardness after 5 times repeat of washing with a neutral B/C/D=10-70/2-40/20-88 (2)
detergent (1 g/liter) at 40 C. for 10 minutes, washing with water for 10 minutes and
drying with press in comparison with that before washing.
0.02s C/C--Ds(0.66. (3)
What is claimed is:
1. An aqueous dispersion of polyester resin which 3. An aqueous dispersion according to claim 1,
comprises wherein the crystalline polyester comprises 50 to
(A) a crystalline polyester having a molecular weight 99.5% by mole of an aromatic polycarboxylic acid se
of 2,500 to 30,000 and a melting point of 70 to 200 lected from the group consisting of terephthalic acid
C. and, comprising polycarboxylic acid compo 45 and isophthalic acid as the polycarboxylic acid compo
nents consisting of 40 to 99.5% by mole of an aro nent and 85 to 100% by mole of a polyol selected from
matic dicarboxylic acid having no metal sulfonate as the group consisting of ethylene glycol and butanediol
group, 59.5 to 0% by mole of an aliphatic or alicyc the polyol component.
lic dicarboxylic acid having 4 to 36 carbon atoms 4. An aqueous dispersion according to claim 1 or 2,
and 0.5 to 10% by mole of an aromatic dicarboxylic 50 wherein the non-crystalline polyester comprises 10 to
acid having a metal sulfonate group, and polyol 80% by mole of terephthalic acid as the polycarboxylic
components consisting of 20 to 100% by mole of an acid component and 20 to 80% by mole of a polyol
aliphatic glycol having 2 to 8 carbon atoms and/or selected from the group consisting of ethylene glycol
an alicyclic glycol having 6 to 12 carbon atoms and and butanediol as the polyol component.
80 to 0% by mole of bisphenol A ethylene oxide or 55 5. An aqueous dispersion according to claim 1 or 2,
propylene oxide adduct, wherein the polyester (B) is copolymerized with a tri
(B) a non-crystalline polyester having a molecular or more polycarboxylic acid selected from trimellitic
weight of 2,500 to 30,000 and a softening point of acid and pyromellitic acid in an amount of 0.01 to 10%
60 to 180 C. and comprising polycarboxylic acid by mole based on the total polycarboxylic acid compo
components consisting of 40 to 99.5% by mole of 60 nentS.
an aromatic dicarboxylic acid having no metal 6. An aqueous dispersion according to claim 1 or 2,
sulfonate group, 59.5 to 0% by mole of an aliphatic wherein the polyester (B) is copolymerized with a tri
or alicyclic dicarboxylic acid having 4 to 36 carbon or more polyvalent polyol selected from trimethylol
atoms and 0.5 to 10% by mole of an aromatic dicar propane, trimethylolethane, glycerine and pentaerythri
boxylic acid having a metal sulfonate group, and 65 tol in an amount of 0.01 to 10% by mole based on the
polyol components consisting of 20 to 100% by total polyol components.
mole of an aliphatic glycol having 2 to 8 carbon 7. An aqueous dispersion according to claim 1 or 2,
atoms and/or an alicyclic glycol having 6 to 12 wherein the polyester (B) is copolymerized with a poly
 33
4,340,519
34
alkylene glycol having a molecular weight of 106 to selected from the group consisting of an amino resin, an
10,000 in an amount of 0.01 to 5% by weight based on epoxy resin and an isocyanate compound. .
the total weight of the polyol components. 10. An aqueous dispersion according to claim 1,
8. An aqueous dispersion according to claim 1 or 2,
wherein the glycol component of the non-crystalline 5 wherein the water-soluble organic compound is a mem
polyester is a combination of ethylene glycol and neo ber selected from the group consisting of an ethylene
pentyl glycol in a molar ratio of 70:30 to 30:70. glycol monoalkyl ether and a monoalcohol having a
9. An aqueous dispersion according to claim 1, which boiling point of 100° C. or higher.
is additionally incorporated with at least one compound k k is k
10

15

20

25

30

35

45

50

55

65