Beruflich Dokumente
Kultur Dokumente
[H]
4,181,761
Ishimoto et al.
[45]
Jan. 1, 1980
Dec. 8, 1978
Japan
'.
52-148197
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
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Bridgeford
Haley
Tatsumi
Tatsumi
Viola
428/420
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ABSTRACT
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
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11
Test method
Elongation
Adhesion
Impact
strength
Water
resistance
Result
140%
100/100
Acceptable
Acceptable
10
12
Results
140%
100/100
Acceptable
Acceptable
4,181,761
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
20
EXAMPLE 2 snd COMPARATIVE EXAMPLE 3
25
30
35
40
45
50
13
EXAMPLE 10
4,181,761
14
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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