Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~1~03~4
SURFACE TREATMENT COMPOSITION AND
SURFACE-TREATED RESIN MOLDING
FIELD OF THE INVENTION
The present invention relates to a surface treatment
composition which is capable of forming coatings having excellent
gas barrier properties, transparency and flexibility, and gas
barrier material and heat sticking preventing coating for heat-
sensitive heat transfer, both of which are surface-treated with
the composition.
DESCRIPTION OF THE RELATED ART
Gas barrier materials having an extremely low level of
permeability to gases such as oxygen, nitrogen, carbon dioxide,
water vapor, etc. are increasingly demanded in the field of
packaging materials. Known methods of giving the gas barrier
properties to molded materials such as plastic films or sheets
include (1) the method of forming a molded product by using a
gas-impermeable material such as an ethylene-vinyl alcohol
copolymer, a vinylidene chloride copolymer, a poly-m-xylylene
adipamide or the like; (2) the method of laminating or coating
such a gas-impermeable material on other materials; (3) the
method of laminating an aluminum foil on a film material; and (4)
the method of depositing a metal oxide.
However, of the gas-impermeable materials used in method
(1), ethylene-vinyl alcohol copolymer and poly-m-xylylene
1
2154364
adipamide have the problem that the gas-barrier properties
significantly deteriorate with moisture absorption due to high
hygroscopicity thereof. Vinylidene chloride copolymers have
chlorine atoms and thus might cause environmental pollution.
In method (3), an aluminum foil-laminated film makes a packaged
content invisible from the outside. In method (4), a metal-
deposited film has the problem that since a flexibility of the
film deteriorates, cracks easily occur in the deposited layer
during packaging, thereby deteriorating the gas barrier
properties.
In order to solve the above problems, research~has been
made for treating the surface of a plastic film with polysiloxane
having a tight molecular structure and excellent weather
resistance, hardness and chemical resistance. However, since
tetraalkoxysilane used as a material for polysiloxane exhibits as
many as four hydrolytic condensation reaction points, the
volumetric shrinkage rate in condensation is large, and it is
thus difficult to obtain a coated film without cracks or pin-
holes.
Therefore, a method for preventing cracks and pinholes
has been proposed in which alkyltrialkoxysilane having only three
hydrolytic condensation reaction points is used singly or in
combination with tetraalkoxysilane for co-hydrolytic
condensation. However, in the present situation, since
alkyltrialkoxysilane has low reactivity, use of alkyltri-
alkoxysilane alone leaves many uncondensed monomers, and
2
2150364
combination with tetraalkoxysilane hardly permits uniform
cohydrolytic condensation. Further, such silane type surface
treatment compositions exhibit no affinity for plastic film
materials and have poor wettability, thereby causing the problem
of have poor membrane-forming properties.
Japanese Patent Laid-Open No. HEI 2-286331 discloses the
method of coating alkoxysilane on a plastic film by hydrolytic
condensation. However, in this method, only an alkoxysilane
component is coated on the film, and thus the flexibility of the
film significantly deteriorates.
From the above viewpoints, for example, Japanese Patent
Laid-Open No.HEI 1-278574 discloses that alkoxysilane hydrolyzate
such as tetraalkoxysilane or the like is combined with a reactive
urethane resin for preventing cracks in a surface-treated
coating. However, since the reactive urethane resin reacts with
an alcohol used as a solvent, the alkoxysilane hydrolyzate and
the reactive urethane resin are not sufficiently compounded and
thus cause phase separation, thereby making the coating opaque.
On the other hand, in recent years, a heat-sensitive
recording system has frequently been used for facsimile and
printers in which a heat-sensitive color-developing layer
comprising two components dispersed therein, which develop a
color on heating, is provided on a substrate. However, this
system has the faults of poor storage stability, liability to
change after recording, and poor solvent resistance.
A .transfer-type heat-sensitive recording system is known as means
3
21503fi4
for removing the above faults.
In the transfer-type heat-sensitive recording system,
printing is made on a receiving sheet (e. g., plain paper) by heat
pulses from a heating head through a heat-sensitive transfer
material. A generally known heat-sensitive transfer material
has a heat transfer ink layer such as a heat-meltable ink layer,
a heat-sublimable dye-containing layer or the like, which is
provided on the side contacting the receiving sheet. Since
there have recently been demand for improving printing
performance and printing speed, a method of decreasing the
thickness of a base film and a method of increasing the quantity
of heat applied to the heating head have been proposed.
However, these methods cause the problem of melting the base film
due to the large heat load on the base film, thereby causing a
trouble in running of the heating head. This phenomenon is
generally known as "heat sticking".
In order to remove this heat sticking, various proposals
have been made. For example, Japanese Patent Laid-Open
No. SHO 55-7467 discloses the method of coating a heat-resistant
resin such as a silicone resin, an epoxy resin or the like on one
side of a base film. However, in the present situation, coating
of such a heat-resistant resin requires heat curing at 100°C or
more for several hours, and additionally the satisfactory effect
in preventing heat sticking cannot be obtained because a silicone
resin has poor adhesion to the base film and an epoxy resin has
poor lubricity of the coating surface.
4
X150364
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to
provide a surface treatment composition which can form a
surface-treated coating exhibiting excellent gas barrier
properties without being affected by humidity, transparency and
flexibility which does not deteriorate the physical properties of
a material to be treated.
The second object of the present invention is to provide
a surface-treated resin molding having the above excellent
characteristics.
The third object of the present invention is to provide a
high-quality coating for preventing heat sticking in heat-
sensitive heat transfer by utilizing the surface treatment
composition.
A surface treatment composition of the present invention
comprises
at least one silane compound component selected from the
group consisting of the following silane compounds:
(1) a silane compound (A) represented by the following
formula (I):
R2 R3
w _
Rl -N-Al -S i - (OR4~ ...
wherein A1 indicates an alkylene group; R1 indicates a hydrogen
atom, a lower alkyl group or - AZ - N - R6
R5
~mo3s4
wherein A2 indicates a direct bond or an alkylene group, and R5
and Rs each indicate a hydrogen atom or a lower alkyl group; R2
indicates a hydrogen atom or a lower alkyl group; R3 indicates
the same or different lower alkyl groups, aryl groups or unsatu-
rated aliphatic residues; R4 indicates a hydrogen atom, a lower
alkyl group or an acyl group; at least one of R1, R2, R5 and R6
is a hydrogen atom; w indicates 0, 1 or 2; z indicates an integer
of 1 to 3; and w + z - 3;
(2) a hydrolytic condensation product (B) of the silane
compound (A): and
(3) a coo-hydrolytic condensation product ~i~) of the
silane compouuci (A) and an organometallic compound (C)
represented by the following formula (II):
R'mlvl ~~ R 8 ~ n ... (I I)
wherein M indicates a metal element; R7 may be the same or
different and indicates a hydrogen atom, a lower alkyl group, an
aryl group or an ,unsaturated aliphatic residue; R8 indicates a
hydrogen atom, a lower alkyl or an acyl group; m~ indicates 0 or a
positive integer; and n indicates an integer of 1 or more; the
value (m + n) being equal to the valency of metal_ element M;
a compound (Ep having at least two functional groups
which can react with annino groups in its molecule; and solvent
(F).
The surface tre,~tment composition may comprise at least
one silane compound component selected from the group consisting
6
~1503~4
of (1) a silane compound (A) represented by the above formula
(I), and (2) a hydrolytic condensation product (B) of a silane
compound (A); an organometallic compound (C) represented by the
above formula (II) and/or a hydrolytic condensation product (G)
of an organometallic compound (C), a compound (E) having at least
two functional groups which can react with amino groups in its
molecule; and solvent (F).
The functional groups in the compound (E) which can react
with amino groups are preferably at least one type selected from
the group consisting of an epoxy group, an isocyanate group, a
carboxyl group and an oxazolinyl group. Further, the compound
(E) preferably has an aromatic ring or a hydrogenated ring
thereof in its molecule.
The above-described surface treatment composition is
useful for gas barrier and can be used for coatings for
preventing heat sticking in heat-sensitive heat transfer. The
present invention includes a surface-treated resin molding in
which at least one surface thereof is treated with the above
surface treatment composition.
BRIEF DESCRIPTION OF THE DRAWING
Fig. 1 is a drawing illustrating an example of
application of a heat sticking preventing coating for heat-
sensitive heat transfer materials.
7
CA 02150364 2000-OS-10
DESCRIPTION OF TIfE PREFERRED EMBODIMENTS
'rte used components used are described in order for
describing the present invention in further detail.
The silane compound (A) used in the present invention and
represented by the following formula (I):
R.2 R3
w
Rl -N-A1 -S i - (OR4~ . (I)
wherein A1 indicates an alkylene group, R1 indicates a hydrogen
atom, a lower alkyl group or
_A2 _N-R6
I
R5
wherein ~1; R2, R3, R4, R5, Rs, w and z indicate the same as the
above;
'is not limited so long as the silane compound has an amino group
and a hydrolytic condensable group in its molecules, as shown in
formula (I).
Examples of such a silane compound(A) include
N-l3(aminoethyl) Y-aminopropyltrimethoxysilane,
N-/3(aminoethyl) Y-aminopropyltriethoxysilane,
N-/3(aminoethyl) Y-aminopropyltriisopropoxysilane,
N-(3(aminoethyl) Y-aminopropyltributoxysilane,
N-p(aminoethyl) Y-aminopropylmethyldimethoxysilane,
N-p(aminoethyl) Y-aminopropylmethyldiethoxysilane,
N-(3(aminoethyl) Y-aminopropylmethyldiisopropoxysilane,
N-(3(aminoethyl) Y-aminopropylmethyldibutoxysilane,
8
215036
N-(3(aminoethyl) Y-aminopropylethyldimethoxysilane,
N-p(aminoethyl) Y-aminopropylethyldiethoxysilane,
N-p(aminoethyl) Y-aminopropylethyldiisopropoxysilane,
N-p(aminoethyl) Y-aminopropylethyldibutoxysilane,
Y-aminopropyltrimethoxysilane,
Y-aminopropyltriethoxysilane,
Y-aminopropyltriisopropoxysilane,
Y-aminopropyltributoxysilane,
Y-aminopropylmethyldimethoxysilane,
Y-aminopropylmethyldiethoxysilane,
Y-aminopropylmethyldiisopropoxysilane,
Y-aminopropylmethyldibutoxysilane,
Y-aminopropylethyldimethoxysilane,
Y-aminopropylethyldiethoxysilane,
Y-aminopropylethyldiisopropoxysilane,
Y-aminopropylethyldibutoxysilane,
Y-aminopropyltriacetoxysilane and the like. One or more than
two of these compounds can be used.
A compound (B) is previously obtained by hydrolytic
condensation of at least one of the above silane compound (A).
For example, when Y-aminopropyltrimethoxysilane is used as
compound (A), hydrolytic condensation reaction is represented by
the formulas below.
H2N-CsHs-Si (OCH~) 3 + 3H20 -~ HZN-C3H6-Si (OH) 3 + 3CH30H
HZN-C3H6-Si(OH)3 -~ HZN-C3H6-Si03,2 + 3/2 H20
9
21503f 4
The reaction of hydrolytic condensation proceeds in the
presence of the silane compound (A) and water, it is favorable
for the surface treatment composition to react in solvent (F)
which will be described below. The molar ratio A/W of the
silane compound (A) to water is preferably 0.1 to 3. With a
molar ratio of less than 0.1, gelation comes to easily occur
during condensation. With a molar ratio of more than 3, much
time is required for the reaction, and the silane compound might
remain unreacted. The reaction time is not limited, but it is
preferable to cvomplete the hydrolytic condensation reaction.
This is because when the silane compound (B) previously obtained
by condensation is used, sufficient hydrolytic condensation can
prevent the occurrence of cracks in a surface-treated coating due
to lE~ss volumetric shrinkage thereof.
The surface treatment composition of the present
inve:ntion can contain a co-hydrolytic condensation product(D) of
the silane compound (A) and an organometallic compound (C). The
org;anometallic compound (C) which can form the product of co-
hydrolytic condensation with the silane compound (A) is not
limited so long as the compound (C) is represented by the formula
(II) below.
R'mM ( O R ° ) ~ ... (I I)
wherein M, R7, R8, m and n indicate the same as the above.
Examples of such an organometallic compound(C) include
alkoxysilanes such as tetramethoxysilane, tetraethoxysilane,
215036
tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane,
methyltriethoxysilane, methyltriisopropoxysilane,
methyltributoxysilane, ethyltrimethoxysilane,
ethyltriethoxysilane, ethyltriisopropoxysilane,
ethyltributoxysilane, dimethyldimethoxysilane,
dimethyldiethoxysilane, dimethyldiisopropoxysilane,
dimethyldibutoxysilane, diethyldimethoxysilane,
diethyldiethoxysilane, diethyldiisopropoxysilane,
diethyldibutoxysilane, vinyltrimethoxysilane,
viriyltriethoxysilane,
Y-glycidoxypropyltrimethoxysilane,
Y-glycidoxypropyltriethoxysilane,
r-methac~,-oxypropyltrimethoxysilane,
Y-chloropr~opyltrimethoxysilane,
Y-mercaptop~ropyltrimethoxysilane and the like; titanium alkoxides
such as titanium tetraethoxide, titanium tetraisopropoxide,
titanium te~~rabutoxide and the like; zirconium alkoxides such as
zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium
tetrabutoxide and the like; aluminum alkoxides such as aluminum
triethoxide, aluminum triisopropoxide, aluminum tributoxide and
the like; acyloxysilanes such as tetraacetoxysilane, methyl-
triacetoxysilane and the like; silanols such as trimethylsilanol
and the like. The co-hydrolytic condensation product (D) is
produced by hydrolysis and condensation of at least one of the
organometallic compounds with the silane compound (A). The
reaction may be effected under the same conditions as the above-
11
2150364
described conditions for hydrolytic condensation of the silane
compound (A).
The silane compound component used in the surface
treatment composition of the present invention comprises at least
one selected from the group consisting of the silane compound
(A), the hydrolytic condensation product (B) of the silane
compound (A), and the co-hydrolytic condensation product (D) of
the organometallic compound (C) and the silane compound (A). In
the present invention, combination of one or both of the silane
compound (A) and the hydrolytic condensation product (B) of the
silane compound (A), and one or both of a hydrolytic condensation
production (G) of the organometallic compound (C) and the
organometallic compound (C) can also be used as the silane
compound component. The organometallic compound (C) or the
hydrolytic condensation product (G) thereof is effective for
improving the chemical resistance and heat resistance of a
coating. In this case, the organometallic compound (C) and/or the
hydrolytic condensation product (G) thereof is preferably used in
an amount of 0 to 200 mol%, and more preferably 0 to 100 mol%,
based on the silane compound component. Use of more than
200mo1% sometimes causes the formation of particles with amine in
the silane compound component, which serves as a catalyst, and
thus rapidly produces gelation.
A compound (E) used in the present invention has at least
two functional groups which can react with the amino groups in
the molecule of the silane compound component, and is used as a
12
X150364
cross-linking agent for the silane compound component. The
functional groups which can react with amino groups are epoxy
groups, carboxyl groups, isocyanate groups, oxazolinyl groups
and the like, and they may be the same or different in the
compound (E). From the viewpoint of reactivity, epoxy or
isocyanate groups are preferable. when it is necessary to
improve the humidity resistance of the surface-treated coating
obtained by the composition of the present invention, the
compound (E) preferably has an aromatic ring or a hydrogenated
ring thereof in its molecule. Examples of such a compound (E)
include aliphatic diglycidyl ethers such as ethylene glycol
diglycidyl ether, diethylene glycol diglycidyl ether, triethylene
glycol diglycidyl ether, tetraethylene glycol diglycidyl ether,
nonaethylene glycol diglycidyl ether, propylene glycol
diglycidylether, dipropylene glycol diglycidyl ether,
tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl
ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl
ether and the like; polyglycidyl ethers such as glycerol
triglycidyl ether, diglycerol triglycidyl ether, triglycidyl
tris(2-hydroxyethyl) isocyanurate, trimethylolpropane triglycidyl
ether, pentaerythritol tetraglycidyl ether and the like;
aliphatic and aromatic diglycidyl esters such as diglycidyl
adipate, diglycidyl o-phthalate and the like; glycidyl compound s
having an aromatic ring or a hydrogenated ring thereof (including
nucleus-substituted derivatives) such as bisphenol A diglycidyl
ether, resorcinol diglycidyl ether, hydroquinone diglycidyl
13
. ~mo3s~
ether, bisphenol S diglycidyl ether, bisphenol r diglycidyl
ether, compounds represented by the following formulas:
\/ CH2 \/ 0~ 0 0 \/ CH \/
I
CH3
0
0 CH3 CH3
CH- CH ~ 0 -
\/ ~~ 0 0
I
w w ( CH3 CH3
C O
/ CH2 \ / N~ ~ N 0
0 ~I
0
\ / N~ CHs
CHs CH3 CH3
OCHCH20 \ / C OCH CHO~ ~ OCO C00
\/ 2 / \
CH3
OCO C00 ~ ~ OCO C00 ~
0
CH3
CH3
I /~7 ~ OCO C00
0~ C-Q-0 0
I
CH3
0
0 II
0!~1~ 0~0 0 H C - 0 - C H 2
~0
0 0
il II
0 ~ CH20C(CHZ),q C- 0- CH2~0
CH3 CH~y3
14
.. ~~~o~s~~
oligomers having glycidyl groups as functional groups, such as
bisphenol A diglycidyl ether oligomer represented by the
following formula:
i Hs OH
CHZ-CH-CHZ-0 ~ ~ i ~ ~ 0-CHZ-CH-CH2-0
CH3 n
~H~
-~C--~0-CH2-CH- CH2
CH3
n - 0 or an integer of 1 or more
isocyanates suci: vs hexamethylene diisocyanate, tolylene
diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene
dii~socyanate, tri_phenylmethane triisocyanate, tolidine
diisocyanate, xyl_ylene diisocyanate, dicyclohexylmethane
diisocyanate and the like; dicarboxylic acids such as tartaric
acid, adipic acids and the like; carboxyl group-containing
polymers such as polyacrylic acid and the like; oxazolinyl
group-containing polymers and the like. At least one of these
compounds can be used.
The used amount of the compound (E) is preferably 0.1 to
300 % by weight, more preferably 1 to 200 % by weight, relative
to the total amount of the silane compound componen t. The
compound (E) reacts with the amino groups in the silane compound
component and functions as a cross-linking agent component. If
the amount of the compound (E) is less than 0.1 % by weight, the
~15036~
obtained coating exhibits insufficient flexibility. The use of
more then 300 % by weight of the compound (E) possibly
deteriorates gas barrier properties, and is thus undesirable.
As described above, the surface treatment composition of
the present invention contains, as the silane compound component
which reacts with the compound (E), the following compounds:
(1) the silane compound (A);
(2) the hydrolytic condensation product (B) of the silane
compound (A);
(3) the co-hydrolytic condensation product (D) of the
silane compound (A) and the organometallic compound (C); or
combination of the compound (A) and/or the compound (B)
and the hydrolytic condensation product (G) of the organometallic
compound (C) and/or the organometallic compound (C). The
surface treatment composition may contain the silane compound in
the following form:
(4) a reaction product (AE) of the silane compound (A)
and the compound (E);
(5) a hydrolytic condensation product (PAE) of the silane
compound (A) before or after reaction with the compound (E);
(6) a reaction product (AEC) of the silane compound (A),
the compound (E) and the organometallic compound (C); or
(7) a (co)-hydrolytic condensation product (PAEC) of the
silane compound (A) before and after reaction with the compound
16 w
;,,~, .
2150364
(E) and the organometallic compound (C).
Each of forms (5) and (7) is further divided into the
following forms:
Form (5)
(8) A reaction product of the hydrolytic condensation
product of the silane compound (A) and the compound (E);
(9) A hydrolytic condensation product of the reaction
product of the silane compound (A) and the compound (E).
Form (7)
(10) A reaction product of the hydrolytic condensation
product of the silane compound (A), the compound (E) and the
organometallic compound (C);
(11) A co-hydrolytic condensation product of the silane
compound (A), the compound (E) and the organometallic compound
(C) after reaction thereof.
Silane compounds in all forms (1) to (11) can be used for
the reactive silane compound component having residual amino
groups or silane portions which can product crosslinking reaction
or hydrolytic condensation.
Solvent (F) used in the present invention is not limited
so long as the solvent will dissolve the silane compound
component and the compound (E). Examples of solvents include
alcohols such as methanol, ethanol, 2-propanol, butanol,
pentanol, ethylene glycol, diethylene glycol, triethylene glycol,
17
CA 02150364 2000-OS-10
ethylene glycol monomethyl ether, diethylene glycol monomethyl
ether, triethylene glycol monomethyl ether and the like; ketones
such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
cyclohexanone and the like; aromatic hydrocarbons such as
toluene, benzene, xylene and the like; hydrocarbons such as
hexane, heptane, octane and the like; acetates such as methyl
acetate, ethyl acetate, propyl acetate, butyl acetate and the
like; other solvents such as ethyl phenol ether, propyl ether,
tetrahydrofuran and the like. Only one or a mixture of .at least
two solvents can be used. Alcohols among these solvents are
preferably used. The hydrolytic condensation reaction is
preferably undergone in these solvents.
The surface treatment composition of the present
invention can contain inorganic and organic various additives
such as a curing catalyst, a wettability improving agent, a
plasticizes, an anti-foaming agent, a thickener etc. within the
range which does not deteriorate the effect of the invention,
according to demand.
A resin molding is used as a substrate to be coated with
the surface treatment composition of the present invention.
The,resin used for molding Is not limited. Examples of such
resins include polyolefin resins such as polyethylene,
polypropylene and the like; polyester resins such as polyethylene
terephthalate, polyethylene isophthalate, polyethylene-2,6-
naphthalate, polybutylene terephthalate, copolymers thereof and
the like; polyamide resins; polyoxymethylene resins;
18
X150364
thermoplastic resins such as polystyrene, poly(meth)acrylate,
polyacrylonitrile, polyvinyl acetate, polycarbonate, cellophane,
polyimide, polyetherimide, polyphenylenesulfone, polysulfone,
polyether ketone, ionomer resins, fluororesins and the like;
thermosetting resins such as melamine resins, polyurethane
resins, epoxy resins, phenolic resins, unsaturated polyester
resins, alkyd resins, urea resins, silicone resins and the like.
The shape of the molding can be selected from a film, a
sheet, a bottle and so on according to application. A thermo-
plastic film is preferable from the viewpoint of the ease of
processing.
The method of coating the resin molding with the surface
treatment composition is not limited, and a roll coating method,
a dip coating method, a bar coating method, a nozzle coating
method and the like or combination thereof is used. The resin
molding can be subjected to surface activation treatment such as
corona treatment, or known anchoring treatments using an urethane
resin and the like before coating. After the resin molding is
coated with the surface treatment composition, lamination
treatment or other known treatments may be made.
After coating, the coated film is cured and dried.
Although the surface treatment composition of the present
invention is cured and dried at room temperature, the resin
molding may be heated to a temperature below the heat resistant
temperature thereof for more rapidly curing and drying it. The
coating thickness after drying is preferably 0.001 to 20 ~cm, more
19
2150364
preferably 0.01 to 10 a m. with a thickness of less than
O.OOlum, a uniform coating cannot be obtained, and pinholes
easily occur. A thickness of more than 20u m is undesirable
because cracks easily occur in the coating.
The surface treatment composition of the present
invention is useful for giving gas barrier properties to the
resin molding, and can also be used for a heat sticking
preventing agent for heat-sensitive transfer. An example of
such application is shown in Fig. 1. A heat transfer ink layer
2 is provided on one side of a base film 1, and a heat sticking
preventing layer 3 comprising a heat sticking preventing agent of
the present iiavention is provided on the other side thereof to
form a heat-sensitive heat transfer material. The heat transfer
ink layer 2 comprises a conventional heat-meltable ink layer or a
heat-sublimatole dye-containing layer, and is formed by a
conventional known coating or printing method. The heat
sticking pre~renting layer 3 of the present invention has heat
resistance, good slip properties and the large ability to prevent
heat stickinig, and can be applied to the base film by a
conventional coating or printing. machine.
If required, an adhesive layer can be interposed between
the base film 1 and the heat sticking preventing.layer 3. The
thickness of the heat sticking preventing layer 3 is preferably
0.1 to 5 a m, The heat sticking preventing layer 3 can be formed
by a conventional known coating or printing method using the
surface treatment composition of the present invention. In the
CA 02150364 2000-OS-10
formation, a curing catalyst may be used according to demand.
A conventional film can be used as the base film.
Examples of such films include polyester films, polycarbonate
films, cellulose acetate films, polypropylene films, cellophane
and the like.
In the surface treatment composition of the present
invention, it is possible to securely prevent the occurrence of
cracks by using, as the silane compound component, a large amount
of the hydrolytic condensation product (B) or (D) which exhibits
less volumetric shrinkage during curing. The combination of the
organometallic compound (C) and the hydrolytic condensation
product (G) thereof is effective for improving the heat
resistance and chemical resistance of the coating.
EXAMPLES
The present invention is described in detail below with
reference to examples, but the invention is not limited to these
examples.
In characteristic tests, the following evaluation methods
were employed:
(Oxygen permeability)
Measured at 20 °C in accordance with JIS K 7126 method B.
(Flexibility)
The surface treatment composition was coated to a pre-
determined thickness on a polyethylene terephthalate (abbreviated
to PET hereinafter) film of 12 u.m, and the dry coated film was
21
CA 02150364 2000-OS-10
then bent at 180°. Mark ~ indicates no occurrence of cracks,
and mark x indicates the occurrence of cracks.
(Transparency)
A 1'ET film which was coated by the same method as in the
flexibility evaluation test was visually compared with an un-
treated film. Mark O indicates no difference in transparency,
and mark x indicates the occurrence of turbidity such as white
turbidity.
REFERENCE (Pretreatment of resin molding)
25 g of urethane coating agent TAKENATE* A-3 (produced by
Takeda Yakuhin-Kogyo-KK.), 150 g of Takerack A-310 (produced by
Takeda Yakuhin-Kogyo-KK.) and 500g of ethyl acetate were mixed to
obtain an urethane undercoating agent. The undercoating agent
was coated to a thickness of 2.0 u.m on a 12~.mPET film by the
dipping method, and then dried at 120°C for 30 minutes. The
thus-obtained film was transparent and exhibited flexibility
shown by mark ~ and oxygen permeability of
70.'Olcc/m2~ 24 hrs ~ atm.
EXAMPLE 1
2 g of ethylene glycol diglycidyl ether (abbreviated to
"LEDGE" hereinafter) was added to a mixture of 15 g of Y-amino-
propyltrimethoxysilane (abbreviated to "APTM" hereinafter) and
120 g of methanol, and the resultant mixture was then stirred at
21 °C for 5 hours to obtain surface treatment composition 1.
* Trade-mark
22
~mo3s4
This composition 1 was coated to a thickness of 0.2 a m by the
dipping method on the resin molding obtained in Reference Example
1, and then dried by allowing it to stand at 21°C for 24 hours.
The thus-obtained surface-treated film was transparency and
exhibited flexibility shown by mark O and oxygen permeability of
6.12 cc/m2~ 24 hrs ~ atm.
EXAMPLE 2
15 g of APTM, 60 g of methanol and 1.5 g of water were
mixed, and the resultant mixture was stirred at 21 °C for 24 hours
to obtain APTM hydrolytic condensation product. 2 g of lEDGE
was then added to the APTM hydrolytic condensation product
solution, and the resultant mixture was stirred at 21 C for 24
hours to obtain a surface treatment composition. The
composition was coated to a thickness of 0.4 a m on the resin
molding obtained in Reference Example 1 by the dipping method,
and then dried by allowing it to stand at 21°C for 24 hours.
The thus-obtained surface treated film was transparency and
exhibited flexibility shown by mark O and oxygen permeability of
2.92 cc/m224 hrs~atm.
EXAMPLES 3 to 13
Surface-treated films were formed by the same method as
Example 2 except that conditions were changed, as shown in Table
1, and then subjected to characteristic tests. The results of
the tests are shown in Table 1.
23
EXAMPLE 14
15 g of APTM, 120 g of methanol and 1.5 g of water were
mixed, and the resultant mixture was stirred at 21 °C for 24
hours to obtain APTM hydrolytic condensation product. 2 g of
lEDGE was then added to the APTM hydrolytic condensation product
solution, and the resultant mixture was stirred at 21°C for 5
hours, and 5 g of tetramethoxysilane (referred to as "TMOS"
hereinafter) was added to the solution to obtain a surface
treatment composition. The composition was coated, dried and
then subjected to characteristic tests by the same method as
Example 1. The obtained results are shown in Table 1.
EXAMPLE 15
15.8 g of TMOS, 124.8 g of methanol, 3.0 g of water and
0.4 g of concentrated hydrochloric acid were mixed, and the
resultant mixture was stirred at 21°C for 24 hours to obtain TMOS
hydrolytic condensation product. 15 g of APTM and 2 g of lEDGE
were then added to the TMOS hydrolytic condensation product
solution, and the resultant mixture was stirred at 21°C for 5
hours to obtain a surface treatment composition. The
composition was coated, dried and then subjected to
characteristic tests by the same method as Example 1. The
obtained results are shown in Table 1.
24
2150364
EXAMPLE 16
15 g APTM, 120 g of methanol and 2 g of lEDGE were
of
mixed, and the resultant mixture was then stirred at 21 C for 5
hours. 5 g of TMOS was then added to the mixture to obtain a
surfacetreatme nt composition. The composition was coated,
dried nd then sub3ected to characteristic tests by the same
a
method as Example 1. The obtained results are shown in Table 1.
The compounds
below
are
abbreviated
as follows:
APTM :Y-aminopropyltrimethoxysilane
APTE :Y-aminopropyltriethoxysilane
NAEAPTM :N-!3(aminoethyl) r-aminopropyl
trimethoxysilane.
TMOS :tetramethoxysilane
TEOS :tetraethoxysilane
MTMOS :methyltrimethoxysilane
TBOT :titanium tetrabutoxide
GPTM :Y-;glycidoxypropyltri~lethoxysilane
VTM :vinyltrimethoxysilane
lEDGE :ethylene glycol diglycidyl ether
2EDGE :diethylene glycol diglycidyl ether
4EDGE :tetraethylene glycol diglycidyl ether
PE4GE :pentaerythritol tetraglycidyl ether
EG :ethylene glycol
HMDA :hexamethylenediamine
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26
CA 02150364 2000-OS-10
COMPARATIVE EXAMPLE 1
15 g of APTM and 120 g of methanol were mixed, coated
directly on the resin molding obtained in Reference Example 1,
and then dried. The coating layer of the thus-obtained surface
treated film had a thickness of O.l~cm and was transparent. The
flexibility was shown by mark x, and the oxygen permeability was
5.98 cc/m2~ 24 hrs~ atm.
COMPARATIVE EXAMPLE 2
15 g of APTM, 60 g of methanol and 1.5 g of water were
mixed, and the resultant mixture was then stirred at 21 °C for 24
hours to obtain an APTM hydrolytic condensation product. This
APTM hydrolytic condensation product was coated directly on the
resin molding obtained in Reference Example 1, and then dried.
The thus-obtained coating layer had a thickness of 0.3u.m and was
transparent. The flexibility was shown by mark x, and the
oxygen permeability was 2.70 cc/m2~24 hrs~atm.
COMPARATIVE EXAMPLES 3 to 10
Surface-treated films were formed by the same method as
Comparative Example 1 except the conditions were changed as shown
in Table 2, and then subjected to characteristic tests. The
obtained results are shown in Table 2.
REFERENCE EXAMPLE
15 g of APTM, 5 g of methanol and 1.5 g of water were
27
CA 02150364 2000-OS-10
mixed, and the resultant mixture was teen stirred at 21 °C for 24
hours to obtain an APTM hydrolytic condensation product. 2 g of
lEDGE was added to the Af'1'M hydrol.yt i a c:ondensati on product: , and
the resultant mixture was then stirred at 21°C for 5 hours to
obtain a surface treatment composition. This surface treatment
composition was thickly coated on the resin molding obtained in
Reference Example 1, and then dried. The thus-obtained coating
layer had a thickness of 21.0 ~ m and was transparent. The
flexibility was shown by mark x, and the oxygen permeability was
69.21 cc/m2~ 24 hrs~ atm.
COMPARATIVE EXAMPLE 11
15 g of APTM, 120 g of methanol and 1.5 g of water were
mixed, and the resultant mixture was then stirred at 21°C.for 24
hours to obtain an APTM hydrolytic condensation product. 5 g of
TMOS was added to the APTM hydrolytic condensation product
solution to obtain a surface treatment composition. This
surface treatment composition was coated, dried and then
subjected to characteristic tests. The obtained results are
shown in Table 2.
COMPARATIVE EXAMPLE 12
15.8 g of TMOS, 124.8 g of methanol, 3.0 g of water and
0.4 g of concentrated hydrochloric acid were mixed, and the
resultant mixture was then stirred at 21°C for 24 hours to
obtain a TMOS hydrolytic condensation product. 15 g of APTM was
28
CA 02150364 2000-OS-10
added to the TMOS hydrolytic condensation product solution to
obtain a surface treatment composition. This surface treatment
composition was coated, dried and then subjected to
characteristic tests by the same method as Example 1. The
obtained results are shown in Table 2.
COMPARATIVE EXAMPLE 13
15 g of APTM and 120 g of methanol were mixed, and 5 g of
TMOS was then added to the resultant to obtain a surface .
treatment composition. This surface treatment composition was
coated, dried and then subjected to characteristic tests by the
same method as Example 1. The obtained results are shown in
Table 2.
29
CA 02150364 2000-OS-10
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EXAMPLE 17
2.0 g of water was added to 100 g of methanol, and the
resultant mixture was stirred. 20 g of Y-aminopropyltri-
methoxysilane was dropwisely added to the mixture at 30°C over 30
minutes. After stirring at 30°C for 30 minutes, 3 g of
diethylene glycol diglycidyl ether was added to the mixture, and
the resultant mixture was further stirred for 1 hour to obtain
polymer solution 1.
The thus-obtained polymer solution 1 was coated on one
side of a PET base film having a thickness of 6u m by a bar
coater, and then dried under heating to form a heat sticking
preventing layer having a thickness of 1.5 a m. A heat transfer
ink layer having a thickness of 2u m was formed on the other side
of the base film to obtain heat-sensitive heat transfer material
(1).
A heat transfer test of the thus-obtained heat-sensitive
heat transfer material (1) was performed on recording paper by
using a thermal head printing test apparatus (produced by
Matsushita-Denshi-Buhin-KK.). In the heat transfer test, the
presence of the heat sticking phenomenon was evaluated by
observing the running state of the thermal head. After the heat
transfer test, the contamination state of the thermal head was
also examined. The results obtained are shown in Table 3. The
test conditions were an applied voltage of 20 V and a printing
speed of 2 milliseconds.
31
2150364
EXAMPLE 18
20 g of r-aminopropyltriethoxysilane and 4 g of ethylene
glycol diglycidyl ether were mixed, and the resultant mixture was
stirred at 30°C for 3 hours. 100 g of ethanol and 2.0 g of
water were dropwisely added to the mixture over 1 hour, and the
resultant mixture was further stirred for 2 hours to obtain
polymer solution 2.
The thus-obtained polymer solution 2 was coated on one
side of a PET base film having a thickness of 6 a m by a bar
coater, and then dried to form a heat sticking preventing layer
having a thickness of 1.5u m. A heat transfer ink layer having
a thickness of 2 u.m was formed on the other side of the base film
to obtain heat-sensitive heat transfer material (2). The
performance of the heat-sensitive heat transfer material (2) was
evaluated by the same method as Example 17. The results
obtained are shown in Table 3.
EXAMPLE 19
1.5 g of water was added to 100 g of ethanol, and the
resultant mixture was then stirred. 20 g of N- a (aminoethyl)
Y-aminopropyltrimethoxysilane was dropwisely added to the mixture
at 30°C over 30 minutes. After stirring at 30°C for 3 hours,
2g of nonaethylene glycol diglycidyl ether was added to the
mixture, the resultant mixture was further stirred for 1 hour to
obtain polymer solution 3.
The thus-obtained polymer solution 3 was coated on one
32
CA 02150364 2000-OS-10
side of a PET base film having a thickness of 6 a m by a bar
coater, and then dried under heating to form a heat sticking
preventing layer having a thickness of 1.5 a m. A heat transfer
ink layer having a thickness of 2 a m was formed on the other side
of the base film to obtain heat-sensitive heat transfer material
(3). The performance of the heat-sensitive heat transfer
material (3) was evaluated by the same method as Example 17.
The obtained results are shown in Table 3.
COMPARATIVE EXAMPLE 14
A heat sticking preventing agent for heat-sensitive heat
transfer material was prepared for comparison by the same method
as Example 17 except that diethylene glycol diglycidyl ether was
not used. Like in Example 17, a heat sticking preventing layer
was formed by using the thus-obtained heat sticking preventing
agent, and a heat transfer ink layer was then provided to obtain
comparative heat transfer material (1). The performance of the
comparative heat transfer material (1) was evaluated by the same
method as Example 17. The obtained results are shown in Table
3.
COMPARATIVE EXAMPLE 15
A polymer solution was prepared by the same method as
Example 18 except that diethylene glycol dimethyl ether was used
in place of ethylene glycol diglycidyl ether. Like in Example
18, a heat sticking preventing layer was formed by using the
33
CA 02150364 2000-OS-10
thus-obtained polymer solution, and a heat transfer ink layer was
then provided to obtain comparative heat transfer material (2).
The performance of the comparative heat transfer material (2) was
evaluated by the same method as Example 17. The obtained
results are shown in Table 3.
COMPARATIVE EXAMPLE 16
A comparative heat transfer material (3) was obtained by
the same method as Example 17 except that the heat sticking
preventing layer was not formed. The performance of the
comparative heat transfer material (3) was evaluated by the same
method as Example 17. The obtained results are shown in Table
3.
Table 3
Heat-sensitive Presence of Contamination
of
heat transfer materialheat sticking thermal head
used in heat transfer
test
Example heat-sensitive No No
17
heat transfer material(1)
Example Heat-sensitive No No
18
heat transfer material(2)
Example . Heat-sensitive No No
19
' heat transfer material(3)
ComparativeComparative slightly presentsNo
Example heat transfer material(1)
1 4
ComparativeComparative present present
Example heat transfer material(2)
1 5
ComparativeComparative present present##
Example heat transfer material(3)
1 6
~ The thermal head was not smoothly run.
~~ The melted polyester film adhered,
34
~15o3s~
EXAMPLE 20
50 g of APTE, 30 g of 2-propanol, and 7 g of xylylene
diisocyanate were charged in a flask equipped with a stirrer, a
thermometer and a condenser, and were reacted under heating at
?0 °C for 3 hours. After cooling, 1.5 g of water and 100 g of
2-propanol were added to the reaction solution to obtain gas
barrier surface treatment composition 20. This composition 20
was coated to a thickness of 2.Ou m on a PET film having a
thickness of 12 a m by a bar coater, and then dried at 80 °C for 10
minutes. The physical properties of the thus-obtained surface-
treated film are shown in Table 4.
EXAMPLES 21 to 26
Surface-treated films were formed by the same method as
Example 20 except that various conditions were changed as shown
in Table 4, and then subjected to characteristic tests. The
results obtained are shown in Table 4.
EXAMPLE 27
50 g of APTE, 3 g of TEOS, 30 g of 2-propanol, and 25 g
of bisphenol A diglycidyl ether were charged in a flask equipped
with a stirrer, a thermometer and a condenser, and were reacted
under heating at 70 °C for 3 hours. After cooling, 1.5 g of
water and 100 g of 2-propanol were added to the reaction solution
to obtain gas barrier surface treatment composition 27. A
surface-treated film was obtained by the same method as Example
CA 02150364 2000-OS-10
20 except that the composition 27 was used. The results of
characteristic evaluation are shown in Table 4.
EXAMPLES 28 and 29
Surface-treated films were formed by the same method as
Example 20 except that various conditions were changed as shown
in.Table 4, and subjected to characteristic tests. The obtained
results are shown in Table 4.
EXAMPLE 30
50 g of APTE, 30 g of 2-propanol, and 1.5 g of water were
charged in a flask equipped with a stirrer, a thermometer and a
condenser, and the resultant mixture was stirred at 21°C for 24
hours to obtain an APTE hydrolytic condensation product. 25 g
of bisphenol A diglycidyl ether and 100 g of 2-propanol were
added to the APTE hydrolytic condensation product solution, and
the resultant mixture was reacted at 70 °C for 3 hours and then
cooled to obtain gas barrier surface treatment composition 30.
A surface-treated film was formed by the same method as Example
20. The results of characteristic evaluation are shown in Table
4.
EXAMPLE 31
50 g of APTE, 5 g TEOS, 30 g of 2-propanol, and 1.5 g of
water were charged in a flask equipped with a stirrer, a
thermometer and a condenser, and the resultant mixture was
36
CA 02150364 2000-OS-10
stirred at 21°C for 24 hours'to obtain a co-hydrolytic
condensation product of Al'TE and TEOS. 15 g of resorcinol
diglycidyl ether and 100 g of 2-propanol were added to the co-
hydrolytic condensation product solution, and the resultant
mixture was reacted at 70°C for 3 hours and then cooled to obtain
gas barrier surface treatment composition 31. A surface-treated
film was formed by the same method as Example 20. The results
of characteristic evaluation are shown in Table 4.
EXAMPLE 32
50 g of APTM, 10 g of bisphenol A diglycidyl ether, and
30 g of 2-propanol were charged in a flask equipped with a
stirrer, a thermometer and a condenser, followed by heating at
70 °C for 3 hours and then cooling to obtain gas barrier surface
treatment composition 32. A surface-treated film was formed by
the same method as Example 20. The results of characteristic
evaluation are shown in Table 4.
EXAMPLE 33
50 g of APTM, 10 g of hydroquinone diglycidyl ether, and
30 g of 2-propanol were charged in a flask equipped with a
stirrer, a thermometer and a condenser, followed by heating at
70°C for 3 hours and then cooling. 5 g of TEOS and 100 g of
2-propanol were further added to the mixture to obtain gas
barrier surface treatment composition 33. A surface-treated
film was formed by the same method as Example 20. The results
37
CA 02150364 2000-OS-10
of characteristic evaluation are shown in Table 4.
EXAMPLE 34
50 g of APTE, 3 g of TMOS and 10 g of resorcinol
diglycidyl ether were charged in a flask equipped with a stirrer,
a thermometer and a condenser, followed by heating at 70 C for 3
hours and then cooling to obtain gas barrier surface treatment
composition 34. A surface-treated film was formed by the same
method as Example 20. The results of characteristic evaluation
are shown in Table 4.
COMPARATIVE EXAMPLE 17
50 g of TEOS, 25 g of bisphenol A diglycidyl ether and 30
g of 2-propanol were charged in a flask equipped with a stirrer,
a thermometer and a condenser, followed by treating at 70 °C for
3 hours and then cooling. 2.0 g of water, 200 g of 2-propanol
and 0.2 g of concentrated hydrochloric acid were added to the
mixture, and the resultant mixture was stirred at 21°C for
24 hours to obtain comparative surface treatment composition 18.
A surface-treated film was formed by the same method as Example
20. The results of characteristic evaluation are shown in Table
5.
COMPARATIVE EXAMPLE 18
50 g of AfTE, 60 g of bisphenol A diglycidyl.ether and 30
g of 2-propanol were charged in a flask equipped with a stirrer,
38
CA 02150364 2000-OS-10
a thermometer and a condenser, followed by heating at 70 C
for 3 hours and then cooling. 1.5 g of water and 100 g of
2-propanol were added to the mixture to obtain comparative
surface treatment composition 19. A surface-treated film was
formed by the same method as Example 20. The results of
characteristic evaluation are shown in Table 5.
COMPARATIVE EXAMPLE 19
A surface-treated film was formed by the same method as
Example 20 except that various conditions were changed as shown
in Table 5, and then subjected to characteristic tests. The
obtained results are shown in Table 5.
In Tables 4 and 5, the compounds below are abbreviated as
follows:
XDI :xylylene diisocyanate
TDI :tolylene diisocyanate
BisADGE :bisphenol A diglycidyl ether
RDGE :resorcinol diglycidyl ether
HQDGE :hydroquinone diglycidyl ether
PhDGE :phenyl diglycidyl ether
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The use of the surface treatment composition of the
present invention enables the formation of a transparent coating
exhibiting excellent gas barrier properties without being
affected by humidity and flexibility. The surface-treated resin
molding of the present invention is useful as a gas barrier
material in the field of packaging materials and the like. The
heat sticking preventing agent coating for heat-sensitive heat
transfer obtained by using the surface treatment composition of
the present invention exhibits excellent heat resistance and slip
properties and can provide a coated film having the high ability
to prevent heat sticking.
41
