Heat Shrinkable Multilayer Film And Heat Shrinkable Label
Abstract:
It is an object of the present invention to provide a heat-shrinkable multilayer film which, in the case of using the heat-shrinkable multilayer film as a heat-shrinkable label for
a container, does not produce delamination in covering a container, is superior in heat resistance, oil resistance, tearing properties along the perforation and appearance and can
prevent the reduction in strength between the layers after a printing step, and a heat-shrinkable label comprising the heat-shrinkable multilayer film as a base film.
The present invention is a heat-shrinkable multilayer film which comprises: an outer surface layer comprising a polyester type resin; and an intermediate layer comprising a
polystyrene type resin,said outer surface layer and said intermediate layer being laminated by interposing an adhesive layer comprising a polyester type elastomer or a modified
polyester type elastomer
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Notices, Deadlines & Correspondence
C/O MITSUBISHI CHEMICAL CORPORATION, 1,TOHOCHO, YOKKAICHI-SHI, MIE 5108530
Specification
DESCRIPTION
HEAT SHRINKABLE MULTILAYER FILM AND HEAT SHRINKABLE LABEL
TECHNICAL FIELD
[0001]
The present invention relates to a heat-shrinkable
multilayer film which, in the case of using the heat-shrinkable
multilayer film as a heat-shrinkable label for a container, does
not produce delamination in covering a container, is superior
in heat resistance, oil resistance, tearing properties along
the perforation and appearance and can prevent the reduction
in strength between the layers after a printing step, and a
heat-shrinkable label conprising the heat-shrinkable
multilayer film as a base film.
BACKGROUND ART
[0002]
In recent years, many containers such as PET bottles and
metal cans are covered with heat-shrinkable labels prepared by
performing printing on a base film of a heat-shrinkable resin
film.
As such a heat-shrinkable resin film, films comprising
polystyrene type resin predominate since it is superior in low
temperature shrinkability. However, since the polystyrene
type resin film has inadequate heat resistance, there was a
problem that for example, the heat-shrinkable resin label may
be shrunk and the label may be distorted or broken when a PET
bottle topples in being heated in a hot warmer equipped in a
convenience store, and the like. Furthermore, the polystyrene
type resin film also has a problem that since it has inadequate
solvent resistance, it may be shrunk or dissolved by the
adhesion of oils when it is used for the packaging of articles
containing oils.
[0003]
On the other hand, efforts to use a polyester type film,
which is superior in heat resistance and solvent resistance,
in place of a polystyrene type resin film as a heat-shrinkable
label are made. But, the polyester type film has a problem that
it tends to produce crinkles when it covers a container since
it has bad low temperature shrinkability and is shrunk rapidly.
Further, perforation for tearing off is often provided on the
shrink film so that the heat-shrinkable label can be easily torn
off and removed from the used container in order to recycle
containers, but in the polyester type film, there was also a
problem that tearing properties along the perforation are poor,
and therefore the heat-shrinkable label cannot be easily torn
off and removed from the container. Furthermore, in the
polyester type film, there was a problem that since it has large
shrinking stress, in the case of using the polyester type film
as a label for hot beverages, the label shrinks and compresses
the container due to heating of the beverages at the time of
sale and thereby a level of the content of the container rises
to cause the content to spill over the container.
[0004]
For this situation, in Patent Document 1, a hard
multilayer shrinkable film obtainable by laminating outer
surface layers comprising a polyester type resin on an
intermediate layer comprising a polystyrene type resin with an
adhesive layer comprising an olefin type resin interposed
between the outer surface layer and the intermediate layer, is
disclosed. Further, in Patent Document 2, a heat-shrinkable
label, which includes a base film obtainable by laminating outer
surface layers comprising a polyester type resin comprising a
specific monomer on both sides of an intermediate layer
comprising a polystyrene type resin, and by laminating the outer
surface layers and the intermediate layer without an adhesive
layer interposed between the outer surface layer and the
intermediate layer, is disclosed. Furthermore, in Patent
Document 3, a laminated film having a surface layer comprising
a polyester type resin, an intermediate layer comprising a
styrene type resin and an adhesive layer comprising an adhesive
resin, is disclosed. The heat-shrinkable labels comprising
these multilayer films are superior in low temperature
shrinkability and tearing properties along the perforation by
the virtue of the intermediate layer comprising a polystyrene
type resin, and further they are also superior in solvent
resistance and heat resistance since the intermediate layer is
covered with the outer surface layers comprising a polyester
type resin.
[0005]
However, if these heat-shrinkable labels cover the
containers actually, there were problems that in the hard
multilayer shrinkable film described in Patent Document 1, the
intermediate layer may be peeled off from the outer surface
layer in covering the container, and in the heat-shrinkable
label described in Patent Document 2, after covering the
container with the heat-shrinkable label, if the films rub
against each other during t ransportation of products or the film
is scratched with a fingernail or a body, peeling may occur
between an intermediate layer and an outer surface layer.
Further, when the heat-shrinkable labels are used for PET
bottles for drinking, decoration of labels is performed by
printing for the purpose of differentiating products from those
of other companies or enhancing images of user. However, since
printing ink used in a pointing step of the label generally
contains an organic solvent, a trace of the organic solvent
remains on the printed surface after printing and drying.
Thereby, a problem that when the heat-shrinkable film described
in Patent Document 3 is used, an adhesive property between the
outer surface layer and the intermediate layer is affected by
a residual organic solvent and adhesion strength between the
outer surface layer and the intermediate layer after a printing
step is significantly recuced in comparison with that before
the printing step has newly arisen.
Accordingly, a heat-shrinkable multilayer film, which,
in the case of using the heat-shrinkable multilayer film as a
heat-shrinkable label for a container, does not produce peel
between the outer surface layer and the intermediate layer in
covering a container, is superior in heat resistance, oil
resistance, tearing properties along the perforation and
appearance, is less-affected by an organic solvent used in a
printing step and has adequate adhesion strength after the
printing step, has been required.
Patent Document 1: Japanese Kokai Publication Sho-61-41543
Patent Document 2: Japanese Kokai Publication 2002-351332
Patent Document 3: Japanese Kokai Publication 2006-15745
DISCLOSURE OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0006]
In view of the above state of the art, it is an object
of the present invention to provide a heat-shrinkable
multilayer film which, in the case of using the heat-shrinkable
multilayer film as a heat-shrinkable label for a container, does
not produce delamination in covering a container, is superior
in heat resistance, oil resistance, tearing properties along
the perforation and appearance and can prevent the reduction
in strength between the layers after a printing step, and a
heat-shrinkable label comprising the heat-shrinkable
multilayer film as a base film.
MEANS FOR SOLVING THE PROBLEMS
[0007]
The present invention is a heat-shrinkable multilayer
film which comprises: an outer surface layer comprising a
polyester type resin; and an intermediate layer comprising a
polystyrene type resin, said outer surface layer and said
intermediate layer being faminated by interposing an adhesive
layer comprising a polyester type elastomer or a modified
polyester type elastomer.
Hereinafter, the present invention will be described in
detail.
[0008]
The present inventors found that in the heat-shrinkable
label comprising the heat-shrinkable multilayer film obtained
by laminating outer surface layers comprising a polyester type
resin on an intermediate layer comprising a polystyrene type
resin with an adhesive layer interposed between the outer
surface layer and the intermediate layer as a base film, the
heat-shrinkable label can stably cover containers without
producing the delamination by bonding the outer surface layers
to the intermediate layer with an adhesive layer comprising a
polyester type elastomer or a modified polyester type elastomer
interposed therebetween. Further, the present inventors found
that, in the case of using such a constitution, the reduction
in strength between the layers after a printing step can be
inhibited. These findings have now led to completion of the
present invention.
[0009]
The heat-shrinkable multilayer film of the present
invention is formed by laminating outer surface layers
comprising a polyester type resin on an intermediate layer
comprising a polystyrene type resin with an adhesive layer
comprising a polyester type elastomer or a modified polyester
type elastomer interposec between the outer surface layer and
the intermediate layer.
[0010]
The polyester type elastomer is preferably a saturated
polyester type elastomer, and particularly preferably a
saturated polyester type elastomer containing polyalkylene
ether glycol segments.
As the saturated polyester type elastomer containing
polyalkylene ether glycol segments, for example, block
copolymers comprising an aromatic polyester as a hard segment
and polyalkylene ether glycol or an aliphatic polyester as a
soft segment are preferable. Furthermore, polyester polyether
block copolymers containing polyalkylene ether glycol as a soft
segment are more preferable.
[0011]
The polyester polyether block copolymer is preferably
produced by polycondensation cf an oligomer obtained by
esterification reaction or transesterification reaction
between (i) aliphatic and/or alicyclic diol having 2 to 12
carbon atoms, (ii) an aromatic and/or aliphatic dicarboxylic
acid or an alkyl ester thereof, and (iii) polyalkylene ether
glycol as raw materials.
[0012]
As the aliphatic and/or alicyclic diol having 2 to 12
carbon atoms, for example, diols ordinarily used as raw
materials for polyesters particularly raw materials for
polyester type elastomers can be used. Specific examples of
the aliphatic and/or alicyclic diol having 2 to 12 carbon atoms
include ethylene glycol, propylene glycol, trimethylene glycol,
1,4-butanediol, 1,4-cyclohexanediol,
1,4-cyclohexanedimethanoI, and the like. Among these diols,
1,4-butanediol and ethylene glycol are preferable, and
1,4-butanediol is particularly preferable. These diols may be
used singly or in combination of two or more species.
[0013]
As the aromatic dicarboxylic acid, those ordinarily used
as raw materials for polyesters, particularly raw materials for
polyester type elastomers can be used. Specific examples of
the aromatic dicarboxylic acid include terephthalic acid,
isophthalic acid, phthalic acid, 2, 6-naphthalene dicarboxylic
acid, and the like. Among these aromatic dicarboxylic acids,
terephthalic acid and 2, 6-naphthalene dicarboxylic acid are
preferable, and terephthalic acid is particularly preferable.
These aromatic dicarboxylic acids may be used singly or in
combination of two or more species.
[0014]
Examples of alkyl esters of the aromatic dicarboxylic
acids include dimethyl esters or diethyl esters of the above
aromatic dicarboxylic acids. Among there, dimethyl
terephthalate and 2, 6-dimethylnaphthalene dicarboxylate are
preferable.
[0015]
As the aliphatic dicarboxylic acid, cyclohexane
dicarboxylic acids are pre ferable. As the alkyl ester thereof,
dimethyl esters or diethyl esters of the cyclohexane
dicarboxylic acids are preferable.
In addition to the above components, a small amount of
a trifunctional alcohol, a tricarboxylic acid or an ester
thereof may be copolymerized therewith. Further, aliphatic
dicarboxylic acids such as adipic acid or dialkyl esters thereof
may also be used as a copolymer component.
[0016]
Examples of the polyalkylene ether glycol include
polyethylene glycol, poly(1,2- and/or 1,3-propylene
ether) glycol, poly (tetramethylene ether) glycol,
poly(hexamethylene ether)glycol and the like.
[0017]
A preferable lower Limit of a number average molecular
weight of the polyalkylene ether glycol is 400, and a preferable
upper limit is 6000. When the number average molecular weight
is 400 or more, a blockingproperty of the copolymer is enhanced,
and when the number averac e molecular weight is 6000 or less,
phase separation in a system becomes hard to occur and physical
properties as a polymer becomes easy to be exibited. More
preferably, the lower limit is 500, and the upper limit is 4000.
Further more preferably, the lower limit is 600, and the upper
limit is 3000. In addition, the number average molecular weight
used herein refers to the value measured by gel permeation
chromatography (GPC) . The calibration for GPC can be performed
by use of, for example, "POLYTETRAHYDROFURAN CALIBRATION KIT"
(manufactured by POLYMER LABORATORIES INC., GB.).
[0018]
Examples of the commercialized product of the polyester
type elastomer include "PRIMALLOY" produced by Mitsubishi
Chemical Corp., "PELPRENE" produced by Toyobo Co., Ltd.,
"Hytrel" produced by Du Pont-Toray Co., Ltd., and the like.
[0019]
When a polyester pclyether block copolymer comprising a
polyester and polyalkylene ether glycol is used as the polyester
type elastomer, a preferable lower limit of the content of the
polyalkylene ether glycoL component is 5% by weight, and a
preferable upper limit if 90% by weight. When the content of
the polyalkylene ether glycol component is 5% by weight or more,
the block copolymer becomes excellent in flexibility and impact
resistance, and when the content is 90% by weight or less, the
block copolymer becomes excellent in hardness and mechanical
strength. More preferably, the lower limit is 30% by weight,
and the upper limit is 80% by weight. Further more preferably,
the lower limit is 55% by weight.
In addition, the consent of the polyalkylene ether glycol
component can be calculated from the chemical shift and content
of hydrogen atoms using nuclear magnetic resonance (NMR)
spectroscopy.
[0020]
The modified polyester type elastomer is obtained by
modifying a polyester type elastomer with a modifying agent.
A modification reaction for obtaining the modified
polyester type elastomer is performed, for example, by reacting
the polyester type elastomer with α,β-ethylenic unsaturated
carboxylic acid as the modifying agent. In the modification
reaction, a radical generator is preferably used. In the
modification reaction, a graft reaction, in which the
a, p-ethylenic unsaturated carboxylic acid or its derivative is
added to the polyester type elastomer, mainly occurs, but a
decomposition reaction also occurs. Consequently, a molecular
weight of the modified polyester type elastomer is lowered and
melt viscosity of the elastomer is lowered.
Further, it is considered that in the modification
reaction, generally, a transesterification reaction, and the
like, also occur as other reactions, and the resulting products
generally become compositions containing an unreacted raw
material and the like, in this case, a lower limit of the
content of the modified polyester type elastomer in the
resulting product is preferably 10% by weight, and more
preferably 30% by weight and the content of the modified
polyester type elastomer is furthermore preferably 100% by
weight.
[0021]
Examples of the α, β-ethylenic unsaturated carboxylic
acid include unsaturated carboxylic acids such as acrylic acid,
maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic
acid, citraconic acid, crotonic acid, isocrotonic acid and the
like; and unsaturated caiboxylic anhydrides such as
2-octene-l-yl-succinic anhydride, 2-dodecene-1-yl-succinic
anhydride, 2-octadecene-1-yl-succinic anhydride, maleic
anhydride, 2,3-dimethylmaleic anhydride, bromomaleic
anhydride, dichloromaleic anhydride, citraconic anhydride,
itaconic anhydride, 1-but ene-3,4-dicarboxylic anhydride,
1-cyclopentene-l,2-dicarkoxylic anhydride,
1,2,3,6-tetrahydrophthalic anhydride,
3,4,5,6-tetrahydrophthalic anhydride,
exo-3,6-epoxy-l,2,3,6-tetrahydrophthalic anhydride,
5-norbornene-2,3-dicarboxylic anhydride,
methyl-5-norbornene-2,3-dicarboxylic anhydride,
endo-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride and
bicyclo [2.2.2] oct-7-ene-2,3,5, 6-tetracarboxylic anhydride.
Among these, acid anhydride s are preferable since they have high
reactivity.
The α,β-ethylenic uisaturated carboxylic acids can be
appropriately selected according to kinds of copolymers
containing a polyalkylene ether glycol segment to be modified
and modification conditions, and may be used in combination of
two or more species. In addition, the α,β-ethylenic
unsaturated carboxylic ands may be used in the form of a
solution obtained by dissolving these compounds in an organic
solvent, or the like.
[0022]
Examples of the radical generator include organic or
inorganic peroxides such as t-butyl hydroperoxide, cumene
hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide,
2,5-dimethyl-2,5-bis(t-butyloxy)hexane,
3,5,5-trimethylhexanonyl peroxide, t-butyl peroxybenzoate,
benzoyl peroxide, dicumyl peroxide,
1,3-bis(t-butylperoxyisopropyl)benzene, dibutyl peroxide,
methyl ethyl ketone peroxide, potassium peroxide and hydrogen
peroxide; azo compounds such as 2,2'-azobisisobutylonitrile,
2,2' -azobis (isobutylamide ) dihalide,
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and
azo-di-t-butane; carbon radical generators such as dicumyl; and
the like.
The radical generator car. be appropriately selected
according to kinds of the polyester type elastomer and kinds
of the α,β-ethylenic unsaturated carboxylic acid, which are
used for the modification reaction, and the modification
conditions, and can be used in combination of two or more species .
Furthermore, the radical generators can be used in the form of
a solution obtained by dissolving these compounds in an organic
solvent, or the like.
[0023]
A preferable lower Limit of the amount of the
α,β-ethylenic unsaturated carboxylic acids to be mixed is 0.01
part by weight with respect to 100 parts by weight of the
polyester type elastomer, and a preferable upper limit is 30.0
parts by weight. When the amount is 0.01 part by weight or more,
the modification reaction c an be adequately performed, and when
the amount is 30.0 parts by weight or less, the modified
polyester type elastomez becomes economically advantageous.
More preferably, the lower limit is 0.05 part by weight and the
upper limit is 5.0 parts by weight, and furthermore preferably,
the lower limit is 0.10 part by weight and the upper limit is
1.0 part by weight.
[0024]
A preferable lower limit of the amount of the radical
generator to be mixed is 0.001 part by weight with respect to
100 parts by weight of the polyester type elastomer, and a
preferable upper limit of the amount is 3.00 parts by weight.
When the amount is 0. 001 part by weight or more, the modification
reaction becomes apt to ocur, and when the amount is 3.00 parts
by weight or less, the deterioration of material strength due
to a reduction in molecular weight (reduction in viscosity) at
the time of modification becomes hard to occur.
More preferably, the lower limit is 0.005 part by weight
and the upper limit is 0.50 part by weight, furthermore
preferably, the lower limit is 0.010 part by weight and the upper
limit is 0.20 part by weight, and particularly preferably, the
upper limit is 0.10 part by weight.
[0025]
As the modification reaction for obtaining the modified
polyester type elastomer, publicly known reaction methods such
as a melt-kneading reaction method, a solution reaction method,
a suspension-dispersion reaction method, and the like can be
used, but the melt-kneading reaction method is generally
preferable because of low cost.
[0026]
In the melt-kneading reaction method, the
above-mentioned respective components are uniformly mixed
together at predetermined blending ratios and then the
resulting mixture is melt-kneaded. In order to mix the
respective components, a Henschel mixer, a ribbon blender, a
v-blender, or the like can oe used. In order to melt-knead the
resulting mixture, a Banbary mixer, a kneader, a roll, a
single-screw kneading extruder or a multi-screw kneading
extruder such as twin-screw kneading extruder can be used
[0027]
A preferable lower limit of a kneading temperature at
which the melt-kneading i s performed is 100°C, and a preferable
upper limit is 300°C. By setting the kneading temperature at
a temperature within this range, the heat deterioration of a
resin can be prevented. More preferably, the lower limit is
120°C, and the upper limit is 280°C, and further more preferably,
the lower limit is 150°C and the upper limit is 250°C.
[0028]
A rubber component such as natural rubber, synthetic
rubber (for example, polylsoprene rubber), and the like and a
softening agent such as process oil may coexist with the
modified polyester type elastomer. By coexistence of the
softening agent, plasticisation of the rubber component can be
promoted and fluidity of the resulting thermoplastic resin
composition can be improved. The softening agent may be any
of paraffinic, naphthenic, and aromatic softening agents.
Further, other components such as a resin, rubber, filler or
additive other than those described above may be added to the
resin components and rubber components within a range not
impairing effects of the present invention.
[0029]
Examples of the filler include calcium carbonate, talc,
silica, kaolin, clay, diatom earth, calcium silicate, mica,
asbestos, alumina, barium sulfate, aluminum sulfate, calcium
sulfate, magnesium carbonate, carbon fiber, glass fiber, glass
sphere, molybdenum sulfide, graphite, Shirasu-balloon, and the
like.
Further, Examples of the additives include
heat-resistant stabilizers, weather-resistant stabilizers,
colorants, antistatic agerts, flame retardants, nucleoators,
lubricants, slip agents, anti-blocking agents, and the like.
[0030]
As the heat-resistant stabilizer, publicly known
heat-resistant stabilizers such as phenole heat-resistant
stabilizers, phosphoric heat-resistant stabilizers and
sulfuric heat-resistant stabilizers can be used. As the
weather-resistant stabilizer, publicly known
weather-resistant stabilizers such as hindered amine
weather-resistant stabilizers and triazole weather-resistant
stabilizers can be used. Examples of the colorant include
carbon black, titanium white, zinc white, red iron oxide, azo
compounds, nitroso compounds, phthalocyanine compounds, and
the like. Further, for all of the antistatic agents, the flame
retardants, the nucleoaagents, the lubricants, the slip agents
and the anti-blocking agents, publicly known substances can be
used.
[0031]
A preferable lower limit of a modification ratio
(grafting rate) of the modified polyester type elastomer is
0.01% by weight, and a preferable upper limit is 10.0% by weight.
When the modification ratio is 0.01% by weight or more, affinity
of the elastomer for a polyester becomes high, and when the
modification ratio is 10.0% by weight or less, reduction in
strength due to the deterioration of a molecule in modification
can be reduced. More preferably, the lower limit is 0.03% by
weight, and the upper limit is 7.3% by weight, and further more
preferably, the lower limit is 0.05% by weight, and the upper
limit is 5.0% by weight.
[0032]
The modification ratio (grafting rate) of the modified
polyester type elastomer can be determined according to the
following equation (1) from spectrums obtained by H1-NMR
measurement. In additior , as equipment to be used for the
H1-NMR measurement, for example, "GSX-400" (manufactured by
JEOL Ltd.) can be used.
[0033]
Grafting rate (weight %) = 100 x (C/3 x 98) /{(Ax 148/4) + (B
x 72/4) + (C/3 x 98) } (1)
In the above equation (1), A is an integral value in an
integral range of 7.8 to 3.4 ppm, B is an integral value in an
integral range of 1.2 to 2.2 ppm, and C is an integral value
in an integral range of 2.4 to 2.9 ppm.
[0034]
A preferable lower limit of a JIS-D hardness of a product
containing the modified polyester type elastomer obtained by
the modification reaction is 1C, and a preferable upper limit
is 80. When the JIS-D hardness is 10 or more, mechanical
strength is improved, and when the JIS-D hardness is 80 or less,
flexibility and impact resistance are improved. More
preferably, the lower Unit is 15, and the upper limit is 70,
and further more pref erab] y, the lower limit is 20, and the upper
limit is 60. In addition, the JIS-D hardness can be measured
by using durometer type-D through a method according to JIS
K6235.
[0035]
Examples of the polystyrene type resin composing the
intermediate layer include an aromatic vinyl
hydrocarbon-conjugated diene copolymer, a mixed resin of an
aromatic vinyl hydrocarbon-conjugated diene copolymer and an
aromatic vinyl hydrocarbon-aliphatic unsaturated carboxylic
acid ester copolymer, and the like.
When the aromatic vinyl hydrocarbon-conjugated diene
copolymer is used, the hea t-shrinkable multilayer film becomes
a heat-shrinkable multilayer film which is hardly broken in an
atmosphere of low temperature and has excellent handleability.
Further, when the mixed resin of an aromatic vinyl
hydrocarbon-conjugated diene copolymer and an aromatic vinyl
hydrocarbon-aliphatic unsaturated carboxylic acid ester
copolymer is used, the hee t-shrinkable multilayer film becomes
a heat-shrinkable multilayer film having excellent low
temperature shrinkability.
[0036]
The aromatic vinyl hydrocarbon-conjugated diene
copolymer is not particularly limited, and examples of the
aromatic vinyl hydrocarbon include styrene, o-methylstyrene,
p-methylstyrene, and the like, and examples of the conjugated
diene include 1,3-butadiene, 2-methyl-l,3-butadiene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene,
and the like. These dienes may be used singly or in combination
of two or more species. Among these, a
styrene-butadiene-styrere copolymer (SBS resin) is suitable
since this copolymer is superior particularly in low
temperature shrinkability and rearing properties along the
perforation. Further, in order to prepare a film with less-fish
eye, it is preferable to use a styrene-isoprene-styrene
copolymer (SIS resin), a styrene-isoprene-butadiene-styrene
copolymer (SIBS resin), and the like, in which
2-methyl-l, 3-butadiene (Isoprene) is used as conjugated diene .
[0037]
When the SBS resin, the SIS resin, or the SIBS resin is
used as the aromatic vinyl hydrocarbon-conjugated diene
copolymer, these resins may be used singly or in combination
of two or more species. When these resins are used in
combination of two or more species, resins may be dry-blended,
or may be used as a compounded resin formed by kneading the resins
in a specific composition with an extruder and pelletizing the
extruded resin.
When such resins are used singly or in combination of two
or more species, the composition preferably has a styrene
content of 65 to 90% by weight and a conjugated diene content
of 10 to 35% by weight. Resins having such a composition are
superior particularly in low temperature shrinkability and
tearing properties along the perforation. On the other hand,
when the conjugated diene content is less than 10% by weight,
the film tends to tear when tension is applied, and the film
may break contingently in converting printing or using the film
as a label. When the conjugated diene content is more than 35%
by weight, extraneous substances such as gel may become apt to
be produced in molding processing the film.
[0038]
The aromatic vinyl hydrocarbon-aliphatic unsaturated
carboxylic acid ester copolymer is not particularly limited,
examples of the aromatic, vinyl hydrocarbon include styrene,
o-methylstyrene, p-methylstyrene, and the like, and examples
of the unsaturated carboxylic acid ester include methylacrylate,
ethylacrylate, propylacrylate, butylacrylate,
methylmethacrylate, ethylmethacrylate, propylmethacrylate,
butylmethacrylate, and the like. These copolymers may be used
singly or in combination of two or more species.
[0039]
When a styrene-buzylacrylate copolymer is used as the
aromatic vinyl hydrocaroon-aliphatic unsaturated carboxylic
acid ester copolymer, substances having a styrene content of
60 to 90% by weight and a butylacrylate content of 10 to 40%
by weight are preferably used. By using an aromatic vinyl
hydrocarbon-aliphatic unsaturated carboxylic acid ester
copolymer having such composition, a heat-shrinkable label
having excellent low temperature resistance and excellent
tearing properties along the perforation can be attained.
[0040]
When a mixed resin of an aromatic vinyl
hydrocarbon-conjugated diene copolymer and an aromatic vinyl
hydrocarbon-aliphatic unsaturated carboxylic acid ester
copolymer is used as the intermediate layer, a preferable lower
limit of an amount of the aromatic vinyl hydrocarbon-conjugated
diene copolymer to be mixed in the mixed resin is 20% by weight,
and a preferable upper limit is 100% by weight. When the amount
is less than 20% by weicrht, low temperature ductility becomes
low and a heat-shrinkable label may be broken due to dropping
it inadvertently during cold storage. The more preferable
lower limit is 30% by weight.
[0041]
In the heat-shrinkable multilayer film of the present
invention, the intermediate layer preferably contains an
ultraviolet absorber. By thus containing the ultraviolet
absorber, it is possible to provide ultraviolet light blocking
properties, and it is possible tc prevent the deterioration of
the contents of a container to enhance a storage property since
particularly a property of blocking ultraviolet light (a
wavelength 380 nm or shorter) emitted from solar light or a
fluorescent lamp is excellent.
Further, by containing the ultraviolet absorber in only
the intermediate layer comprising a polystyrene type resin,
problems such as heat deterioration and roll contamination in
containing the ultraviolet absorber in the polyester type resin
can be solved. Further, since a desired ultraviolet light
blocking property can be achieved even when the content of the
ultraviolet absorber is low, the heat-shrinkable multilayer
film of the present invention becomes advantageous in the cost.
[0042]
The ultraviolet absorber is not particularly limited, and
examples of the ultraviolet absorber include benzophenone type
ultraviolet absorbers such as 2,4-dihydroxybenzophenone,
2,2',4,4'-tetrahydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and
2-hydroxy-4-n-octoxybenzophenone; benzotriazole type
ultraviolet absorbers such as
2-(2'-hydroxy-4'-n-octoxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-n-methoxyphenyl)benzotriazole,
2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotria
zole,
2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and
2-[2'-hydroxy-3'-(3'',4" ,5" , 6" -tetrahydrophthalimidemeth
yl)-5'-methylphenyl]benzotriazole; benzoate type ultraviolet
absorbers such as
2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate;
salicylate type ultraviolet absorbers such as
p-t-butylphenylsalicylate; cyanoacrylate type ultraviolet
absorber such as ethyl-2-cyano-3,3-diphenyl acrylate, and
octyl-2-cyano-3,3-diphenyl acrylate; and the like.
Among these,
2-(2'-hydroxy-5'-n-methoxyphenyl)benzotriazole, and
2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotria
zole are preferable since they have excellent balance between
ultraviolet light absorbancy and heat resistance.
[0043]
Apreferable lower limit of the content of the ultraviolet
absorber, depending on the thickness of the intermediate layer,
is 1 part by weight with respect to 100 parts by weight of
materials, such as a base resin, and a recycle material,
composing an intermediate- layer, and a preferable upper limit
is 10 parts by weight. When the content is less than 1 part
by weight, ultraviolet light blocking properties become
inadequate and there may be cases where a resin film cannot
prevent the deterioration of the contents of a container in
using the resin film as a heat-shrinkable label of a container,
and when the content is more than 10 parts by weight, mechanical
strength of the heat-shrankable multilayer film is decreased
and break of the film may occur in converting printing or using
the resin film as a heat-shrinkable label. The more preferable
lower limit of the content of the ultraviolet absorber is 2 parts
by weight and the more preferable upper limit is 8 parts by
weight.
[0044]
The polyester type resin composing the outer surface
layers can be prepared by polycondensating dicarboxylic acid
with diol.
The dicarboxylic acid is not particularly limited, and
examples of the dicarboxylic acid include o-phthalic acid,
terephthalicacid, isophthalicacid, succinic acid, adipicacid,
sebacic acid, azelaic acid, octylsuccinic acid,
cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid,
fumaric acid, maleic acid, itaconic acid, and
decamethylenecarboxylic icid, and anhydrides and lower alkyl
esters thereof.
The diol is not particularly limited, and examples of the
diol include aliphatic dlols such as ethylene glycol,
1,3-propanediol, 1,4-butanediol, diethylene glycol,
1,5-pentanediol, 1,6-hexanediol, dipropylene glycol,
triethylene glycol, tetraethylene glycol, 1,2-propanediol,
1,3-butanediol, 2,3-buta lediol, neopentyl
glycol(2,2-dimethylpropane-1,3-diol), 1,2-hexanediol,
2,5-hexanediol, 2-methyl-2,4-pentanediol,
3-methyl-1,3-pentanediol, and 2-ethyl-1,3-hexanediol;
alicyclic diols such as 2,2-bis(4-hydroxycyclohexyl)propane,
alkylene oxide addition product of
2,2-bis(4-hydroxycyclohe