Note: Descriptions are shown in the official language in which they were submitted.
This invention relates to resin compositions for peel-off
coatings.
A variety of coating compositions have hitherto been used
for forming peel-off coatings or strippable coatings that are
serviceable for temporary protection of the surfaces of shaped
articles such as parts of electrical appliances or machines, kit-
chenwares, and the like. For example, aqueous coating composi-
tions comprising a synthetic resin emulsion, such as polyvinyl
acetate emulsion or an acrylic resin emulsion, are most exten-
sively used. Such peel-off coating compositions based on an
aqueous polymer emulsion, however, are not satisfactory in stor-
age stability, thermal resistance and water resistance and other
properties of the resultant coatings. As a further example are
aqueous coating compositions prepared by admixing some floury
materials, such as calcium carbonate, titanium dioxide and the
like, silicone resins, and aqueous emulsion of paraffin wax and
other supplemental ingredients. These compositions are also de-
fective owing to instability in long storage, delay in drying
after application, etc. (See, for example, Japanese Patent Pub-
lication No. 14770/73.)
In addition, solvent-type compositions for peel-off coat-
ings are known. They are prepared by dissolving a polyvinyl bu-
tyral resin and a plasticizer in an organic solvent. However,
their formulation is disadvantaged by restrictions in the selec-
tion and amount of plasticizers to be used. In addition, bleed-
ing or migration of plasticizer often takes place, while the re-
sultant coatings sometimes exhibit low peelability when applied
to articles made of certain materials.
It is an object of this invention to provide a resin com-
position for peel-off coatings useful for temporary protection of
.. ~ .
s
the surfaces of shaped articles, which avoids or reduces the
above-described problems encountered in the prior art eomposi-
tions, i.e. rigorism in formulation, instability in storage, de-
lay in drying, possibility of bleeding of plasticizer or other
components, imperfect peelability of the resultant coatings, etc.
According to one aspect of this invention there is pro-
vided a resin composition for peel-off coatings consisting essen-
tially of
(A) 100 parts by weight of at least one polyvinyl acetal resin.
(B) 1 to 30 parts by weight of an organopolysiloxane represented
by the average formula:
[(Rl )mSiO4-~3 (R2 ) nsiO3-n
2 x 1 2 ¦ -- (I)
(CH2t--aO~C2H40) b~C3H60~HJ Y
wherein Rl and R2 are halogen-substituted or unsubstituted
monovalent hydroearbon groups, m is an integer from 1 to 3,
n is 0 or a positive integer, a is 0 or an integer from 1 to
5, b is an integer from 2 to 40, e is 0 or an integer from 1
to 40, and x and y are integers from 2 to 50.
According to another aspect of this invention there is
provided a method of preparing a resin composition as reeited
above eomprising blending eomponents (A) and (B) as defined above.
The term "peel-off eoatings" as used herein denotes eoat-
ing films which are formed on the surfaces of a shaped article to
temporarily proteet the surfaees from external damage of a meeh-
anical or chemical nature during storage andjor transportation,
and which ean be peeled off mainly by hand, without being torn
into small pieees, immediately prior to use of the shaped article,
so that the intrinsic surfaees of the shaped artiele are exposed.
~69~
Any shaped articles including parts of eleetric applian-
ces and machines, kitchenwares, and the like ean be eoated with
the resin eomposition when temporary protection is required.
Further, those articles eoated with the peel-off eoating eompo-
sition may be used as sueh and, when the surface of the eoating
film becomes stained with dirty matter, sueh as soot or grease,
the coating film may readily be peeled off to expose a fresh sur-
faee, which can then be re-coated with the same composition.
Generally it is required that peel-off coatings adhere
firmly to the surface of the shaped article without lifting be-
fore they are intentionally peeled off. The peelability of the
eoatings should be maintained through the lapse of time and even
in hot eonditions. The peel-off eoatings should have enough
meehanieal strength, water resistance and ehemical resistanee.
On the other hand, the peel-off eoating compositions should be
suitable for application by known methods, such as spraying or
brushing. The layer of the coating composition applied to vari-
ous surfaces should promptly dry and form films with a high de-
gree of continuity. Resin compositions according to embodiments
of the present invention satisfy all of these requirements.
The resin compositions are applicable to the various sur-
faces, such as metals, plastics, ceramics and the like. The
coating films formed are clear in appearance and have sufficient
hardness, tensile strength and elongation.
Polyvinyl acetal resins whieh form component (A) in the
resin composition include, for example, polyvinyl formal resins
and polyvinyl butyral resins which are commereially available.
It is preferred that the polyvinyl formal resins have a degree of
polymerization in the range from 400 to 1,000 and eontain at
least 30 mole ~ of the formal component, and that the polyvinyl
6~
butyral resins have a degree of polymerization in the range from
400 to 1,100 and contain at least 30 mole ~ of the butyral compo-
nent. The above-mentioned ranges of polymerization degrees for
the polyvinyl formal resins and the polyvinyl butyral resins are
not absolutely restrictive, but it may be acceptable that the
average of polymerization degrees of any polyvinyl formal resins
or polyvinyl butyral resins used falls in the range. Further,
component (A) may be a mixture of at least one polyvinyl formal
resin and at least one polyvinyl butyral resin.
Organopolysiloxane which form component (B) in accordance
with the present invention are represented by the above-given
average formula (I), in which symbols Rl and R2 are halogen-sub-
stituted or unsubstituted monovalent hydrocarbon groups, such as
alkyl groups (e.g., methyl, ethyl and propyl groups), alkenyl
groups (e.g., vinyl, allyl and hexenyl groups), cycloalkyl groups
(e.g., cyclohexyl and cycloheptyl groups), aryl groups (e.g.,
phenyl, tolyl and xylyl groups), aralkyl groups (e.g., benzyl and
phenylethyl groups) and halogen-substituted monovalent hydrocar-
bon groups (e.g., chlorophenyl, tetrachlorophenyl, chloromethyl
and pentafluorobutyl groups).
It is natural that the molecule of component (B) is com-
posed of siloxane units in which the group represented by symbol
Rl and R2 is not limited to only one specific group. Different
Rl groups and different R2 groups may be present in the molecule.
Similarly, the value denoted by m, n, a, b or c is not limited to
one specific value in the molecule.
Among the oxyalkylene-containing organopolysiloxanes in
conformity with the average formula (I) for component (B) are
preferred the linear organopolysiloxanes represented by the fol-
lowing general formula:
6~Q~S
R3 sio~ sio~ sl-o 1 siR3 . . . ( II )
lRI X-2 (CH2t~0~C2H40~C3El60~HJ v
where Rl, R2, x, y, b and c have the same meanings as defined
previously and a' is a positive integer from 1 to 5, from the
standpoint of the compatibility of component (B) with component
(~) and the stability of component (B) against hydrolysis.
Illustrative of component (B) in the resin composition in
conformitv with the general formula (II) are the organopolysilox-
anes expressed by the following formulas.
fH3 ~fH3l ~ fH3 1 fH3
C'13-SiO t SiO ~ 7iO I Si-CH3 (III)
CH3 ~CH3)3al(cH2t~o-~c2H4ot~tc3H6ot~HJ2 CH3
fH3 ~ fM3l ~ fH3 ¦ fH3
CH3-SiO 7io. ~sio- _ fi-CH3 ... (IV)
CH3 ~CH3 38 l(CH2 ~ ~-~C2H40 ~ C3H60 ~ H loCH3
o fH3 ~fH3l ~ fH3 1 fH3 .
t I ~ 7 _ fi-CH3 ... (V)
CH3 ~cH3J3~3l~(cH2t~o-tc2H4ot~c3H6ot~H 36CH3
fH3 ~ fH3 1 fH3
CH3-SiO- - sio - ,Si-CH3 ... (VI)
CH3 (CH2 ~ O-~C2H40 ~ H 5 CH3
fH3 ~ fH3 1 fH3
CH3-7iO t SiO - Si-CH3 ... (VII)
CH3 l(CH2 ~ O-~C2H40~H, ~5 CH3
., ~
~1~6g~5
fH3 ~ fH3 fH3
CH3-SiO t SiO Si-CH3 ... (VIII)
CH3 (CH2~ 0-~C2H40~ H 38 CH3
CH3 ~CH3l ~ fH3 1 fH3
~ fi-CH3 ... (IX)
CH3 ~CH3)3a ~(CH2~ 0--tC2H40 ~ H, 38 CH3
fH3 ~fH3l ~fH3 1 fH
CH3-SiO- SiO ~ SiO - Si-CH3 ... (X)
CH3 CH3 5 ~(cH2 ~ o-tc2H4o ~ c3H6o ~ H~ 38 CH3
fH3 ~fH3l ~ fH3 CH3
7 t I ~ I ~ Si-CH3 ... (XI)*
CH3 ~CH3)27 ~c2H4o ~ H~3 CH3
CU3-Si ~OSl~ O-tCZ~O ~ C3H~O ~ H~ ... (XII)~
fH3~ fH3~ fH3 fH3
CH3-SiO SiO- - Sio- Si- CH3 ... (XIII)*
l ! I
CH3 ~CH3 3 1 CH3
(C2H~,ot~H
in accordance with General Formula I.
The polyoxyalkylene groups in component (B) may be bonded
to the silicon atoms through Si-C linkages or Si-O-C linkages,
although the Si-O-C linkages are preferred owing to their rela-
tively high stability against hydrolysis. Further these polyoxy-
alkylene groups have hydroxy qroups at the terminals, by which
component (B) is rendered sufficiently compatible with component
11~69~5
(A), and the coating films formed have excellent physical proper-
ties as well as easiness in peeling-off. On the other hand, when
the polyoxvalkylene groups bonded to the silicon atoms have a
monovalent hvdrocarbon group, such as an alkyl group, an aryl
group or the like at the terminals, the organopolysiloxanes con-
cerned have lower compatibility with the polyvinyl acetal resins
and are less suitable for formulating peel-off coating composi-
tions.
In the resin composition 1 to 30 parts by weight, prefer-
ably 5 to 20 parts by weight, of component (B) should be incor-
porated uer 100 parts by weight of component (A). If the amount
of component (B) used is smaller than 1 part by weight per 100
parts by weight of (A), the coatings obtained cannot be easily
peeled off, while amounts of (B) used in excess of 30 parts by
weight bring about inferior properties and economical disadvan-
tages to the resultant coatings.
The resin compositions can be prepared simply by blending
component (A) with component (B). In the blending, it is prefer-
red to use an organic solvent or solvents. Included among such
organic solvents are alcohols such as methanol, ethanol, propanol
and butanol, aliphatic hydrocarbons such as hexane and pentane,
aromatic hydrocarbons such as benzene, toluene and xylene, ke-
tones such as acetone and methyl ethyl ketone, ethers such as di-
ethyl ether, dioxane and tetrahydrofuran, esters such as ethyl
acetate, propyl acetate and butyl acetate, and chlorinated hydro-
carbons such as trichloroethylene and carbon tetrachloride.
I~hen, in particular, the resin composition is to be applied to a
shaped article havinq portions of plastics, for example, from
acrylic resin, polystyrene or the like, it is preferred to use
alcohols, especially saturated alcohols having 1 to 4 carbon
~p~ 25
atoms, so that swelling or dissolution of the plastic portion may
be prevented. The amount of the organic solvent used is not nar-
rowly critical. In practice the amount of the organic solvent is
not less than 5% by weight based on the total of components (A) and
(B), so as to obtain a suitable viscosity of the coating composi-
tion. The organic solvent is added to components (A) and (B) and
mixed together with stirring, preferably in the presence of heat,
to obtain a better peelability. The temperature in this case is
between about 40 and about 150C depending on the kind, degree of
polymerization, etc. of the polyvinyl acetal resin, with stirring
continued for about 1 to about 6 hours.
In addition to the organic solvents, various other addi-
tives, including plasticizers, such as phthalic esters, phospho-
ric esters, fatty acid esters and g1YCO1 derivatives, fatty sub-
stances such as vegetable oils, cellulose derivatives and pig-
ments may be incorporated in the compositions to improve the pro-
perties, for example, softness of the resultant coating films.
The resin compositions are useful as the protective coat-
ing for various shaped articles of metals, plastics, ceramics as
well as for painted surfaces. The articles include, for example,
electric appliances such as ventilating fans, kitchen supplies,
building materials, automobiles and the like.
The peel-off coatings are useful not only for the protec-
tion of the surfaces of any article in storage or transportation
prior to use but also for the protection of the articles durinq
use. When the coating articles in use become stained on their
surfaces, the coatings can be readily removed bv peeling off and
then the exposed surfaces can be re-coated with the same composi~
tion. Even if the surface to be re-coated is oily or greasy to
some extent, the re-coating work can be easily performed to
,. ,
i9~5
produce new coating films with satisfactory results.
The following examnles illustrate embodiments of the pre-
sent invention. In the examples, parts are all parts by weight.
Further in the examples, the peeling-off tests were carried out
by either of the following three methods, involving accelerated
aging.
Method I: Clean aluminum plates were coated with the
specified peel-off coating compositions, and the resulting coat-
ings were subjected to heat treatment at 80C for 100 hours and
thereupon their peelability was determined.
Method II: Aluminum plates covered by thin layers of
soybean oil were coated with the specified peel-off coating com-
positions and treated in the same manner as in Method I to deter-
mine the peelability of coatings so formed.
Method III: Aluminum, polystyrene resin and glass plates
were individually coated with the specified peel-off coating com-
positions, and the thus resulting coatings were subjected to
treatment first by heating at 70C for 5 hours and then by allow-
ing to stand at room temperature for 1 hour, such treatment being
repeated for 50 cycles. Thereupon the coatings were tested for
peelability.
The results of the peel-off tests are expressed severally
by symbols A, B, and C as follows.
A: The coating film was easily peeled off without
trouble, such as tearing of the film into pieces.
B: Part of the coating film remained unpeeled and adher-
ing to the substrate, due to resistance to the peeling-off oper-
ation.
C: Peeling-off was impossible due to adhesion of the
coating film to the substrate.
~6~5
EXAMPLE 1
Into a vessel equipped with a stirrer were charged lO0
parts of a mixed polyvinyl butyral resin composed of P(l), P(2)
and P(3) given below in equal amounts, 20 parts of the organo-
polysiloxane as expressed by the aforementioned formula (VIII),
510 parts of methanol and 60 parts of ethanol, followed by mixina
with stirring for 2 hours at room temperature, to obtain a clear
solution.
P(l): A polyvinyl butyral resin havinq 2 mole ~ of un-
saponified acetyl groups, 35 mole % of hydroxy
groups and 63 mole % of butyral substitution,
with a degree of polymerization 1300.
P(2): A polyvinyl butyral resin having the chemicalassay identical to P(l) but with a degree of
polymerization 600.
P(3): A polyvinyl butyral resin having the chemical
assay identical to P(l) but with a degree of
polymerization 400.
The solution of the resin composition thus obtained was
applied to an aluminum plate by the brush coating method. The
coating film formed was determined with respect to its physical
properties and tested for peelability. The results are shown in
Table I. In this table and certain tables to follow, "hardness"
expressed by mark "H" or "2H" was determined in accordance with
the method for determination of hardness by use of pencils as
described in JaPanese Industrial Standard (JIS) K 5400-1970, 6.14.
i9'~5
TABLE I
Physica~ Proper-tie 5 :
Appearance .............................. Clear
Hardness .................................... H
Tensilé Strength ................... 200 kg/cm2
Maximum Elongation ......................... 10
Pee~abi~ity:
In accordance with Method I ................. B
In accordance with Method II ................ A
EXAMPLE 2
. . . _
The same procedure as in Example 1 was repeated except
the stirring of the mixture was carried out at 60C, instead of
room temperature, to obtain a clear solution. Similar tests on
- the coating resulted as shown in Table II.
TABLE II
PhysicaZ Properties:
Appearance .............................. Clear
Hardness ................................... 2H
Tensile strength .................. 230 kg/cm 2
Maximum Elongation ........................ 10%
Pee~abi~ity:
In accordance with Method I ................. A
In accordance with Method II ................ A
EXAMPLE 3
The same procedure as in Example 1 was repeated except
that the organopolysiloxane as expressed by the aforementioned
formula (V) was employed instead of the organopolysiloxane of
69~5
formula (VIII) to obtain a simi]arly clear solution. The results
of similar tests on the thus obtained coating were as shown in
Table III.
TABLE III
PhysicaZ Properties:
Appearance ......................... Clear
Hardness ............................... H
PeeZabiZity:
In accordance with Method I ............ B
In accordance with Method II ........... A
EXAMPLE 4
The same procedure as in Example 3 was repeated except
that the stirring of the mixture was carried out at 50C, instead
of room temperature, to obtain a clear solution. Similar tests
on the coating resulted as shown in Table IV.
TABLE IV
PhysicaZ Properties:
Appearance ......................... Clear
Hardness .............................. 2H
PeeZabiZity:
In accordance with Method I ............ A
In accordance with Method II ........... A
EXAMPLE 5
Into a vessel equipped with a stirrer were charged 100
parts of polyvinylbutyral resin P(2) as used in Example 1, 20
parts of the organopolysiloxane expressed by the aforementioned
formula (IX), 10 parts of butylphthalylbutyl glycolate, 10 parts
6~1~5
of glycerol tributyrate, 240 parts of methanol and 560 parts of
ethanol, followed by mixing with stirring at 50C for 2 hours,
to obtain a clear solution.
The thus obtained solution and the coating film formed
therefrom were determined with respect to their various proper-
ties, and further the coating film was tested for peelability.
The results are set out in Table V.
TABLE V
Of the SoZution:
Viscosity, at 25C ............. 200 cps
Surface Tension ............ 15 dynes/cm
Of the Coating Fi Zm:
Tack-free time, at 25C .......... 5 min
Tensile Strength ............ 110 kg/cm2
Maximum Elongation ................ 100%
PeeZ~biZity: (in accordance with Method III)
Aluminum plate ....................... A
Polystyrene Resin Plate .............. A
Glass Plate .......................... A
Apart from the above, the same solution of resinous com-
position was applied on a methylmethacrylate-styrene copolymer
resin plate by the aerosol-type spray method. The coating film
thus formed was allowed to age at room temperature for 3 months,
and then tested for peelability, to find that the peeling opera-
tion was easy and the exPosed substrate surface was in good con-
dition.
13
~?69~S
EXAMPLE 6
Into a vessel equipped with a stirrer were charged 100
parts of a mixture of polyvinyl butyral resins P(l), P(2), and
P(3) in a weight ratio of 2:1:1, 20 parts of the orqanopolysilox-
ane as used in Example 5, 10 parts of nitrocellulose, 10 parts of
triethyleneglycol and 700 parts of ethanol, followed by mixing
with stirring at 60C for 2 hours, to obtain a clear solution.
The various properties of the thus-obtained solution and
the coating film formed therefrom as well as the peelability of
the coating film were determined in the same fashion as in Exam-
ple 5, with the results as shown in Table VI.
TABLE VI
Of the SoZution:
Viscosity, at 25C ............................ 200 cps
Surface Tension ........................... 15 dynes/cm
Of the Coating:
Tensile Strength ........................... 110 kg/cm2
Maximum Elongation ............................... 100~ !
PeeZabiZity: (in accordance with Method III)
Aluminum Plate ...................................... A
Polystyrene Resin Plate ............................. A
Glass Plate ......................................... A
EXAMPLE 7
Into a vessel equipped with a stirrer were charged 100
parts of the same mixed polyvinyl butyral resins as used in Ex-
ample 1, 20 parts of organopolysiloxane expressed by the afore-
mentioned formula (X), 250 parts of methanol and 250 parts of
ethanol, followed by mixing with stirring at 60C for 2 hours, to
6~5
obtain a clear solution.
The thus-obtained solution and the coating film formed
therefrom were determined with respect to their various proper-
ties and further the coating film was tested for peelability.
The results are set out in Table VII.
TABLE VII
Of the SoZution:
Viscosity, at 25C ............. 300 cps
Surface Tension ............ 10 dynes/cm
Of the Coating:
Tensile Strength ............ 130 kg/cm2
Maximum Elongation ................. 100
PeeZabiZity: (in accordance with Method III)
Aluminum Plate ....................... A
Polystyrene Resin Plate .............. A
Glass Plate .......................... A
EXAMPLE 8
Into a vessel equipped with a stirrer were charged 100
parts of a mixture of polyvinyl butyral resins P(l), P(2) and
P(3) in a weight ratio of 1:1:1, 20 parts of the organopolysilox-
ane as expressed by the aforementioned formula (XII), 510 parts
of methanol, 60 parts of ethanol, followed by mixing with stir-
ring at 60C for 2 hours, to obtain a clear solution.
This solution was used to form a coating film in the same
manner as in Example 1 and the resulting coating film was observed
or tested for its various properties and peelability, with the
results as shown in Table VIII.
6~1~S
TABLE VIII
PhysieaZ Properties:
Appearance ............................. Clear
Hardness .................................. 2H
TensiLe Strength .................. 220 kg/cm2
Maximum Elongation ................ ,... 10
PeeZabiZity:
In accordance with Method I ........... .... A
In accordance with Method II .......... .... A
EXAMPLE 9
The same procedure as in Example 8 was repeated except
only that the organopolysiloxane used was one expressed by the
aforementioned formula (XIII) instead of formula (XII), to obtain
a similarly clear solution. Similar observations or tests were
carried out for the coating film formed from the solution, with
the results identical to those shown in Table VIII of Example 8.
_ AMPLE 10
The same procedure as in Example 1 was repeated except
that the organopolysiloxane was employed in an amount of 3 parts
or 30 parts instead of 20 parts and that the temperature at which
stirring was conducted was 60C instead of room temperature, re-
sulting in producing a similarly clear solution. Similar obser-
vations and tests were carried out with the coatinq films formed
from these two solutions, with the results dS set out in Table IX.
16
6~S
TABLE IX
Amount of Organopolysiloxane3 parts 30 parts
PhysicaZ Properties:
Appearance ..................... Clear Clear
Hardness ....................... 2H 2H
Tensile Strength ............... 240 kg/cm2 200 kg/cm2
Maximum Elongation ............. 10% 10%
Pe e Zab i Z i ty :
In accordance with Method I A A
In accordance with Method II A A
EXAMPLE 11
For comparative purposes, the same procedure as in Exam-
ple 1 was repeated except that the organopolysiloxane used was
one of those expressed by the undermentioned formulas, instead of
that expressed by formula (VIII) and that the temperature at
which stirring was conducted was 60C, instead of room tempera-
ture, resulting in producing a solution which was opaque in
appearance.
fH3
(a) CH3-Si -Ofi-OC2Hs
CH3 3
fH3 ~ fH3 ¦ CH3
(b) CH3-SiOt SiO ! Si-CH3
CH3 1(CH 2~0 - tC2 H 4 O~COCH3J3 8 CH3
f 3 ~ICH3l ~ fH3 1 CH3
(c) CH3-SiO~ SiO ~ SiO l Si-CH3
CH3 lCH3J 27 O CH3
(C H O) C H
- ~ 2 4 48 4 9 3
i9~
(d) CH3-Si -Of ~ O--~C~H40 ~ C3H60 ~ C4Hsl
fH3 ~CH31 ¦ CH3 1 CH3
(e) CH3-fiO- fiO~ fiO ~ - fi-CH3
CH3 CH3 27 ~(CH2~o--~C2H4o) 24 (c3H6o ~ C4Hs 3 CH
Then, using this solution a coating film was prepared in
the same fashion as in Example 1 and subjected to observations or
tests with respect to its appearance, physical properties and
peelability. The results are shown in Table X.
TABLE X
--------- OrganopoZysi?o~cane ---------
(a) (b) (c) (d) (e)
Appearance ................ Opaque lucanent Opaque Opaque Opaque
Hardness .................. 2H 2H 2H 2H 2H
Tensile strength, kg/cm2 260 230 * * *
Maximum elongation, ~ ..... 10 10 * * *
Peelability: Method I C C C C C
Peelability: Method II B B B B B
*Film obtained was of dimensions insufficient for determining the property.
