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United States Patent [19]

[H]

4,181,761

Ishimoto et al.

[45]

Jan. 1, 1980

[54] SHAPED ARTICLES OF ETHYLENE-VINYL


ACETATE COPOLYMER HAVING A
COATING OF NCO-FREE
RADICAL-CONTAINING SYNTHETIC
RESIN PAINT
[75] Inventors: Ryoji Ishimoto; Katsuhiko Hasuo,
both of Ichihara; Masanori Hisatomi,
Kisarazu; Kensaku Yamawaki,
Ichihara; Sadao Masuda, Chiba;
Seiichi Tada, Ichihara, all of Japan
[73] Assignee:

Mitsui Polychemicals Co., Ltd.,


Tokyo, Japan

[21] Appl. No.: 967,713


[22] Filed:
[30]

Dec. 8, 1978

Foreign Application Priority Data

Dec. 12, 1977 [JP]

Japan

'.

52-148197

[51] Int. a.2


B60R 13/00; B60R 13/02
[52] U.S. Cl
428/31; 293/1;
428/409; 428/420; 428/423; 428/425; 428/520;
428/522
[58] Field of Search
428/420, 423, 522, 520,
428/425, 409, 31; 293/1, 126, 128
[56]

References Cited
U.S. PATENT DOCUMENTS

3,198,692
3,790,437
3,877,969
3,889,031
3,949,114

8/1965
2/1974
4/1975
6/1975
4/1976

Bridgeford
Haley
Tatsumi
Tatsumi
Viola

428/420
428/425
428/425
428/425
428/425

4,082,854

4/1978

Yamada

428/522

FOREIGN PATENT DOCUMENTS


49-41088 7/1974 Japan .
49-31785 12/1974 Japan .
52-27453 1/1977 Japan .
Primary ExaminerEllis P. Robinson
Attorney, Agent, or FirmSherman & Shalloway
[57]

ABSTRACT

A shaped article composed of a substrate of an EVA


copolymer and a coating of a paint containing an NCOfree radical bonded firmly to the substrate, said substrate being either
.,..(.). shaped article of EVA copolymer having a
vinyl acetate content of about 3 to about 35% by
weight, the article having a coating on its surface
formed from a solution of a resin selected from
specified resins (aj), (32), (33) and (34),
(B) a shaped article of a blend of EVA copolymer
having the vinyl acetate content as defined above
1
with a resin selected from specified resins (bi), (b2),
(ba) snd (b4),
(B') 3 shaped article of a graft copolymer of EVA
having the vinyl acetate content as defined above,
and grafted thereto, at least one specified monomer, or
(B") a shaped article resulting from the saponificstion
of the surface of a shaped article of EVA copolymer having the vinyl acetate content as defined
above.
5 Claims, No Drawings

4,181,761
likely to affect the desirable properties of the EVA
copolymers, and therefore, such a modifying procedure
is difficult to perform commercially. Another method
of improvement would be to form on the surface of
such an EVA copolymer srticle a coating of a material
capable of improving abrasion resistance, for example a
paint capable of imparting such a property. However,
This invention relates to shaped articles of an ethyas is well known, such a paint cannot be adhered firmly
lene-vinyl acetate copolymer (to be sometimes referred
because ofthe poor surface activity ofthe EVA copolyto hereinbelow as "EVA copolymer") having a surface
of improved physical properties, especially scratch or 10 mer article. It is difficult therefore to utilize the coating
technique. In order to improve the adhesion of the
abrasion resistance, without adversely affecting the
surface of the EVA copolymer article and to form a
desirable properties of the shaped articles themselves.
firmly 3dhering costing of a suitable material on it, it
Specifically, it relates to shaped articles of EVA cowould be feasible to employ a flame spray treatment,
polymer having a firmly bonded coating of an isocyanato-free radical-containing synthetic resin paint such as a 15 corona discharge treatment, a treatment with a mixture
of chromic acid and sulfuric acid, etc. which are the
polyurethane-type paint which has previously been
generally known surface treating methods for olefinic
unable to be bonded firmly to the surfaces of shaped
resins. The flame spray treatment and corona discharge
articles from EVA copolymer.
treatment however, have the defect that shaped articles
More specifically, the invention relates to a shaped
article comprising (A) a shaped article of an EVA co- 20 of complex configurations cannot be uniformly treated,
or long periods of time are required, or the working
polymer of a specified vinyl acetate content having a
efficiency is poor. The mixture of chromic acid and
coating formed from a solution of a resin selected from
sulfuric acid, on the other hand, degrades the EVA
specified resins (ai), (a2), (33) and (34) fonned on the
copolymer or is likely to become a source of pollution.
surface of (A), and (C) a coating having an elongation
of at least 10% and composed of an isocyanate-free 25
The present inventors made investigations in an atradical-containing synthetic resin paint; or comprising a
tempt to provide a method for improving the surface
shaped article (B) of a blend ofthe EVA copolymer and
characteristics of shaped articles of EVA copolymer
a specified amount of a resin selected from specified
which has not been commercially practised in the past,
resins (bi), (hz), (ba) and (bi), a shaped article (B') ofa
and shaped articles of EVA copolymer having imgraft copolymer composed of an EVA copolymer of a 30
proved surface characteristics.
specified vinyl acetate content and a specified monomer
These investigations led to the discovery that shaped
grafted thereto, or (B") a shaped article resulting from
articles
of EVA copolymers having improved surface
the saponification ofthe surface of a shaped article of an
characteristics such as abrasion or scratch resistance
EVA copolymer of a specified vinyl acetate content
and formed on the surface of (B), (B') or (B"), the afore- 35 and appearance can be provided without adversely
affecting the desirable properties of the EVA copolysaid coating (C).
mer by forming a coating on the surface of a shaped
The invention also relates to a method for improving
article (A) of an EVA copolymer having a specified
the surface adhesiveness of a shaped article of an EVA
vinyl acetate content from a solution of a resin selected
copolymer which can be sdvantsgeously utilized in
providing the aforesaid shaped articles having the coat- 40 from the group consisting of (ai), (32), (33) snd (34), 3nd
then forming on the resulting costing a firmly adhering
ing (C).
coating (C) having an elongation of at least 10% from a
EVA copolymers have many advantages including
paint capable of forming a coated film at a temperature
good pliability, rubbery elasticity, ease of molding and
below
the heat softening temperature or heat distortion
low cost, and are widely used as films, sheets, laminates,
foams, adhesives, and other various kinds of shaped 45 temperature of the shaped article of the EVA copolymer; or by forming the coating (C) on the surface of a
articles. The shaped articles of EVA copolymers, howshaped article (B) of a blend of the aforesaid EVA coever, are limited in their application because of the
polymer and a specified amount of a resin selected from
unsatisfactory physical properties of their surfaces, esthe group consisting of (bi), (b2), (hs) and (b4), or a
pecially their poor abrasion or scratch resistance, and
their utilization at present is confined to applicstions 50 shaped article (B') of a graft copolymer of an EVA
copolymer of a specified vinyl acetate content and a
vvhich utilize their pliability and rubbery elasticity. In
monomer grafted thereto, or a shaped article (B") reshaped articles which require abrasion resistance or
sulting from the saponificstion of the surface of a
scratch resistance, only temporary measures such ss
shaped article of an EVA copolymer of a specified
delustering or embossing treatment are taken to hide
scratches on the surface of the shaped article. It has 55 vinyl acetate copolymer.
It is an object of this invention therefore to provide a
been desired therefore to provide shaped articles of
shaped article of an ethylene-vinyl acetate copolymer
EVA copolymers having improved surface properties
having improved surface characteristics.
which can fmd practical application. For examples,
Another object of this invention is to provide a
much interest is aroused in the pliability, rubbery elasticity, good shapability and low cost of EVA copoly- 60 method for improving the surface adhesiveness of a
shaped article of an ethylene-vinyl acetate copolymer,
mers in automotive applications such as bumper cards
which can be utilized as a substrate in providing the
and decorative components, but the poor surface charaforesaid shaped article of improved surface characteracteristics of these shaped articles greatly limit their
istics.
utilization.
Modification of the surfaces of such shaped articles 65
The shaped article in accordance with this invention
would be feasible to improve the surface characteristics
comprises a substrate substantially of an ethylene-vinyl
of such EVA copolymer shaped articles. However,
acetate copolymer and formed on its surface, (C) a
attempt to impart the desired improved properties is
coating having an elongation of at least 10% formed
SHAPED ARTICLES OF ETHYLENE-VINYL
ACETATE COPOLYMER HAVING A COATING OF
NCO-FSES RADICAL-CONTAINING SYNTHETIC
SESIN PAINT
5

4,181,761

from a synthetic resin paint containing an NCO-free


radical; said substrate being either
(A) a shaped article of an ethylene-vinyl acetate copolymer having a vinyl acetste content of about 3 to
about 35% by weight, preferably about 5 to about 25% 5
by weight, said shaped article having a coating on its
surface formed from a solution of a resin selected from
the group consisting of
(aj) a partially saponified product having a degree of
saponificstion of up to about 50% of an ethylene-vinyl 10
acetste copolymer having a vinyl acetate content of
about 12 to about 45% by weight,
(32) a graft copolymer of ssid psrtislly saponified
ethylene-vinyl acetste copolymer (ai) and a carboxylcontaining monomer grafted thereto,
15
(33) a graft copolymer of sn ethylene-vinyl acetate
copolymer having a vinyl acetste content ofabout 12 to
about 45% by weight snd grafted thereto, st lesst one
monomer hsving s radical selected from the group
consisting of hydroxyl, carboxyl, acid anhydride, alk- 20
oxy and glycidyl rsdicsls, and
(34) s copolymer of ethylene, 3n unsaturated ester and
at least one monomer having a radicsl selected from the
group consisting of hydroxyl, csrboxyl, slkoxy snd
glycidyl radicsls, ssid copolymer Imving an ethylene 25
content of 3bout 55 to sbout 88% by weight,
(B) A shsped srticle of s blend of sn ethylene-vinyl
scetste copolymer hsving s vinyl scetste content of
sbout 3 to sbout 35% by weight with a resin selected
from the group consisting of
30
(bi) sbout 5 to sbout 30 psrts by weight, bssed on the
blend, of s ssponificstion product of an ethylene-vinyl
acetate copolymer hsving 3 vinyl acetate content of
about 5 to about 90% by weight,
(62) ahout 5 to about 30% by weight, based on the 35
weight of the blend, of a copolymer of ethylene and at
least one monomer having a radicsl selected from the
group consisting of hydroxyl, csrboxyl, slkoxy snd
glycidyl radicsls, ssid copolymer hsving sn ethylene
content of sbout 70 to sbout 98%,
40
(bi) about 2 to about 30% by weight, based on the
blend, of a copolymer of ethylene, sn unsaturated ester
and at least one monomer having a radicsl selected from
the group consisting of hydroxyl, carboxyl, alkoxy and
glycidyl radicals, said copolymer having an ethylene 45
content of about 55 to about 98% by weight, and
(b4) about 0.5 to about 30% by weight, based on the
blend, of a graft copolymer of a polymer of an a-olefin
or a copolymer of sn a-olefin with up to 45% by weight
of snother copolymerizable monomer, and grafted 50
thereto, st least one monomer having a radicsl selected
from the group consisting of hydroxyl, csrboxyl, acid
anhydride, alkoxy and glycidyl radicals,
(B') a shaped article of a graft copolymer of an ethylene-vinyl acetate copolymer having a vinyl acetate 55
content ofabout 3 to about 35% by weight, and grafted
thereto, at least one monomer having a radical selected
from the group consisting of hydroxyl carboxyl, acid
anhydride, alkoxy and glycidyl radicals, or
(B") a shaped article resulting from the saponification 60
of the surface of a shaped article of an ethylene-vinyl
acetate copolymer having a vinyl acetate content of 3 to
35% by weight.
The surface adhesiveness of the shaped article of
EVA copolymer (substrate) used to provide the shaped 65
articles of this invention is improved either by forming
a coating on the surface of a shaped article of an EVA
copolymer having a vinyl acetate content of about 3 to

about 35% by weight from a solution ofa resin selected


from the group consisting of (aj), (32), (33) and (34); or
by shaping a blend ofthe EVA copolymer and the resin
(bi), (b2), Q33) or (b4), or grafting a specific monomer to
the EVA copolymer and then shaping the graft copolymer, or shaping the EVA copolymer and saponifying
the surface of the shsped article.
The EVA copolymer having a vinyl acetste content
of about 3 to about 35% by weight, preferably sbout 5
to about 25% by weight, used to form the shaped articles of this invention is preferably prepared by bulk
polymerization through a high pressure method. A
composition ofthe EVA copolymer for preparing such
shaped articles may contain conventional additives.
Examples of such other additives, based on the weight
of the EVA copolymer or the blend of the EVA copolymer snd the resin selected from (bi) to (b4), sre up
to sbout 30% by weight of other olefinic resins such 3s
polyethylene, polypropylene or an ethylene-propylene
copolymer; up to sbout 30% by weight of fillers such ss
glsss fibers, glsss spheres, ssbestos, cslcium csrbonste,
silics and clay; up to about 20% by weight of pigments
and other coloring agents such as carbon black and
titanium oxide; up to about 0.5% by weight of known
oxidation inhibitors; and up to about 1 % by weight of
known weatherability stabilizers.
If the EVA copolymer has a vinyl acetate content of
less than about 3 % by weight, the shaped article lacks
pliability snd does not exhibit the chsracteristics of
EVA copolymer. On the other hand, ifthe vinyl scetste
content exceeds sbout 35% by weight, the copolymer is
difficult to fsbricste into srticles, snd the resulting srticles hsve low thermal stability.
In the present invention, any known melt-shaping
techniques can be used to produce the shaped article of
the EVA copolymer (or EVA copolymer composition)
or EVA copolymer blend (or EVA copolymer blend
composition). For exsmple, injection molding, extrusion molding, and compression molding can be utilized.
The configuration of the shaped article can be selected
as desired, and may be in the form of films, sheets,
plates, rods, tubes and other solid forms such as automobile finishing or trimming parts. The shaped articles
may be of any desired structure such as a multilsyer
laminate or foamed structure. The shaped articles may
also be in the cured state.
According to one embodiment of the present invention, a coating is formed on the surface of the shaped
article ofthe EVA copolymer from a solution of at least
one resin selected from (ai) to (34).
The partislly saponified product (si) of the E V A
copolymer has a degree of saponificstion (the ratio of
those acetste groups in the EVA copolymer which
hsve been converted to hydroxyl groups) of up to sbout
50%, ususlly sbout 0.5 to sbout 40%, preferably about
2 to about 30%. If the degree of saponification is extremely small, the adhesion of the coated film to the
paint tends to be insufficient. On the other hand, if the
degree of saponification exceeds about 50%, the adhesion of the coated film to the EVA shaped article is
insufficient, and the saponified copolymer has poor
solubility in solvents. The EVA copolymer to be saponified has a vinyl acetate content of about 12 to about
45%. Ifthe vinyl acetate content is less than about 12%
by weight, the copolymer has poor solubility in solvents. If it exceeds about 45% by weight, the adhesion
of the coated film to the EVA shaped article is low.

4,181,761

The method for producing the partially saponified


Specific examples of the copolymer (34) include terEVA copolymer is well known. For example, it can be
polymers derived from ethylene/unsaturated carboxprepared by dissolving the EVA copolymer in an orylic acid esters/hydroxyalkyl esters of unsaturated carganic solvent such as toluene or xylene, reacting it with
boxylic acids, such ss sn ethylene/methyl scrylste/hy3 lower slcohol such ss methanol or ethanol snd sn 5 droxyethyl scrylste terpolymer, 3n ethylene/ethyl
slksli such 3s sodium methykte snd sodium hydroxide
scrylate/hydroxyethyl acrylate terpo ymer, an
at 40 to 60 C. (if desired, in the presence of a suitable
ethylene/butyl acrylate/hydroxyethyl acrylate terpolyamount of water), adding methanol with stirring sfter
mer an
ethylene/methyltfu^f/b^^^
the reaction to precipitate the resulting polymer, and
acrylate terpolymer an ethylene/ethyl methscrylste/sepsrsting, wssWng and drying the polymer.
10 hydroxyethyl acrylate terpolymer and an ethylene/buThe grafting monomer having a carboxyl group used
tyl methacrylste/hydroxyethyl ^thscrylste terpo yto form the graft copolymer (az) includes, for example,
jnep terpolymers denved from e hylene/viny esters/scrylic seid" methscrylic scid msleic scid, fumaric
hydroxyalkyl esters of unsati^trated ^boxyhc acids,
acid, croton c acid, itaconic acid, and citraconic acid.
*. as an ethylene/vinyl acetate/hydroxyethyl acryAcid anhydrides which will for^ free csrboxylic acids '^^^^tZ^^Ss^Z
by estenfication reaction with the hydroxyl groups of
^
^ y ^
^
J e d csrboxylk acid esters/unthe partially saponified EVA copolymer (aOcan^so be
saturated carbo
l i c a c i d s > s u c h a s a n ethylene/methyl
used as the grafting monomer. Examples of the acid
^
ol
m ethylene/glycoi
anhydndes are maleic aiJiydnde, fumanc anhydnde, 2Q a c r ^ a t e / a c r ^ i c a c i d terpolymer, an ethylene/butyl
iconic anhydnde, and phthalic anhydnde.
acrylate/acrylic acid terpolymers, an ethylene/methyl
The ratio ofthe monomer grafted m the graft copolyterpolymer,
an
acr;jate/methacrylic
acid
mer (az) is preferably about 0.05 to 3% by weight bssed
e t h y l e n e / e t h y l acrylste/methscrylic scid terpolymer,
on the graft copolymer.
an ethylene/methyl methacrylate/acrylic acid terpolyExamples ofthe grafting monomer used to form the 25 m e r ) ^ ethylene/ethyl methacrylate/acrylic acid tergraft copolymer (33) mclude hydroxyl-containing monp 0 i y m e r ! a n ethylene/methyl methacrylate/methacryomers such 3s hydroxyalkyl esters of unsaturated carl i c a c i d t e r p o i y m e r and an ethylene/butyl methaboxylic acids (e.g., hydroxyethyl acrylate, hydroxycryiate/methacrylic acid terpolymer; terpolymers deethyl methacrylate, hydroxypropyl acrykte or hydroxr i v e d f r o m gthylene/vinyl esters/unsstursted csrboxypropyl methscrylste) snd chlorohydroxyslkyl esters 30 y j i c a c i d S ) s u c h a s ^ gthylene/vinyl scetste/scrylic
of unssturated carboxylic acids (e.g., chlorohydroxa c i d terpolymer, and an ethylene/vinyl acetate/methayethyl acrylate, chlorohydroxyethyl methacrylate,
c r y i j c a c j d terpolymer; terpolymers derived from
chlorohydroxypropyl acrylate or chlorohydroxypropyl
ethylene/unsaturated carboxylic acid esters/alkoxyvimethacrylate); carboxyl-containing monomers such as
n y i siianes, such as an ethylene/methyl acrylate/trimeunsaturated carboxylic acids (e.g., acrylic acid, meth- 35 thoxyvinylsilane terpolymer, an ethylene/ethyl
acrylic acid, maleic acid, fumaric acid, itaconic acid,
acrylate/trimethoxyvinylsilane
terpolymer,
an
crotonic acid or citraconic acid); monomers containing
ethylene/methyl methacrylate/trimethoxyvinylsilane
an acid anhydride radical such as unsaturated carboxterpolymer and an ethylene/butyl methacrylate/trimeylic snhydrides (e.g., msleic anhydride, itaconic anhythoxyvinylsilane terpolymer; terpolymers derived from
dride, citraconic anhydride, maleic anhydride/styrene, 40 ethylene/vinyl esters/alkoxyvinylsilanes such as an
maleic anhydride/vinyl acetate, maleic anhyethylene/vinyl acetate/trimethoxyvinylsilane terpolydride/ethylene, maleic anhydride/propylene, or maleic
m er; terpolymers derived from ethylene/unsaturated
anhydride/butene); alkoxy-containing monomers such
carboxylic acid esters/glycidyl esters of unsaturated
ss alkoxyvinyl silanes (e.g., trimethoxyvinyl silane, triecarboxylic acids, such as an ethylene/methyl acrylate/thoxyvinyl silane or dimethoxyethoxy vinyl silane) and 45 glycidyl acrylate terpolymer, an ethylene/ethyl
alkylalkoxyvinyl silanes (e.g., methyldimethoxyvinyl
acrylate/glycidyl methacrylate terpolymer and an
silane or methyldiethoxyvinyl silane); and glycidyl-conethylene/butyl methacrylate/glycidyl methacrylate
taining monomers such as glycidyl esters or unsaturated
terpolymer; and terpolymers derived from ethylene/vicarboxylic acids (e.g., glycidyl acrylate or glycidyl
nyl esters/glycidyl esters of unsaturated carboxylic
methacrylate).
50 acids, such as an ethylene/vinyl acetate/glycidyl acryThe grafting ratio of such a monomer is preferably
late terpolymer and an ethylene/vinyl acetate/glycidyl
about 0.02 to 5% by weight based on the graft copolymethacrylate terpolymer.
mer.
In the above embodiment of the present invention,
The copolymer (34) is a terpolymer of ethylene, an
the surface of the shaped article composed of EVA
unsaturated ester snd st lesst one monomer having a 55 copolymer is coated with a solution of at least one resin
radical selected from the group consisting of a hydroxyl
selected from (ai) to (34). A solvent cspsble of disrsdicsl, csrboxyl radical, alkoxy radicsl snd glycidyl
solving the polymer st s temperature of not more thsn
radical. Examples of the unsaturated ester are vinyl
30 C. is preferably used to form the solution. Exsmples
esters snd unssturated csrboxylic acid esters. Specific
of such a solvent are benzene, toluene, xylene, ethylbenexamples of the vinyl esters are vinyl formate, vinyl 60 zene, isopropylbenzene, butylbenzene, diethylbenzene,
acetate, vinyl propionate, vinyl butyrate and vinyl benamylbenzene, amyltoluene, cymene, cyclohexane, cyzoate. Examples of the unsaturated carboxylic acid
cloheptane, cyclooctane, methylcyclohexane, ethylcyesters include methyl acrylate, methyl methacrylate,
clohexane, hexane, heptane, octane, nonane, decane,
ethyl acrylate, ethyl methacrylate, propyl acrylate,
dodecane, dichloroethane, trichloroethane, tetrachloropropyl methacrylate, butyl acrylate, butyl methacry- 65 ethane, dichloroethylene, trichloroethylene, tetrachloIste, smyl scrylste, smyl methscrylste, hexyl scrylate,
roethylene, dichloropropane, trichloropropane, chlohexyl methacrylate, octyl acrylate, octyl methacrylate,
robutane, chloropentane, chloro-2-ethylhexane, chlorododecyl acrylate, and doecyl methacrylate.
benzene, dichlorobenzene, trichlorobenzene, chlorotol-

4,181,761

uene, dioxane, and tetrahydrofuran. Various known


According to a further einbodiment of the invention,
coating techniques can be used which include dip coatthe surface of a shaped article of the above EVA coing, spray coating, roll coating, brush coating or shower
polymer is saponified to form a shaped article (B")
coating. The coating formed is then dried by desired
having improved surface adhesion. The saponification
means such as air drying at room temperature, air spray- 5 in this embodiment can be achieved, for example, by
ing at room temperature, drying in a hot air oven or
dipping the shaped article of EVA copolymer in an
drying in a hot air tunnel. Preferably, the drying is
alkaline solution containing a lower alcohol as a main
carried out at a temperature below the softening temingredient. Examples of the lower alcohol are methaperature or heat distortion temperature of the substrate
nol, ethanol and propanol.
shaped article. For example, drying temperatures of 1 In the present invention, the coating (C) having an
about 0 to about 80 C. can be used. The resin concenelongation of at least 10% and composed of a synthetic
tration of the coating solution is not critical, and may,
resin paint containing an NCO-free radical is fonned on
for example, be within the range of about 1 to about
the surface of the shaped article (A) of the EVA co10%.
polymer having the coating of a resin selected from (ai)
The above coating procedure can markedly improve 15 to (34), or on the surfsce of the shaped article (B), (B')
or (B") described hereinabove.
the adhesion strength between the coated film and the
The coated surface of the shaped article (A) or the
surface ofthe shaped article composed of EVA copolysurface ofthe shaped article (B), (B') or (B") contains an
mer.
active hydrogen-containing functional group, or a
According to another embodiment of this invention,
a blend of the aforesaid EVA copolymer with at least 20 group capable of fonning an active hydrogen-containing functional group by hydrolysis, and exhibits markone resin selected from (bi) to (bn) above is shaped to
edly improved adhesion to the coating (C). The concenform a shsped srticle having markedly improved surtration of the functional group in the coated surface of
face adhesion.
the shaped article (A) is generally at least about
The saponified resin (bi) is a saponification product
-8
-7
25 1X IO mole, preferably at least about 1X IO mole,
of an EVA copolymer having a vinyl acetate content of
per gram of the coating on the shaped article (A). For
5 to 90% by weight. If its vinyl acetate content is outexample,
the concentration of the functional group is
side this range, the resulting blend gives a shaped article
8
about
1X10mole to about 1X10- 3 mole per gram of
having insufficient adhesion. The saponification prodthe
coating.
uct has a degree of saponification of preferably 1 to
30
The hydroxyl group concentration on the surface of
100%.
the shaped article (B") is 5 X10- 6 to 5X10- 3 mole per
The copolymer (bz) is s copolymer of ethylene with
gram of the surface layer of the saponified EVA coa monomer having a radical selected from hydroxyl,
polymer. This concentration range is estimated as folcarboxyl, alkoxy and glycidyl radicals. This copolymer
lows:
has an ethylene content of about 70 to about 98% by 35
The upper limit is obtained by calculating the hyweight. Ifthe ethylene content is lower than about 70%
droxyl group concentration ofa 100% saponified prodby weight, the copolymer is difficult to synthesize, and
uct ofthe EVA copolymer since this saponified product
its compatibility with the EVA copolymer is reduced.
permits sufficient adhesion ofa polyurethane paint. The
If the ethylene content is higher than about 98% by
lower
limit is an approximate value calculated on the
weight, a shaped article prepsred from the resulting 40
basis
of
the fact that in a certain test, a 5% saponified
blend does not show sufficient adhesion to a paint.
product of an EVA copolymer having a vinyl acetate
Hence, the ethylene content of the copolymer (bz)
content of 14% showed fairly good adhesion to a polyshould be within the above-specified range.
urethane paint even when it was diluted to 10 times with
The copolymer (ba) is a terpolymer of ethylene, an
the above EVA copolymer.
unsaturated ester and at least one monomer having a 45 The synthetic resin paint containing an NCO-free
radical selected from the group consisting of hydroxyl,
radical used to form the coating (C) may be those which
carboxyl, alkoxy and glycidyl radicals. This terpolymer
can form a dry coating having an elongation of at least
has an ethylene content of about 55 to 98% by weight.
10% at a temperature below the softening or heat disThe unsaturated ester may be those used in the resin (34)
tortion temperature of the shaped article (A), (B), (B')
described hereinabove.
50 or (B"). Preferably, the coating has an elongation of
In the graft copolymer OH), the trunk polymer is a
about 20% to about 500%.
homopolymer of an a-olefin or a copolymer of it with
The elongation of the coating is measured as follows:
snother copolymerizsble monomer. The a-olefin may
The paint is coated to a thickness of lOfi on a mold
hsve 2 to 5 csrbon stoms. Exsmples of such polymer or
releasing paper, and the coated film is used as a test
copolymer sre sn ethylene/vinyl scetate copolymer, an 55 specimen. The elongation (%) of the test specimen is
ethylene/propylene copolymer, polyethylene, and
measured in accordance with ASTM D-412-51T.
polypropylene. The grafting monomer may be the same
Examples of such as synthetic resin paint are polyolmonomers as described hereinabove with regard to the
curable and catslyst-cursble two-pscksge polyurethane
graft copolymer (33).
paints and moisture curable, heat-curable (blocked), and
According to still another embodiment of the inven- 60 oxygen-curable (oil-modified) one-package polyuretion, a graft copolymer obtained by grafting the same
thane paints. Of these, the polyol-curable two-package
grafting monomer as used in resin (33) to the EVA
polyurethane paints are preferred.
copolymer is shsped to form 3 shsped srticle (B') havThe isocyanate component as a main ingredient of
ing markedly improved surface adhesion. The grafting
such polyurethane paints include aromatic hydrocarreaction can be performed in the solution or melt phase 65 bons having an isocyanate group, aliphatic hydrocarusing a radicsl initistor. The preferred grafting ratio in
bons having an isocyanste group, hydrogenation prodthis resction is 0.02 to 5% by weight bssed on the graft
ucts thereof, and adducts thereof with di- to pentahycopolymer.
dric alcohols. Trimethylol propane is most frequently

4,181,761

11

to it were melt-blended by an extruder. The blend was


then press-molded to form a test specimen having a size
of 150X80X2 mm.
The test specimen was coated to a thickness of 35/x
with a two-package polyurethane paint (UREOL EVA, 5
a trademsrk for s product of Kawakami Paint Co., Ltd.,
Japan) by a spray gun. The coating v/as tested for the
items shown in Table 2.
Table 2
Test item

Test method

Elongation
Adhesion
Impact
strength
Water
resistance

Tensile speed 2C0 mm/min.


Crosscut tape test
Du Pont method, 500 g-J"50 cm
Tap water, 40 C , 10 days

Result
140%
100/100
Acceptable
Acceptable

10

12

to a thickness of 50JU with a two-package polyurethane


paint (UREOL EVA, trademark) by a spray gun.
The coating was tested for the items shown in Table
3 by the same methods as shown in Table 2. The results
are shown in Table 3.
Table 3
Test item
Elongation
Adhesion
Impact strength
Water resistance

Results
140%
100/100
Acceptable
Acceptable

The results show thst the surface ofthe shaped article


15 of the EVA copolymer has satisfsctory costsbility.
EXAMPLE 7

An EVA copolymer hsving a vinyl scetste content


The results show that a coating of polyurethane can
of 6% by weight snd a melt index of 25 wss injectionbe formed with satisfactory adhesion on the surface of a
shsped srticle of EVA copolymer.
20 molded to form s test specimen having a size of
150X150X2 mm.
EXAMPLE 4
The test specimen was dipped at 40 C. for 2 minutes
in a 3% toluene solution of a psrtislly ssponified EVA
Ninety parts of an EVA copolymer having a vinyl
copolymer obtsined by ssponifying sn EVA copolymer
acetate content of 10% by weight and a melt index of 20
(EVAFLEX V-561) and 10 parts of a graft copolymer 25 hsving s vinyl scetste content of 19% by weight snd a
melt index of 400 (EV-410, a trademsrk for s product of
of low-density polyethylene having a melt index of 23
Mitsui Polychemicsls Co., Ltd.) to a ssponificstion
and 3% by weight were melt-blended by an extruder,
degree of 10%, snd then dried for 15 minutes in the sir.
and the blend was press-molded to form a test specimen
Then, s two-pscksge polyurethane paint (UREOL
having a size of 150 X 80x2 mm. The test specimen was
coated to a thickness of 35/1 by a two-psckage polyure- 30 EVA, trademsrk) wss coated to a thickness of 35ju, by a
spray gun on the resulting coating.
thane paint (UREOL EVA, trademark).
The coating did not show peeling in the crosscut tape
A crosscut tape test was peformed on the resulting
test.
coating, and it was found thst the costing did not peel
off at all. When this test was performed after dipping
EXAMPLE 8
the test specimen in warm water at 40 C. for 10 days, 35
Ninety parts of an EVA copolymer having a vinyl
the coating did not peel off at all.
acetste content of 14% by weight and a melt index of 15
EXAMPLE 5
snd 10 parts of saponified EVA copolymer obtsined by
ssponifying sn EVA copolymer hsving s vinyl scetste
Ninety-five parts of an EVA copolymer hsving s
vinyl scetate content of 6% by weight and melt index of 40 content of 33% and a melt index of 31 (EV-150, a trademsrk for a product of Mitsui Polychemicals Co., Ltd.)
25 (P-0607, a trademark for a product of Mitsui Polyto a saponificstion degree of 90% were melt-blended by
chemicals Co., Ltd.) and 5 parts of a graft copolymer of
an extruder, and the blend was press-molded to form a
an EVA copolymer having a vinyl scetste content of
test specimen having a size of 1 5 0 x 8 0 x 2 mm.
28% and a melt index of 150 and 2.5% by weight of
msleic snhydride were melt-blended by sn extruder, 45
The test specimen was coated to a thickness of 35jLt
and the blend wss injection-molded to form s test speciwith a two-package polyurethane paint to form a coatmen hsving 3 size of 150x80x2 mm.
ing having an elongation of 100 to 110%.
The test specimen was coated to a thickness of 35/x
The coating did not show peeling in the crosscut tape
with a two-package polyurethane paint (UREOL EVA,
test.
trademark). In a crosscut tape test, the resulting coating 50
EXAMPLE 9
showed no peeling at all. When the crosscut tape test
was performed after dipping the test specimen in warm
An EVA copolymer having s vinyl acetate content
water at 40 C. for 10 days, no peeling of the coating
of 12% by weight and a melt index of 12 (P-1207, a
occurred.
trademsrk for a product of Mitsui Polychemicals Co.,
5 5 Ltd.) was injection-molded to form a test specimen
EXAMPLE 6
hsving s size of 150 X 150X2 mm.
An EVA copolymer (V-561, trademark) having a
The test specimen wss costed st 25 C. by s spray gun
vinyl acetate content of 10% by weight and a melt index
a 2% toluene solution of a polymer obtained by saponiof 20 was injection-molded to form a test specimen
fying an EVA copolymer having a vinyl acetate conhaving a size of 150 X 150 X 2 mm.
60 tent of 28% by weight and a melt index of 150 (EV-220,
A 3% tetrachloroethylene solution of a partially saa trademark for a product of Mitsui Polychemicals Co.,
ponified EVA copolymer obtained by saponifying an
Ltd.) to a saponification degree of 10%, and grafting
EVA copolymer having a vinyl acetate content of 28%
0.3% by weight of acrylic acid to the copolymer. The
by weight and a melt index of 150 (EV-220, a trademark
coating was dried for 15 minutes in the air, and then
for a product of Mitsui Polychemicals Co., Ltd.) to a 65 further coated by a spray gun with a two-pscksge polysaponification degree of 10% was coated on the test
urethsne psint (UREOL EVA, trademsrk).
specimen by a spray gun st 25 C , and dried for 15
The final costing obtained did not show peeling in the
minutes. The surface of the coating was further coated
crosscut tape test.

4,181,761

used as the polyol for forming such adducts. Exsmples


ofthe polyol component, snother main ingredient ofthe
polyurethsne paints, are polyester polyols, polyether
polyols, acrylic polyols, and vinyl polyols. Usually,
such polyurethane-type psints contsin s pigment, a
solvent and optionsl costing sids such 3S a plssticizer,
drying agent, curing agent, antiskinning agent, thickener, gloss-imparting agent, smoothing agent, S3g inhibitor, sntiseptic, snticorrosive sgent, mold proofing
3gent or ultraviolet sbsorber.
Any known techniques csn be used to form the costing (C) in this invention. Exsmples sre spray coating by
a spray gun, electrostatic coating, dip coating, brush
coating or roll costing.
The present invention thus provides shsped srticles
of EVA copolymer hsving a specific costing firmly
adhering to it, which are free from the conventional
defects such as poor scratch resistance or poor decorative quality. By using a polyurethane-type paint hsving
flexibility to form the specific coating on the shaped
article from the resins (ai) to (34), the sppesrance ofthe
shsped article is satisfactory for practicsl purposes. The
shaped articles of the present invention are useful in
various applications, but an especially preferred application is in interior and exterior finishing or trimming
parts of automobiles. Specifically, the interior finishing
or trimming parts include dashboards, arm chairs and
door handles. The exterior finishing or trimming parts
include molded articles for bumpers, and mudguards.
The molded articles for bumpers mean molded articles
including 3 reinforcing metsl inside which 3re used 3S
bumpers themselves, and those molded articles which
supplement the function of bumpers and also have a
decorating function. These molded articles are used to
cover a part or the whole of a bumper, snd have the
function of alleviating the extemal force which the
bumper undergoes and thus allevisting the force which
the sutomobile body receives from the bumper.
The following Exsmples snd Compsrstive Exsmples
illustrate the present invention in greater detail. The
invention should be construed not to be limited by these
specific examples. All parts in these exsmples 3re by
weight unless otherwise specified.
EXAMPLE 1 snd COMPARATIVE EXAMPLES 1
snd 2
Eighty parts of an EVA copolymer having a vinyl
acetate content of 14% by weight and a melt index of 15
(EVAFLEX P-1407, a trademune for a product of Mitsui Polychemical Co., Ltd., Japan), 10 psrts of a master
bstch of EVAFLEX P-1407 contsining 10% by weight
of carbon black, and 10 parts of a graft copolymer of
styrene and 2% by weight of maleic anhydride were
melt-blended. The blend was press-molded to form a
test specimen having a size of 150 X 150x2 mm.
The test specimen was coated to a thickness of 100^,
[specimen (A)] with a two-package black polyurethsne
psint (the coating had an elongation of 110 to 110%).
A crosscut tape test was performed on the resulting
coating, and it was found that the coating did not peel
off at sil from the surfsce of the specimen.
Sepsrstely, 90 parts of EVAFLEX P-1407 snd 10
psrts of the master bstch contsining carbon black were
melt-blended, and the blend was press-molded to form a
specimen having a size of 150x150x2 mm [specimen
(B)].
A test specimen (C) was prepared by coating the
specimen (B) in the same way as in the preparation of

10

the sample (A). The specimen (C) was subjected to the


ssme crosscut tape test ss sbove.
The specimens (A) snd (B) were tested for sppesrances and sbrasion indices by a TABER sbrssion tester.
5 The results sre shown in Tsble 1. As is clesrly seen from
Tsble 1, the specimen (A) hsving the urethsne costing
showed fsr better results.
Tsble 1
10

Example 1
(specimen A)
Good

Appearance

15

Abrasion index
(mg/1000 cycles)

6.6

Comparative
Example 1
(specimen B)

Comparative
Example 2
(specimen C)

Poor
(insufficient
gloss)
14 .

(*)
Crosscut tape
test (adhesion)

100/100

0/100

(*) Abrasion loss in accordance with ASTM D-1242-56.

20
EXAMPLE 2 snd COMPARATIVE EXAMPLE 3

25

30

35

40

45

50

Eighty psrts of 3n EVA copolymer hsving 3 vinyl


scetste content of 14% by weight snd a melt index of 15
(EVAFLEX P-1407, trademsrk), 10 psrts of s msster
bstch of EVAFLEX P-1407 contsining 10% by weight
of csrbon blsck, snd 10 psrts of s graft copolymer consisting of EVA copolymer hsving s vinyl scetste content of 19% by weight snd a melt index of 10 3nd 2% by
weight of msleic snhydride grafted to it were meltblended, snd the blend wss injection-molded under the
following conditions to form s cover for the side ends of
sn sutomobile bumper.
Cylinder temperature: 180 C.
Mold temperature: 25 C.
Injection pressure: 1050 kg/cm 2
Weight of the molded srticle: 400 g
A two-pscksge polyurethsne psint wss sprayed onto
the resulting molded srticle to form 3 costing hsving sn
elongstion of 118%. The costed bumper cover had
better gloss and appesrance than the uncoated bumper
cover (Comparstive Example 3).
The costed and uncosted bumper covers were esch
rubbed strongly 20 times with s brush in wster contsining 3 detergent to examine the state of scratch on their
surfaces. The trace of brushing was clearly seen in the
uncoated bumper cover (Comparative Example 3), but
wss scsrcely observed in the costed one.
COMPARATIVE EXAMPLE 4

Eighty psrts ofthe ssme E V A F L E X P-1407 ss used


in Exsmple 2 snd 10 psrts of the ssme msster bstch ss
used in Exsmple 2 were melt-blended, snd the blend
wss injection-molded under the ssme conditions ss in
55 Exsmple 2 to form sn sutomobile bumper cover. The
molded srticle wss costed with the ssme two-pscksge
polyurethane paint as used in Example 2. When the
coated bumper cover was subjected to a crosscut tape
test, the result was 0/100.
60
EXAMPLE 3
Ninety-eight parts of an EVA copolymer having a
vinyl acetate content of 10% by weight and a melt index
of 20 (EVAFLEX V-561, a trademark for a product of
65 Mitsui Polychemicals Co., Ltd.) and 2 parts of a graft
copolymer consisting of EVA copolymer having a
vinyl acetate content of 14% by weight and s melt index
of 15 snd 1.5% by weight of msleic anhydride grafted

13
EXAMPLE 10

4,181,761

14

gun with a two-package polyurethane paint (UREOL


EVA, trademark). The coating obtained peeled off in
the crosscut tape test.

An EVA copolymer having a vinyl acetate content


of 10% by weight and a melt index of 20 was injectionEXAMPLE 14
molded to form a test specimen having a size of 5
A test specimen having a size of 150 X 80 X 2 mm was
150x80x2 mm. The test specimen was dipped for 30
injection-molded using an EVA copolymer having a
seconds at 40 C. in s 2% toluene solution of a polymer
vinyl acetate content of 14% and a melt index of 15
obtained by grafting 0.5% by weight of maleic anhy(P-1407, trademark).
dride to an EVA copolymer having a vinyl acetate
The test specimen was dipped at 40 C. for 10 minutes
content of 19% by weight and a melt index of 400 (EV- 10
in a solution consisting of 85.7% by weight of isopropa410, a trademsrk for s product of Mitsui Polychemicsls
nol, 12.0% by weight of methanol and 2.3% by weight
Co., Ltd.), snd then dried in the sir for 15 minutes. A
of sodium methylate, washed with water, and then
two-psckage polyurethane paint (UREOL EVA, tradedried. A two-package polyurethane paint (UREOL
mark) was brush-coated on the resulting coating.
The final coating obtained did not show peeling in the 15 EVA, trademark) was brush-coated on the resulting
coating, snd dried st 40 C. for 3 dsys. The finsl costing
crosscut tape test.
obtsined did not show peeling in the crosscut tspe test.
EXAMPLE 11
Whst we clsim is:
1. A shspe srticle comprising s substrate substsntially
An EVA copolymer having a vinyl acetate content
of 14% by weight and a melt index of 15 (P-1407, trade- 20 of an ethylene-vinyl acetate copolymer and formed on
its surface, (C) a coating having an elongstion of at least
mark) wss injection-molded to form s test specimen
10% formed from a synthetic resin paint containing an
hsving s size of 150x80x2 mm. The test specimen wss
NCO-free radical; said substrate being either
dipped for 30 seconds st 30 C. in a 2% xylene solution
(A) a shaped article of an ethylene-vinyl acetate coof a terpolymer of ethylene/vinyl acetate/methacrylic
polymer having a vinyl acetate content of about 3
acid having a vinyl acetate content of 25% by weight 25
to about 35% by weight, said shaped article having
and an acid value of 6, and then dried in the air for 30
a coating on its surface formed from a solution of a
minutes. A two-package polyurethane resin paint
resin selected from the group consisting of
(UREOL EVA) was brush-coated on the resulting
(ai) a partially saponified product having a degree of
coating:
ssponificstion of up to sbout 50% of sn ethyleneThe final coating obtained did not show peeling in the 30
vinyl scetate copolymer having a vinyl acetate
crosscut tape test.
content ofabout 12 to about 45% by weight,
EXAMPLE 12
(az) a graft copolymer of said partially saponified
ethylene-vinyl acetate copolymer (ai) and a carSeventy parts of an EVA copolymer having a vinyl
boxyl-containing monomer grafted thereto,
acetate content of 19% by weight and a melt index of 15 35
(33) a graft copolymer of an ethylene-vinyl scetste
(P-l907, a trademark for a product of Mitsui Polycopolymer hsving a vinyl 3cet3te content of sbout
chemicals Co., Ltd.) and 30 parts of an ethylene/vinyl
12 to sbout 45% by weight 3nd grafted thereto, st
acetate/glycidyl methacrylate terpolymer (BOND
lesst one monomer hsving a radicsl selected from
FAST 2B, a trademark for a product of Sumitomo
the group consisting hydroxyl, csrboxyl, scid snChemicals Co., Ltd.) were melt-blended, and the blend 40
hydride, slkoxy snd glycidyl rsdicsls, snd
was injection-molded to form a test specimen having a
(34) 3 copolymer of ethylene, sn unssturated ester and
size of 150x80x2 mm.
at least one monomer having a radical selected
A two-package polyurethane paint (UREOL EVA,
from the group consisting of hydroxyl, carboxyl,
trademark) was coated on the test specimen by a spray
alkoxy and glycidyl radicsls, ssid copolymer hsvgun. The final coating obtained did not show peeling in 45
ing sn ethylene content of sbout 55 to sbout 88%
the crosscut tape test.
by weight,
EXAMPLE 13
(B) u shsped srticle of a blend of an ethylene-vinyl
scetste copolymer hsving a vinyl scetste content
Seventy five parts of an EVA copolymer having a
of sbout 3 to sbout 35% by weight with 3 resin
vinyl acetate content of 14% by weight and a melt index 50
selected from the group consisting of
of 15 (P-1407, trademark) and 25 parts of an ethylene/(bj) sbout 5 to about 30 parts by weight, based on the
vinyl acetate/methacrylic acid terpolymer were meltblend, of a saponificstion product of sn ethyleneblended, and the blend was press-molded to form a test
vinyl scetste copolymer hsving s vinyl scetste
specimen having a size of 150x80x20 mm. The test
content of sbout 5 to about 90% by weight,
specimen was coated by a spray gun with a two-pack- 55
(bz) about 5 to about 30% by weight, bssed on the
age polyurethane paint (UREOL EVA, trademark).
weight of the blend, of a copolymer of ethylene
The coating did not show peeling in the crosscut tape
snd st lesst one monomer having a radicsl selected
test.
from the group consisting of hydroxyl, csrboxyl,
COMPARATIVE EXAMPLE 5
alkoxy and glycidyl radicals, said copolymer hsv60
ing 3n ethylene content of sbout 70 to sbout 98%,
A test specimen having a size of 150 X 80x2 mm was
(bs) sbout 2 to sbout 30% by weight, based on the
prepared by injection molding using an EVA copolyblend, of a copolymer of ethylene, an unsaturated
mer having a vinyl acetate content of 10% by weight
ester snd st lesst one monomer hsving s radical
and a melt index of 20 (V-561, trademark) and sn EVA
selected from the group consisting of hydroxyl,
copolymer hsving a vinyl acetate content of 19% by 65
csrboxyl, alkoxy and glycidyl radicals, said coweight and a melt index (P-l907, a trademark for a
polymer hsving sn ethylene content of sbout 55 to
product of Mitsui Polychemical Co., Ltd.). The test
sbout 98% by weight, snd
specimen was coated to a thickness of 35p, by a spray

4,181,761
15
(b4) about 0.5 to about 30% by weight, based on the
., A r
a.
i
r
i
>
blend, of a graft copolymer of a polymer of an
a-olefm or a copolymer of an a-olefin with up to
45% by weight of another copolymerizable monomer, and grafted thereto, at least one monomer
having a radical selected from the group consisting
, ,
,
,
.
.. , . ..

,
of hydroxyl, carboxyl, acid anhydnde, alkoxy and
glycidyl radicals,
(B') a shaped article of graft copolymer of an ethylene-vinyl acetate copolymer having a vinyl acetate content of about 3 to about 35% by weight,
, , ,
,
,
and grafted thereto, at lesst one monomer having a
radical selected from the group consisting of hydroxyl, carboxyl, acid anhydride, alkoxy and glycidyl radicals, or
(B") a shsped article resulting from the saponification
* ,
1,
* L
J
1 *
1- t
of the surface of a shaped article of an ethylenevinyl acetate copolymer having a vinyl acetate
content of 3 to 35% by weight.

16
2. The shaped article ofclaim 1 which is a component
part for the interior or exterior finishing or trimming of
p

bil
3 -j^^ s h a p e d ^^^ o f claim 1 wherein the grafting
5 monomer in resins (33) and Ou) is a monomer selected
from the group consisting of hydroxyalkyl esters of
unsaturated carboxylic acids, chlorohydroxyalkyl esters of unsaturated carboxylic acids, unsaturated car^ ^ ^
u n s a t u r a t e d 'caIboxy]iC add anhydrides,
10 alkoxyvinylsilanes, alkylalkoxyvinylsilanes and glycidyl esters of unsaturated carboxylic acids,
* The shaped article ofclaim 1 wherein the comono^
mer havin
8 t h f specified radical in (34), (bz) and (bj) is
a monomer selected from the group consistmg of hy15 d r o x y a l k y l e s t e r s o f unsaturated carboxylic acids, chlorohydroxyalkyl esters of unsaturated carboxylic acids,
unsaturated carboxylic acids, alkoxyvinylsilanes, alkylalkoxy vinylsilanes and glycidyl esters of unsaturated
, carboxylic acids.
- , . , . .
20
5. The shaped article ofclaim 1 wherein the unsatu^
^
^
boxylic
acid
ester
rated
in
i s aa u n s a t u r a t e d car
o r a vinyl ester.
* * * * *
25

30

35

40

45

50

55

60

65