DESCRIPTION
LAMINATE, PACKAGING MATERIAL USING THE SAME AND PRODUCTION PROCESS
FOR THE SAME
5 Technical Field
The present invention r e l a t e s to a laminate having a t l e a s t
a layer for deposition and a packaging material using the laminate.
Moreparticularly, thepresentinventionrelatestoalaminatehaving
10 a t l e a s t a polyolefin resin layer, a l a y e r f o r deposition and an
inorganic layer laminated in t h i s order, a packaging material using
the laminate, and a production process for the laminate.
Background A r t
15 [0002]
In order to fill-package a variety of foods and beverages,
cosmetics, pharmaceutical products, miscellaneous goods and other
a r t i c l e s , plasticflexiblepackagingbagsofvarious shapeshavebeen
developed and put i n t o practical use in the past. As laminated
20 materials (laminates) that are packaging materials for forming the
packagingbags, a v a r i e t y o f gas b a r r i e r m a t e r i a l s havingproperties
to prevent permeation of oxygen gas, water vapor and the like have
been used from the viewpoints of protection of q u a l i t i e s of the contents,
demand for extension of storage time, etc. However, there is aproblem
thatsunlightfromthe sun, fluorescent light froma fluorescent lamp,
or the like is transmitted, and this transmitted light exerts influence
on the contents to cause decomposition of the contents, change of
properties thereof or photo deterioration such as discoloration and
5 others. Onthis account, avarietyoflight-shieldingmaterialshave
been also studiedandproposed. As themost popular material to impart
a gas barrier function or a light-shielding function, a laminated
film of an aluminum foil and a resin, an aluminum-deposited film or
the like has been used.
10 [0003]
Polyolefin-based resins including polypropylene are
inexpensive, are excellent in moldability and are excellent also in
oil resistance, sealing properties, etc., and therefore, they can
exhibit excellent performance also in the case where they are used
15 as such packaging materials as above (e.g., patent literatures 1 and
2). However,thepolyolefin-basedresinsgenerallyhavepooradhesion
to different materials, and hence, when a laminate of, for example,
an inorganic layer of deposited aluminurnor the like and such a resin
is formed, deposition strength (bond strength) between the
20 polyolefin-based resin layer and the inorganic layer is poor, and
dependingupontheuseenvironrnentortheusepurpose, aninterlaminar
peel (delamination) phenomenon sometimes takes place. In order to
prevent such delamination, various methods have been proposed, and
a part of them have been put into practical use. For example, for
thepurposeofenhancingadhesiontometals, etc., amethodofgrafting
maleic anhydride or the like on polypropylene through a specific
technique has been proposed, or for the purpose of imparting
flexibilitytopolypropyleneinherentlyhavingapropertyofrigidity,
5 a method of compounding a soft rubber has been proposed (patent
literatures 3 and 4).
[00041
On the other hand, in order to allow resin packaging bags for
variousfoodsincludingsnacks, particularlyinsidepartsofthebags,
10 tohavebrightness andgloss, thebags are sometimes requiredtohave
metallicappearance (glitterfee1ing)orpearl-likeappearance. Also
the aforesaid packaging bags formed of aluminum foils or
aluminum-deposited films are no exception, and for example, strong
packaging bags hardly suffering delamination and having sufficient
15 glitter feeling on the interior parts have been desiredby customers
in a specific region or food makers.
[0005]
Enhancement of delaminationpreventionperformancehasbecome
feasiblebytheaforesaidvariousproposalsincludingagraftingmethod
20 and a rubber compounding method, but it is still difficult to allow
the packaging bags to simultaneously exhibit glitter feeling, and
the need for it by the customers has increased.
Citation List
Patent Literature
[00061
Patent l i t e r a t u r e 1: WO 2007/086425 A1
Patent l i t e r a t u r e 2: WO 2012/077706 A1
Patent l i t e r a t u r e 3: WO 2010/120295 A1
Patent l i t e r a t u r e 4: WO 2013/119316 A1
Summary of Invention
Technical Problem
10 [0007]
Thepresent inventionhas beenmade to solve the above problem,
and addresses the problem of providing a laminate having a layer for
deposition and a laminated film, each of which has sufficient
delamination prevention performance, simultaneously has good
15 appearance and an inorganic layer surface imparted with brightness
andisexcellentalsoingasbarrierproperties, preferablyalaminate
and a laminated filmmainly for packaging foods, each of which has
a t l e a s t a polyolefin resin layer, a layer for deposition and an
inorganic layer laminated i n t h i s order.
Solution to Problem
[0008]
Inorder t o solve theaboveproblem, thepresent inventors have
earnestly studied, and as a r e s u l t , they have found that the above
problem can be solved by contriving composition of the layer for
deposition, and have completed the present invention.
[0009]
That is to say, according tothepresent invention, alaminate,
5 a packaging material and a production process for them, which are
described below, are provided.
[OOlO]
The laminate of the present invention is characterized in that
the laminate has at least a layer (11) for deposition and preferably
10 has at least a polyolefin-based resin layer (I), a layer (11) for
deposition and an inorganic layer (111) in this order, the layer (11)
fordepositioncomprisesa composition (P) foralayer for deposition
andpolypropylene (D) andisdifferentfromthepolyolefin-basedresin
layer (I), the composition (P) for a layer for deposition is obtained
15 by melt-kneading 30 to 85% by weight of isotactic polypropylene (A),
70 to 15% by weight of apropylene-based copoly.m er. (B) (witht he proviso
that the total of (A) and (B) is 100% by weight), and if necessary,
an additive, a part or all of the isotactic polypropylene (A) and/or
thepropylene-basedcopolymer (B) hasbeengraft-modifiedwithagraft
20 monomer ( C ) , andthepropylene-basedcopolymer (B) is different from
the isotactic polypropylene (A) and (i) contains 45 to 89% by mol
of constituent units (U3) derived from propylene and 11 to 55% by
molof constituent units (Uo) derivedf romat least onea-olefin selected
from ethylene and a-olefins of 4 to 20 carbon atoms (with the proviso
that the total of the constituent units (U3) derived from propylene
and the constituent units (Uo) derived from the a-olefin is 100% by
mol) .
[OOll]
5 The laminate of the present invention has at least a
polyolefin-based resin layer (I), a layer (11) for deposition which
comprises a composition (P) for a layer for deposition, andan inorganic
layer (111) in this order, and in the composition (P) for a layer
for deposition, a graft monomer (C), preferably an unsaturated
10 carboxylicacidand/oritsderivative ( C ) , hasbeensubjectedtograft
additioninanamount of 0.001to 5partsbyweightbasedon100weight
of a composition comprising 30 to 85% by weight of isotactic
polypropylene (A) and 70 to 15% by weight of a propylene-based copolymer
(B) which is def inedby the later-describedrequirement (i) , preferably
15 defined by the requirement (i) and the requirement (ii) or (iii),
more preferably defined by the requirements (i) to (iii) (with the
proviso that the total of the component (A) and the component (B)
is 100% by weight).
[0012]
The inorganic layer (111) is preferably a layer containing
aluminum.
[0013]
Thepackagingmaterialofthepresentinventionusesthelaminate
of the present invention.
[00141
The production process for a laminate having at least a layer
for deposition according to the present invention is characterized
by comprising a step (1) of melt-kneading 30 to 85% by weight of
5 (graft-modified) isotactic polypropylene (A), 70 to 15% by weight
ofa (graft-modified) propylene-basedcopolymer (B) (withtheproviso
that the total of (A) and (B) is 100% by weight), and if necessary,
an additive to produce a composition (P) for a layer for deposition,
and a step (2) of producing a layer for deposition comprising the
10 composition (P) for a layer for deposition and polypropylene (D).
Advantageous Effects of Invention
[00151
Thereareprovidedalaminateinwhichapolyolefinresinlayer,
15 a layer for deposition and an inorganic layer are laminated in this
order and which has sufficient delamination prevention performance,
has good appearance, has an inorganic layer surface imparted with
glitter feeling and is excellent also in gas barrier properties, a
packagingmaterialusing the laminate, and a production process for
20 the laminate.
[0016]
The packaging material of the present invention has the
above-mentioned performance, is excellent in flexibility and is
extremely strong.
Description of Embodiments
[0017]
Embodiments for carrying out the present invention will be
5 hereinafter described in detail for each constituent feature, but
they are exemplary embodiments of the present invention, and the
present invention is not limited to the contents of them at all.
[0018]

The polyolefin-based resin layer (I) in the present invention
is not specifically restricted provided that it is a layer formed
of polyolefin. For example, polyolefin-based resins such as
polyethylene, specifically low-density polyethylene (LDPE),
high-density polyethylene (HDPE) or the like, acid-modified
15 polyethylene, polypropylene, acid-modified polypropylene, a
propylene/a-olefin copolymer, an ethylene/vinyl acetate copolymer,
anethylene/(meth)acrylicestercopolymer,anethylene/(meth)acrylic
acid copolymer and an ionomer, are used. Of these, polyethylene,
polypropylene andapropylene/a-olefincopolymerarepreferablyused
20 from the viewpoints of protection of the contents of packaging
materials, low-temperature sealingproperties, etc. Further, since
good moldability can be obtained, homopolypropylene, a
propylene/ethylene random copolymer and a propylene/butene random
copolymer are particularly preferably used. As the polypropylene
or the propylene/cc-olefin copolymer, the later-described i s o t a c t i c
polypropylene ( A ) , propylene-based copolymer (B) or polypropylene
(D) may be used. These polyolefins may be used singly or as a mixture
of two ormore kinds. Fromthe viewpoint that alaminate having good
5 appearanceisobtained, it i s p r e f e r a b l e t o u s e t h e samepolypropylene
a s t h e polypropylene (D) .
[0019]
The resin layer (I) is not specifically r e s t r i c t e d , but it is
preferably a film usually having a thickness of 1 pm to 1000 pm,
10 preferably 1 t o 200 pm.
[0020]
I n t h e r e s i n l a y e r ( I ) , additives, suchasultravioletabsorbing
agent, antioxidant, a n t i s t a t i c agent, surface active agent, pigment,
fluorescent brightener, inorganic p a r t i c l e s , specifically s i l i c a ,
15 calciumcarbonate, titaniumoxide andthe l i k e , andorganicparticles
containingacrylicresin, styrene r e s i n o r the l i k e a s a constituent,
may be contained when needed, within l i m i t s not detrimental t o the
e f f e c t s of the present invention.
[0021]
As the resin layer (I), a layer formed of one or more resins
selected from polyolefins, such as polyethylene,
poly-4-methyl-1-pentene and polybutene; cyclic olefin polymers;
polyvinylalcohol; anethylene/vinylalcoholcopolymer;polystyrene;
polyesters, such as polyethylene terephthalate, polybutylene
terephthalate and polyethylene naphthalate; polyamides, such as
nylon-6, nylon-11 and polymetaxylene adipamide; polycarbonate;
polyvinyl chloride; polyvinylidene chloride; polyimide;
polyethersulfone; polyacrylics; polyallylate; triacetylcellulose;
5 polyphenylene sulfide; and the like, may be used instead of the
polyolefin-based resin layer (I) or together with the resin layer
(I), within limits not detrimental to the effects of the present
invention.
[0022]
10 From the viewpoints of good extensibility, transparency and
rigidity, preferable is a resinlayermade of a filmformedof polyolefin,
suchaspolyethylene,poly-4-methyl-l-penteneorpolybutene, acyclic
olefin polymer, polyimide, polyethyleneterephthalate, polyamide or
the like among the above resins. The thickness of the film is the
15 same as that previously described.
[DO231

Thelayer (11) fordepositionaccordingtothepresentinvention
comprises a composition ( P ) for a layer for deposition and
20 polypropylene (D) that are described later. The layer (11) for
deposition is different from the polyolefin-based resin layer (I).
[0024]
It is presumed that excellent adhesion of the layer (11) for
deposition tothe inorganic layer (111) is attributableto a reaction
of a functional group of graft-modifiedisotactic polypropylene (A)
or graft-modified propylene-based copolymer (B), or graft-modified
isotactic polypropylene (A) and graft-modified propylene-based
copolymer (B) , with a hydrogen group or a hydroxyl groupon the inorganic
5 layer surface, such as a hydrogen group derived fromwater or a hydroxyl
groupderivedfromanoxidefilm, andattributabletoaphysicaleffect
duetoflexibilityofapropylene-basedcopolymer (B). It ispresumed
that the propylene-based copolymer (B) is completely compatibilized
inthelayer (11) fordepositionorextremelyfinelydispersedtherein
10 totherebyimpartbrightnessorglossandtransparencytothelaminate.
The layer for deposition comprises polypropylene (D), preferablythe
same polypropylene as the polypropylene for forming the
polyolefin-basedresinlayer (I), togetherwith the composition (P),
and therefore, good moldability can be obtained while excellent
15 adhesion between layers is maintained. On that account, a laminate
having high interlaminar peel strength and having good appearance
(brightness, gloss, transparency) can be obtained economically.
[0025]
The composition (P) for a layer for deposition is obtained by
20 melt-kneading 30 to 85% by weight of isotactic polypropylene (A),
70 to 15% by weight of a propylene-based copolymer (B) (with the proviso
that the total of (A) and (B) is 100% by weight), and if necessary,
an additive, and a part or all of the isotactic polypropylene (A)
and/orthepropylene-basedcopolymer (B) hasbeengraft-modifiedwith
a graft monomer (C)
[00261
It is also preferable that the layer for deposition (11)
comprises a melt kneadate and the polypropylene (D), in said melt
5 kneadate, a graft monomer (C), preferably an unsaturated carboxylic
acidand/oritsderivative (C),havingbeensubjectedtograftaddition
in an amount of 0.001 to 5 parts by weight based on 100 weight of
a composition comprising 30 to 85% by weight of the isotactic
polypropylene (A), 7Oto15%byweightofthepropylene-basedcopolymer
10 (B), and if necessary, an additive (with the proviso that the total
of the component (A) and the component (B) is 100% by weight).
[0027]
The layer (11) for deposition is not specifically restricted,
but it usually has a thickness of 1 pm to 1000 pm, preferably 1 to
15 100 pm.
[00281
In the layer (11) for deposition, additives described for the
aforesaidresinlayer (11) maybecontainedwhenneeded, withinlimits
not detrimental to the effects of the present invention.
20 [00291
The components are described in detail hereinafter.
[0030]
( (A) Isotactic polypropylene)
As the isotactic polypropylene (A) (also referred to as a
"component (A) ") for use in the present invention, a homopolymer of
propylene or a propylene/a-olefin copolymer can be mentioned. The
propylene/a-olefin copolymer is different from the later-described
propylene-based copolymer (B) .
5 [0031]
The a-olefin species is not s p e c i f i c a l l y r e s t r i c t e d , but
ethylene and/or an a-olefin of 4 t o 20 carbon atoms can be preferably
mentioned. These a-olefins may be used singly o r i n combination of
two or more kinds. Examples of a-olefins of 2 to 20 carbon atoms
10 other than propylene include ethylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and
1-decene. In the present invention, a more preferred a-olefin is
e t h y l e n e o r a n a - o l e f i n o f 4 t o 1 0 carbonatoms, andaboveall, ethylene
or an a-olefin of 4 t o 8 carbon atoms is particularly preferable.
15 [OD321
Here, the content of constituent units derived frompropylene
in the propylene/a-olefin copolymer is preferablynot less than 90%
by mol based on 100% by mol of the t o t a l of the constituent units
derivedfrompropylene andconstituent units derivedfromana-olefin
20 of 2 to 20 carbon atoms other than propylene.
[00331
The melt flow r a t e (MFR) of the polypropylene (A) i s not
specifically r e s t r i c t e d , but it is preferably 0 . 1 to 100 9/10 min,
more preferably 0.5 t o 50 9/10 min. In the present specification,
not only for the isotactic polypropylene (A) but also for the
propylene-based copolymer (B) and the polypropylene ( D ) , MFR is a
value measured at 230°C under a load of 2.16 kg in accordance with
ASTM D 1238.
5 [0034]
The melting point (Tm) of the polypropylene (A), which is
observedin DSCmeasurementinwhichthepolypropyleneismaintained
at 200°C for 10 minutes in a DSC measurement apparatus, then cooled
down to -20 "C at a cooling rate of 10 "C/min, maintained at -20°C for
10 lminuteandthenheatedagainataheatingrateoflO"C/min, isusually
higherthan120'Cbutnothigherthan170'C, preferably130 to 160°C.
[0035]
The density of the polypropylene (A), as measured by a density
gradienttubemethodinaccordancewithJISK7112,isnotspecifically
15 restricted, but it is usually 0.900 to 0.920 g/cm3, preferably 0.900
to 0.915 g/cm3. If the density is less than 0.900 g/cm3, transparency
or blocking resistance of the layer (11) for deposition is sometimes
deteriorated. On the other hand, if the densityis higher than 0.920
g/cm3, transparency and impact resistance of the layer (11) for
20 deposition are liable to be lowered.
[0036]
The molecular weight distribution (Mw/Mn, Mw: weight-average
molecular weight, Mn: number-average molecular weight, both being
in terms of polystyrene) of the polypropylene (A), as measured by
gel permeationchromatography (GPC), is not s p e c i f i c a l l y r e s t r i c t e d ,
but it is preferably not more than 10.0, more preferably not more
than 8.5. Although the lower l i m i t is not s p e c i f i c a l l y r e s t r i c t e d ,
it is 1 . 8 .
5 [0037]
The production process for the polypropylene (A) is not
specifically r e s t r i c t e d , and the polypropylene can be produced by
a well-known process using a well-known catalyst such as a
Ziegler-Natta c a t a l y s t o r a metallocene catalyst. Further, a
10 c r y s t a l l i n e polymer can be preferably used, and in the case of a
copolymer, the copolymer may be a random copolymer or may be a block
copolymer. Moreover, there is no specific limitation also on the
stereoregularityandthemolecularweightprovidedthatsatisfactory
moldabilityis obtainedandthe resultingmoldedproducthas strength
15 towithstanduse. Itisalsopossibletouseacommerciallyavailable
resin as it is.
[0038]
Theisotacticpolypropylene (A) preferablyusedinthepresent
invention i s homopolypropylene, a propylene/ethylene random
20 copolymer, a propylene/l-butene random copolymer or a
propylene/ethylene/l-butene random copolymer.
[0039]
Tothepolypropylene (A), additives, suchasantioxidant, l i g h t
s t a b i l i z e r , ultravioletabsorbingagent,metallicsoap, hydrochloric
acid absorbent, lubricant, antistatic agent, anti-fogging agent and
anti-blocking agent, maybe addedwithout deviating fromthe object
of the present invention. The amount of such an additive added has
onlyto be within limits not detrimental tothe object ofthe present
5 invention though it varies depending upon the type of the additive.
The amount thereof is usually not more than 3 parts by weight based
on 100 parts by weight of the polypropylene.
[0040]
( (B) Propylene-based copolymer)
10 The propylene-based copolymer (B) (also referred to as a
"component (B)" ) in the present invention satisfies the following
requirement (i), preferably satisfies the requirement (i) and the
requirement (ii) or (iii), and more preferably satisfies all of the
requirements (i) to (iii). The propylene-based copolymer (B) is
15 different from the isotactic polypropylene (A).
[0041]
(i) The propylene-based copolymer contains constituent units
(U3)d erivedfrompropylene inamounts of 45 to 89% bymol andconstituent
units (Uo) derived from at least one a-olefin selected from ethylene
20 and a-olefins of 4 to 20 carbon atoms in the total amount of 11 to
55% by mol (with the proviso that the total of the constituent units
(U3) derived from propylene and the constituent units (Uo) derived
from the a-olefin is 100% by mol).
[0042]
(ii) The melting point (Tm) as measured by a differential
scanning calorimeter is not higher than 120°C, or the melting point
is not observed. As for the method for measuring the melting point,
the working examples can be referred to.
5 [0043]
(iii) The molecular weight distribution (Mw/Mn) as determined
by gel permeation chromatography (GPC) is in the range of 1.0 to 3.0.
[0044]
As ethylene and the a-olefin of 4 to 20 carbon atoms in the
10 requirement (i), straight-chain or branched a-olefins can be
mentioned.
[0045]
Examples of the straight-chain a-olefins include
straight-chain a-olefins of 2 to 20 carbon atoms except propylene,
15 suchas ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecne,l-octadeceneandl-eicosene.
Of these, straight-chain a-olefins of 2 to 10 carbon atoms, such as
ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene andl-decene, are
preferable.
20 [0046]
Examples ofthe brancheda-olefins include brancheda-olefins
of 4 to 20 carbon atoms, suchas 3-methyl-1-butene, 4-methyl-1-pentene,
3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene,
4-methyl-1-hexene, 4,4,-dimethyl-1-hexene, 4-ethyl-1-hexne and
3-ethyl-1-hexene. Preferablearebrancheda-olefinsof5to10carbon
atoms.
[0047]
The above a-olefins may be uses singly or i n combination of
5 two or more kinds.
[0048]
With r e g a r d t o t h e amount of c o n s t i t u e n t skeleton a t t r i b u t a b l e
t o each o l e f i n i n the requirement (i)t,h e amount of the c o n s t i t u e n t
u n i t s (U3) derived from propylene is 45 t o 89% by mol, preferably
10 52 t o 85% by mol, more preferably 60 t o 82% by mol. The t o t a l amount
of the c o n s t i t u e n t u n i t s (Uo) derivedfromat l e a s t onea-olefin selected
from ethylene and a-olefins of 4 t o 20 carbon atoms is usually 11
t o 55% by mol, preferably 15 t o 48% by mol, more preferably 18 t o
40% by mol. Here, the t o t a l of the c o n s t i t u e n t u n i t s (U3) derived
15 frompropyleneandtheconstituentunits (Uo) derivedfromthea-olefin
is 100% by mol. From the viewpoint of ease of obtaining, the
propylene-based copolymer is preferably a propylene-basedcopolymer
containing only the c o n s t i t u e n t u n i t s (U2) derived from ethylene or
containing only the c o n s t i t u e n t u n i t s (U4) derived from 1-butene or
20 containingbothof t h e c o n s t i t u e n t u n i t s ( ~ b2 4 ) derivedfromethylene
andl-butene, a s t h e c o n s t i t u e n t u n i t s (Uo) d e r i v e d f r o m t h e a - o l e f i n .
[0049]
In thecasewhere the c o n s t i t u e n t u n i t s (U2) derivedfromethylene
and the c o n s t i t u e n t u n i t s (U4-20) derived from an a-olefin of 4 t o
20 carbon atoms a r e both contained a s t h e c o n s t i t u e n t u n i t s (Uo) derived
from the a-olefin, the amount of the c o n s t i t u e n t u n i t s (UZ) derived
from ethylene is usually 10 t o 25% by mol, preferably 10 t o 23% by
mol, more preferably12 t o 17% bymol, with the proviso t h a t t h e t o t a l
5 o f t h e c o n s t i t u e n t u n i t s (U3) derivedfrompropylene, the c o n s t i t u e n t
u n i t s (UZ) derived from ethylene and t h e c o n s t i t u e n t u n i t s (U4-Z0)
derived from an a-olefin of 4 t o 20 carbon atoms is 100% by mol. The
amount of the c o n s t i t u e n t u n i t s (U4-20) derived from an a-olefin is
usually 1 t o 30% by mol, preferably 5 t o 25% by mol, more preferably
10 6 t o 23% by mol, with the proviso t h a t the t o t a l of U3, UZ and U4-20
is 100% by mol. As the copolymer, a propylene/ethylene/l-butene
terpolymer is preferable.
In the case where only the c o n s t i t u e n t u n i t s (UZ) derived from
15 ethylene are contained as the c o n s t i t u e n t u n i t s (Uo) derived from
the a-olefin, the amount of the c o n s t i t u e n t u n i t s (UZ) derived from
ethylene is usually 11 t o 55% by mol, preferably 15 t o 48% by mol,
more preferably 18 t o 40% by mol, based on 100% by mol of t h e t o t a l
of the c o n s t i t u e n t u n i t s (U3) derivedfrompropyleneand the c o n s t i t u e n t
20 u n i t s (U2) derivedfromethylene. Whenthepropylene-basedcopolymer
(B) is a propylene/ethylene bipolymer, t h i s bipolymer is p r e f e r a b l e
because of e x c e l l e n t balance between r i g i d i t y and ease of handling
during molding.
[0051]
In the case where the propylene-based copolymer (B) contains
the constituent units (U4-z0)d erivedfromana-olefinof4to20 carbon
atoms in the present invention, the constituent units (U4) derived
from 1-butene are preferably used as the constituent units (U4-~~).
5 The amount of the constituent units (U4) derived from 1-butene is
usuallyllto 55% bymol, preferably15to 48% bymol, more preferably
18 to 40% by mol, based on 100% by mol of the total of the constituent
units (U3) derived frompropylene and the constituent units (U4) derived
from 1-butene. The reason is that 1-butene is one of stably obtainable
10 olefins among the a-olefins of 4 to 20 carbon atoms and that when
the layer (11) for deposition is formed from a composition composed
of a melt kneadate of the isotactic polypropylene (A) and the
propylene-based copolymer (B) and publicly known polypropylene,
selection of 1-butene enhances compatibility of both resins of the
15 propylene-based copolymer (B) and the polypropylene with each other
tothereby improveproperties ofthe layer (11) for deposition. From
suchviewpoints, thepropylene-basedcopolymer (B) isalsopreferably
a propylene/l-butene blpolymer or a propylene/ethylene/l-butene
terpolymer.
20 [00521
The amount (% by mol) of the constituent units derived from
eachcomonomerinthepropylene-basedcopolymer (B) canbedetermined
by a publicly known technique for analyzing '?-NMR spectrum.
[0053]
As long as the effects of the present invention are exerted,
the propylene-based copolymer (B) may contain, for example, cyclic
olefins, conjugateddienes, non-conjugatedpolyenes, aromaticvinyl
compounds, functionalgroup-containingvinylcompounds,etc.insmall
5 amounts as the monomers to constitute an olefin-based polymer, when
needed. The amount of constituent units of thesemonomers is usually
not more than 10% by weight, preferably not more than 5% by weight,
based on 100% by weight of a l l of the constituent units.
[0054]
In the case where a melting point (Tm) e x i s t s with regard t o
the requirement (ii),th e melting point is preferably in the range
of40t0120°C. Whenthemeltingpoint i s i n t h e rangeof45to115"C,
f l e x i b i l i t y is increased during deposition, and therefore, the
deposition strength is enhanced, so t h a t such a range ismore pref erable.
15 The expression "melting point is not observed" means that a crystal
melting peak having a crystal melting heat of not l e s s than 1 J/g
is not observed in the range of -150 to 200°C. The melting point
(Tm) is ameltingpointdetectedona DSC curve obtainedby subjecting
a specimen to conditioning a t 23 "Ck2 "C for not shorter than 72 hours,
20 thereafter cooling the specimen down to -40°C and heating it a t a
heating rate of 1O0C/min.
[00551
With regard t o the requirement (iii),M w/Mn is preferably in
the range of 1.0 to 2.8. When Mw/Mn is in the range of 1 . 0 to 2.5,
molding appearance becomes b e t t e r , so that such a range is more
preferable.
[0056]
MFR of the propylene-based copolymer (B) is not specifically
5 r e s t r i c t e d , but it is preferably 0.1to100 g/lOmin, more preferably
0.5 to 50 g/10 min.
[0057]
The density of the copolymer ( B ) , as measured by a density
gradienttubemethodinaccordancewithJISK7112, i s n o t specifically
10 r e s t r i c t e d , but it is preferably 0.800 to 0.900 g/cm3, more preferably
0.820 t o 0.890 g/cm3.
[0058]
The production process f o r t h e propylene-based copolymer (B)
is not specifically r e s t r i c t e d , and the copolymer can be produced
15 by a well-known process using a well-known catalyst such as a
Ziegler-Natta catalystorametallocene catalyst. Aspubliclyknown
literaturesinwhichaproductionprocessusingametallocenecatalyst
is disclosed, Japanese Patent Publication No. 1994-820 and Japanese
Patent No. 3580428 having been applied by the present applicant and
20 already laidopen, etc. canbementioned. Further, there is no specific
l i m i t a t i o n a l s o on the stereoregularity and the molecular weight
providedthat satisfactorymoldabilityis obtainedandthe resulting
molded product has strength t o withstand use. It i s also possible
to use a commercially available resin as it i s .
[0059]
Composition (P) for layer for deposition
The composition ( P ) for a layer for deposition according to
thepresentinventionisobtainedbymelt-kneading30to85%byweight,
5 preferably 40 to 80% by weight, more preferably 45 to 75% by weight,
of the i s o t a c t i c polypropylene ( A ) , 70 to 15% by weight, preferably
60 t o 20% by weight, more preferably 55 to 25% by weight, of the
propylene-basedcopolymer ( B ) , andifnecessary, the later-described
additive (with the proviso that the t o t a l of the component (A) and
10 the component (B) is 100% by weight). Prior t o the melt kneading,
a part or a l l of the i s o t a c t i c polypropylene (A) and/or the
propylene-based copolymer (B) has been graft-modified with a graft
monomer (C) . That is to say, in the raw materials of the composition
(P), a graft-modified product is included.
15 [00601
In the composition (P) for a layer for deposition according
to the present invention, a graft monomer ( C ) , preferably an
unsaturated carboxylic acid and/or its derivative ( C ) , has been
subjected to graft addition in an amount of 0.001 t o 5 parts by weight
20 based on 100 parts by weight of a composition composed of 30 to 85%
by weight, preferably 40 to 80% by weight, more preferably 45 to 75%
byweight, oftheisotacticpolypropylene (A) and70to15%byweight,
preferably 60 to 20% by weight, more preferably 55 to 25% by weight,
ofthepropylene-based copolymer (B) (withthe provisothat t h e t o t a l
of the component (A) and the component (B) is 100% by weight).
[0061]
In the present invention, by adjusting the component ratios
of the component (A) and the component (B) to the above ranges, it
5 becomes possible to obtain an adhesive excellent not only in initial
adhesion but also in adhesion after heat history.
[0062]
In the composition (P) for a layer for deposition according
tothe present invention, bothofthe component (A) and the component
10 (B) to constitute the composition (P) may have been partially
graft-modified, or any one of the component (A) and the co~nponent
(B) may have been partially graft-modified. Examples of the graft
monomers (C) include unsaturated carboxylic acids, such as acrylic
acid, methacrylic acid, a-ethylacrylic acid, maleic acid, fumaric
15 acid, itaconic acid, citraconic acid, tetrahydrophthalic acid,
methyltetrahydrophthalic acid, crotonic acid,
endocis-bicyclo[2,2,l]hept-5-ene-2,3-dicarboxylic acid (Nadic
acidTM) and
methyl-endocis-bicyclo[2,2,l]hept-5-endo-2,3-dicarboxylic acid
20 (~eth~lnadaicci dTM), and derivatives, such as acid halides, nitriles,
amides,imides,acidanhydridesandestersofunsaturateddicarboxylic
acids. Specificexamplesofsuchderivativesincludemalenylchloride,
maleimide, maleic anhydride, citraconic anhydride, monomethyl
maleate, dimethyl maleate, (meth)acrylonitrile, acrylamide,
malenylimide, N-alkyl-substituted (meth)acrylamides, carboxylic
acid vinyl esters, glycidyl methacrylate, 2-hydroxyethyl
methacrylate, 2-(N,N-dimethy1amino)ethyl methacrylate, monomethyl
maleate and dimethyl maleate. These compounds (graft monomers) can
5 be used singly or in combination. Of these, unsaturated carboxylic
acids and/ortheir derivatives canbe preferably used. Examples of
the unsaturated carboxylic acids and/or their derivatives include
unsaturated compounds having one or more carboxylic acid groups and
saltsthereof, estersofunsaturatedcarboxylicacidcompoundshaving
10 acarboxylicacidgroupandalkylalcohols, andunsaturatedcompounds
having one or more carboxylic anhydride groups (e.g., anhydrides of
unsaturated dicarboxylic acids). Examples of unsaturated groups
include a vinyl group, a vinylene group and an unsaturated cyclic
hydrocarbongroup. Whentheunsaturatedcarboxylicacidsand/ortheir
15 derivatives areusedinthepresent invention, theycanbeusedsingly
or can be used in combination of two or more kinds. Of these, more
preferably used are unsaturated dicarboxylic acids, such as maleic
acid, Nadic acidTM and itaconic acid, or acid anhydrides thereof, and
acrylic acid and methacrylic acid, or derivatives thereof;
20 particularlypreferablyusedaremaleicacidand~adicacidTMor, acid
anhydrides thereof; and most preferably used is maleic anhydride.
[0063]
Thecontent ofthegraftmonomer (C) isusually0.001to 5parts
by weight, preferably 0.01 to 3 parts by weight, based on 100 parts
by weight of the composition ( P ) . The graft quantity of the graft
monomer (C) is usually 0.001 to 5 parts by weight, preferably 0.01
to 3partsbyweight, b a s e d o n 1 0 0 w e i g h t o f t h e t o t a l o f t h e i s o t a c t i c
polypropylene (A) and the propylene-based polymer (B). Since the
5 content and the graft quantity of the graft monomer (C) are in the
aboveranges, thelayer (11) fordepositioncomprisingthecomposition
(P) for a layer for deposition according to the present invention
exhibits high bond strength to the inorganic layer (111). Control
of the content and the graft quantity of the graft monomer can be
10 easily carried out by, for example, properly selecting the grafting
conditions.
[0064]
(Grafting method)
When the graft monomer is grafted in the present invention,
15 the grafting method is not specifically restricted, and hitherto
publicly known graft polymerization such as solution method or melt
kneading method can be adopted. Examples of such methods include
a method comprising melting a polymer and adding a graft monomer to
themelttoperformgraftreactionandamethodcomprisingdissolving
20 a polymer in a solvent to give a solution and adding a graft monomer
to the solution to perform graft reaction.
[0065]
In the graft modification, it is preferable to graft-modify
the component (A) and/or the component (B) with the graft monomer
in the presence of a radical i n i t i a t o r such as an organic peroxide
or an azo compound. The radical i n i t i a t o r can be used by mixing it
asitiswiththecomponent (A), thecomponent (B) andthegraftmonomer,
but it can be also used a f t e r it is dissolved i n a small amount of
5 an organic solvent. The organic solvent can be used without any
r e s t r i c t i o n provided that it is an organic solvent capable of
dissolving the radical i n i t i a t o r . In t h e g r a f t modification, a
reducing substance may be used. By the use of the reducing substance,
the graft quantity of the graft monomer can be increased.
10 [0066]
Thegraftmodificationcanbecarriedoutbyahithertopublicly
known method, and for example, the graft modification can be carried
out by dissolving the component (A) and/or the component (B) in an
organic solvent, then adding a graft monomer, a radical i n i t i a t o r ,
15 etc. tothesolutionandallowingthemtoreactwitheachotherusually
a t a temperature of 70 t o 200°C usually for 0.5 t o 15 hours. Further,
by allowing the component (A) and/or the component (B) to react with
a graft monomer in the absence of a solvent using an extruder or the
like, a modified product can be also produced.
20 [0067]
Examples of the organic peroxides include dicumyl peroxide,
di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,
n-butyl-4,4-bis(t-butylperoxy)valerate, benzoyl peroxide,
p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl
peroxybenzoate, t-butyl perbenzoate, t-butylperoxy isopropyl
5 carbonate, diacetyl peroxide, lauroyl peroxide and t-butylcumyl
peroxide.
[0068]
Examples of the azo compounds include
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
10 2,2'-azobis(2-methylbutylnitrile), 2,2'-azobis(isobutyronitri1e)
and dimethyl-2,2'-azobis(2-methylpropionate).
These organic peroxides or azo compounds may be used singly,
or may be used in combination of two or more kinds.
15 [0070]
The amount of the organic peroxide or the azo compound used
is usually 0.01 to 30 parts by weight based on 100 parts by weight
of the (co)polymer used for the graft reaction.
(Production process for composition (P) for layer for
deposition)
The production process for the composition (P) for a layer for
deposition according to the present invention is not specifically
restricted, and publicly known processes can be adopted without any
restriction. For example, graft modification is carried out in the
simultaneous presence of the isotactic polypropylene (A) and the
propylene-based copolymer (B) or carried out by graft-modifying a
part or all of the component (A) and the component (B) and then mixing
5 unmodified residues of the components. Thereafter, the
later-describedarbitrarycomponents (additives) areadded, andthen
the mixture is melt-kneaded, whereby a composition for a layer for
depositionthatisamodifiedpolyolefincompositioncanbe obtained.
[00721
It is also preferable to obtain the composition (P) by
graft-modifying a part of the isotactic polypropylene (A) with an
unsaturated carboxylic acid and/or its derivative (C) and then
melt-mixing an unmodified component (A) and the propylene-based
copolymer (B) .
15 [0073]
Inthepresent invention, aprocess comprisinggraft-modifying
a part or all of the isotactic propylene (A) and then melt-mixing
the graft-modified product, the propylene-based copolymer (B), and
if necessary, additives is preferable. In the present invention,
20 aprocesscomprisinggraft-modifyingapartoftheisotacticpropylene
(A) and then melt-mixing an unmodified component (A) and the
propylene-based copolymer (B) is preferable.
[00741
As the melt kneading method, for example, a method comprising
dryblendingtheresincompositionandthenmelt-kneadingthedryblend
by a single screw or twin-screw extruder, a Banbury mixer, a roll,
any of various kneaders, orthe like canbementioned, andanextruder
ispreferablyusedindustrially. Thetemperatureinthemelt kneading
5 is not specifically restricted provided that the components (A) and
(B) aremelted, but in general, themelt kneading is carried out usually
in the temperature range of 160 to 300°C, preferably 180 to 250°C.
[0075]
With the composition (P) for a layer for deposition according
10 to the present invention, other elastomers capable of being mixed
can be blended within limits not detrimental to the object of the
present invention. When other elastomers are blended, the amount
thereof is usually less than 10 parts by weight based on 100 parts
by weight of the composition (P) for a layer for deposition. The
15 elastomersmaybeblendedsimultaneouslywithblendingoftheaforesaid
components (A) and (B) , or may be mixed with a composition containing
the components (A) and (B) after the composition is obtained.
[0076]
To the composition (P) for a layer for deposition according
20 tothepresentinvention, additives, suchaspubliclyknownprocessing
stabilizer, heat stabilizer, heat aging resisting agent, filler,
tackifier, processingaid, anti-agingagent, weathering stabilizer,
antistatic agent, colorant, lubricant and thickening agent, can be
also addedwithinlimits not detrimental tothe object ofthe present
invention. These additives are not specifically restricted as long
as the effects of the present invention are exerted, and the amount
thereof is usually not more than 5 parts by weight, preferably not
more than 1 part byweight, basedon 10Oparts byweight of the composition
5 (P), though it depends upon the intended use or the type. In the
present invention, a so-calledtackifiercanbe addedforthepurpose
of imparting tack. Examples of substances to impart tack include
rosinderivatives, terpene resin, petroleumresin, andhydrogenation
products thereof. Of these, hydrogenated terpene resin and
10 hydrogenated petroleum resin are preferable.
[0077]
Even when only the composition (P) for a layer for deposition
is used or even when a blend of the composition (P) for a layer for
deposition, the elastomer and various additives is used, the layer
15 (11) for deposition sufficientlyexhibitsthe effects ofthe present
invention. However, depending upon the intended use or the use
environment in which a packaging material in final form is used, a
layer (11) fordepositioncomprisingacompositionfurthercontaining
publicly known polypropylene (D) in addition to the composition (P)
20 for a layer for deposition is preferably used. If the layer (11)
for depositionis obtainedby aprocess includinga step (1) of producing
the composition (P) for a layer for deposition anda step (2) of producing
a layer for deposition containing the composition (P) for a layer
for deposition and the polypropylene (D), a laminate including the
layer (11) for deposition has s u f f i c i e n t delamination prevention
performance. Further, thelayer (11) fordepositionhasgoodadhesion
to the inorganic layer, and therefore, brightness of the inorganic
layer is enhanced. Forthe reasonthat the layer (11) for deposition
5 contains agraft-modifiedproductandhas f l e x i b i l i t y , the inorganic
layer is preferably an aluminum f o i l or an aluminum deposition film
layer. Sincethe layer (11) fordepositionisparticularlyexcellent
inadhesion t o an aluminumfoilor analuminumdeposition filmlayer,
g l i t t e r f e e l i n g (gloss) inherentinaluminumcanbeespeciallybrought
10 out.
100781
The polypropylene (D) is, for example, a homopolymer of propylene,
a propylene/a-olefin copolymer or the aforesaid i s o t a c t i c
polypropylene (A), and from the viewpoints of economy, v e r s a t i l i t y ,
15 ease of obtaining, etc., a homopolymer of propylene or a
propylene/a-olefin copolymer is preferable. Although the a-olefin
. .
species in the propylenela-olefin copolymeris not s p e c i f i c a l l y
restricted, it is preferably ethylene and/or an a-olefin of 4 t o 20
carbon atoms. These a-olefins may be used singly or in combination
20 oftwoormore kinds. Thea-olefinsandthecontent oftheconstituent
u n i t s a r e the same as those describedin the section of the polypropylene
(A) .
[0079]
The polypropylene (D) may be the same as or different from the
polypropylene ( A ) .
The polypropylene (D) may be the same as or d i f f e r e n t from the
propylene-basedcopolymer (B), butfromtheviewpointofmoldability,
they are preferablydifferentfromeach other. As the polypropylene
5 ( D ) , a graft-modified product obtained from the component (A) may
be used, but from the viewpoint of economy, an unmodified substance
is preferable.
[OOBO]
The melt flow r a t e (MFR) of the polypropylene ( D ) is not
10 s p e c i f i c a l l y r e s t r i c t e d a s long as the e f f e c t s of the present invention
are e x e r t e d , b u t it is p r e f e r a b l y 0 . 1 t o 100 g/lOmin,morepreferably
0.5 t o 50 g/10 min.
[OOBl]
The melting point (Tm) of the polypropylene ( D ) , as observed
15 by DSC measurement, is not s p e c i f i c a l l y r e s t r i c t e d a s long as the
e f f e c t s of the present invention are e x e r t e d , b u t it is usually 130
t o 165"C, preferably 132 to162 "C. Themethod formeasuring themelting
point is i d e n t i c a l with t h a t f o r the polypropylene ( A ) .
[0082]
The density of the polypropylene (D) , as measured by a density
gradienttubemethodinaccordancewithJISK7112,isnotspecifically
restrictedaslongastheeffectsofthepresentinventionareexerted,
but it is usually 0.900 t o 0.920 g/cm3, preferably 0.905 t o 0.915
g/cm3. If t h e d e n s i t y is less than 0.900 g/cm3, transparencyorblocking
resistanceofthelayer (11) fordepositionissometimesdeteriorated.
On the other hand, if the density is higher than 0.920 g/cm3,
transparency and impact resistance of the layer (11) for deposition
are liable to be lowered.
5 [0083]
The molecular weight distribution (Mw/Mn, Mw: weight-average
molecular weight, Mn: number-average molecular weight, both being
in terms of polystyrene) of the polypropylene (D), as measured by
gel permeationchromatography (GPC), isnot specificallyrestricted,
10 but it is preferably not more than 3.5, more preferably not more than
3.0. Although the lower limit is not specifically restricted, it
is 1.8.
[0084]
To the polypropylene (D) , such various additives as described
15 for the polypropylene (A) may be added without deviating from the
object ofthepresent invention. Theamount of suchanadditive added
has only to be within limits not detrimental to the object of the
present invention though it varies depending upon the type of the
additive. The amount thereof is usually not more than 3 parts by
20 weight based on 100 parts by weight of the polypropylene.
[0085]
The production process for the polypropylene (D) is identical
with that for the polypropylene (A).
[0086]
Whenthe polypropylene (D) isblendedwiththe composition (P)
for a layer for deposition and the blend is used for the layer (11)
for deposition, the blending ratio (ratio by weight) between the
composition (P) for a layer for deposition and the polypropylene (D)
5 is not specifically restricted, but it is usually in the range of
95:5to5:95,preferablyintherangeof80:2Oto2O:8O,morepreferably
in the range of 70:30 to 30:70. For preparing the layer (11) for
deposition from the composition (P) for a layer for deposition and
publicly knownpolypropylenethatis usedwhenneeded, hitherto known
10 processes can be used without any restriction.
[0087]

The inorganic layer (111) is not specifically restricted as
long as the effects of the present invention are exerted, and for
15 example, metals containing elements, such as gold (Au) , copper (Cu) ,
iron (F), chromium (Cr), zinc (Zn), cobalt (Co), aluminum (Al),
titanium (Ti), tin (Sn) , indium (In) and silicon (Si) , and inorganic
compounds,suchasoxides,nitrides,nitroxides,sulfides,phosphides,
phosphorus oxides, phosphorus nitrides andphosphorus nitroxides of
20 the above elements can be mentioned.
[0088]
As preferred inorganic matters used for the inorganic layer
(111) in the present invention, metals, metal oxides, etc. can be
mentioned. The metal used for the inorganic layer (11) is not
specificallyrestrictedaslongastheeffectsofthepresentinvention
are exerted, but aluminum, gold, copper, iron, etc. can be mentioned,
and as the metal oxides, oxides of these metals can be mentioned.
[0089]
5 As the inorganic layer (111) ofthe present invention, ametal
foil can be used as it is, or a layer of a deposition film can be
formed. In the case of a metal foil, one of the above metals or an
alloy of two or more of them may be used. In the case of a deposition
film, one ormoremetalsmaybeused. Specific examples of preferred
10 layers among such layers include an aluminum foil, a gold foil, an
aluminum deposition layer, a silica deposition layer, an alumina
deposition layer and a silica-alumina binary deposition layer. Of
these, an aluminum foil or an aluminum deposition film layer is
particularly preferable because they are inexpensive, have high
15 barrier properties and can impart light-shielding properties.
[0090]
For forming the inorganic layer (111) on the layer (11) for
deposition, a vapor phase process, a wet process or the like can be
mentioned.
20 [0091]
As methods for forming the layer by a vapor phase process,
publicly knownmethods, e.g., chemicalvapordepositionmethods, such
as chemical vapor deposition (CVD), catalyst CVD (CAT-CVD),
low-pressureCVDandplasmaCVD;andphysicalvapordepositionmethods
(PVD), such as vacuum deposition (reactive vacuum deposition),
sputtering (reactive sputtering) and ion plating (reactive ion
p l a t i n g ) , can be mentioned.
[00921
5 In the case of a metal f o i l , the thickness of the inorganic
layer (111) is usually 0.1 t o 100 )m, preferably1 to 50 pm, particularly
preferably 3 to 30 pm. In the case of an inorganic deposition film,
the thickness thereof is usually 10 to 5000 A, preferably 50 to 1000
A, more preferably 100 to 600 A, p a r t i c u l a r l y preferably 300 to 500
10 . If the thickness of the inorganic layer is too small, sufficient
b a r r i e r properties are not obtainedin some cases. If the thickness
thereof is too large, theweightofapackagingmaterialis increased
tomake handling inconvenient, andin the case o f a deposition layer,
cracks a r e l i a b l e t o occur.
15 [0093]

A transparent sealant layer ( I V ) can be also used by providing
it adjacently to the inorganic layer (111) though the sealant layer
is not essential in the laminate of the present invention. In t h i s
20 case, the laminate is a laminate having a polyolefin resin layer ( I ) ,
a layer (11) for deposition formed of a composition (P) for a layer
for deposition, preferably a layer (11) for deposition comprising
the composition (P) and polypropylene (D) , an inorganic layer (111)
andatransparent sealant layer ( I V ) that arelaminatedinthisorder.
By providing the transparent sealant layer (IV), this layer exerts
a heat-sealing function and can simultaneously maintain brightness
of the adjacent inorganic layer (111) because of transparency.
[00941
5 As resins employable for the transparent sealant layer (IV),
publiclyknownpolyethylene-basedresins,polypropylene-basedresins
andcyclicpolyolefin-basedresins are usedwithoutanyrestriction.
From the viewpoints of transparency, rigidity, low-temperature
heat-sealing properties, heat-sealing strength, low-temperature
10 impact strength, etc., it is preferable to use, for example, a
composition composed of apolypropylene resin, an ethylene/a-olefin
copolymerandapropylene/a-olefincopolymeroracompositioncomposed
of a polypropylene resin, an ethylene/a-olefin copolymer and a
1-butene/a-olefin copolymer.
15 [0095]
For forming the transparent sealant layer (IV), a method of
directly extrusion-coating the inorganic layer (111) with the above
resin or composition or a method of dry-laminating a laminate
includingthepolyolefinresinlayer (I), thelayer (11) fordeposition
20 and the inorganic layer (111) with a sealant film or coextruding the
laminate and a sealant film can be adopted.
[0096]
The sealant film can be produced by molding the above resin
orresincompositionintoafilm. Formoldingitintoa film, publicly
knownmethodsbywhichpolyolefinfilmscanbeobtained, suchascasting,
inflation method and extrusion coating, can be adopted, but from the
viewpointthatthelaminateofthepresentinventioncanbeefficiently
obtained, extrusioncoatingispreferable. Inthecaseofthecasting
5 and the inflation method, a good film having a uniform thickness can
be produced usually under the conditions of a resin temperature of
160 to 240'C. In the case of the extrusion coating, conditions of
a resin temperature of 200 to 320°C can be usually adopted.
[00971
The thickness of the transparent sealant layer (sealant film)
is not specifically restricted as long as the effects of the present
invention are exerted, but it is usually 1 to 100 pm, preferably 3
In the laminate of the present invention, to the surfaces of
the inorganic layer (111) and the transparent sealant layer (IV),
publiclyknownvariouscoatingagents, e.g.,variousresinswithwhich
coating is possible, such as polyester-based, polyurethane-based,
20 acrylic, polyvinyl acetate-based and ionomer-based resins, may be
applied in order to enhance surface protection, printability,
lamination suitability, etc.
[00991
The surface of each layer to constitute the laminate of the
present invention may have been subjected to surface treatment or
undercoating. Examples of the surface treatments include ozone
treatment, corona discharge treatment, plasma treatment, glow
discharge treatment, reverse sputteringtreatment, flame treatment,
5 chromic acid treatment, solvent treatment and surface-roughening
treatment. Anchor coating agents canbe composedof various resins,
such as thermoplastic resins, thermosetting resins, light-curable
resins and coupling agents. By particularly carrying out corona
discharge treatment or plasma treatment, oxygen permeability and
10 moisture permeability are lowered, whereby a laminate having more
excellent gas barrier properties can be obtained. By particularly
subjecting the surface of the layer (11) for deposition to the above
surface treatment, particularly preferably corona discharge
treatment, plasmatreatmentorozonetreatment, adhesionofthelayer
15 for deposition to the inorganic layer (111) becomes better.
[OlOO]

The laminate of the present invention can be produced by a
publicly known method. For example, the laminate can be produced
20 by coextrusionmethods, such as T-diemethod, inflationmethod, casting,
tube extrusion and extrusion coating. Further, a method comprising
producing a single layer or multilayer film and then subjecting the
film to dry lamination by heating can be given as an example. In
thepresent invention, acoextrusionmethodinwhichpluralcomponents
are fed t o a multilayer extrusion machine to produce a laminate is
preferably used from the viewpoint of productivity.
[OlOl]

5 Thelaminateofthepresentinventionisexcellentinbrightness
( g l i t t e r feeling) and transparency, has high interlaminar peel
strengthandisexcellentalsoingasbarrierproperties,andtherefore,
it is preferably used in various f i e l d s . For example, food f i e l d ,
such a s f i e l d of food packaging films or food containers, e. g., cups,
10 b o t t l e s , t r a y s , tubesandBIB (bag-in-box) , canbementioned. However,
also because of excellent gas b a r r i e r properties, the laminate can
be preferably used also in non-food applications such as pipes.
[0102]
(Packaging material)
The packagingmaterial o f t h e present invention comprises the
laminateofthepresent invention, andispreferablyusedasamaterial
(packaging material) of packaging containers or packaging bags for
foods and beverages, cosmetics or miscellaneous goods or for food
packaging, f i l l i n g packaging or fiber packaging.
The packaging container or the packaging bag may be obtained
by forming a laminate in the form of a film or a sheet into a desired
shape throughvacuum forming or pressure forming, ormaybe obtained
by producing a laminate so as to have a desired shape of a packaging
container or a packaging bag. The packaging container and the
packaging bag have their inner surfaces with excellent brightness
(glitter feeling) and transparency, have high interlaminar peel
strength and are excellent also in gas barrier properties.
5 [0104]
The packaging container or the packaging bag containing the
contentsisobtainedbyfillingacontainerorabagwiththecontents,
then covering it with a publicly known film as a cover material and
heat-sealing the top and the sides of the container. The container
10 and the bag are preferably utilized for packaging instant noodles,
miso, jelly, pudding, snacks, etc.
Examples
The present invention is further described with reference to
the following examples and comparative examples, but it should be
construed that the present invention is in no way limited to those
examples as long as they do not depart from the spirit of the present
invention.
(Various measuring methods)
In the examples, etc., measurements were carried out in
accordance with the following methods.
[01071
[Melt flow rate (MFR, g/10 min) 1
Unless otherwise noted, melt flow rate was measured at 230°C
under a load of 2.16 kg in accordance with ASTM D 1238.
[0108]
[Density (g/cm3)1
Density was measured in accordance with JIS K 7112.
[0109]
[Melting point (Tm, 'C) 1
Meltingpoint was determined fromanendothermic curve of DSC.
10 In the DSC measurement of the melting points of the component (A),
a graft-modified product of the component (A) and the component (D) ,
a specimen was maintained at 200°C for 10 minutes in an apparatus,
then cooled down to -20'C at a cooling rate of 1O0C/min, maintained
at-20"Cfor1minuteandthenheatedagainataheatingrateof10"C/min
15 to obtain a DSC curve, and an endothermic peak on the DSC curve was
taken as a melting point (Tm) of the component (A) .
[OllO]
With regard to the component (B) and a graft-modified product
ofthe component (B), a specimenhavingbeensubjectedtoconditioning
20 at 23"C+2"C for not shorter than 72 hours was cooled down to -40'C
andheatedundertheconditionsofaheatingrateof10"C/mintoobtain
a DSC curve. An endothermic peak detected on the DSC curve was taken
as a melting point (Tm) .
[Olll]
[Weight-average molecular weight (Mw), number-average
molecular weight (Mn) and molecular weight distribution (Mw/Mn)]
Weight-averagemolecularweight(Mw),number-averagemolecular
weight (Mn) and molecular weight distribution (Mw/Mn) were measured
5 in the following manner using Alliance GPC-2000. That is to say,
separation columns of TSKgel GMHG-HT X 2tTSKgel GMH6-HTL X 2 each having
a column size of a diameter of 7.5 mm and a length of 300 mm were
used. The column temperature was set to 140°C. Using
orthodichlorobenzene (available fromWako Pure Chemicalindustries,
10 Ltd.) as a mobile phase and using 0.025% by weight of BHT
(butylhydroxytoluene) (available fromTakeda PharmaceuticalCompany
Limited) as an antioxidant, a sample was moved at 1.0 ml/min. The
sample concentration was 0.1% by weight, and the injection quantity
of the sample was 500 microliters. As a detector, a differential
15 refractometer was used. As standard polystyrene, polystyrene
available from Tosoh Corporation was used.
[0112]
[Interlaminarbond strengthbetween layer (11) for deposition
and inorganic layer (111) (unit: N/15 mm)]
Using a T-die extruder, a film of an ethylene/acrylic acid
copolymer (EAA, available from DuPont-Mitsui Polychemicals, Co.,
Ltd.) having a thickness of 50 was produced. The resulting
ethylene/acrylic acid copolymer film and an aluminum-deposited film
(film having a layer for deposition and an inorganic layer (111))
having a thickness of 50 pm were bonded under pressure at 105°C and
0.3 MPa for 10 seconds by means of a heat sealer in such a manner
thatthedepositedsurfacebecameanadhesivesurface. Thislaminated
film was cut into a size of 15 mm (width) X 80 mm (length) (film
5 direction agreed with longitudinal direction), and using a tensile
tester, a tensile test of T-type was carried out at a pulling rate
of 300 mm/min, and a T-peel strength during peeling was taken as a
deposition strength. In Table 1, the bond strength is referred to
as aluminum deposition strength.
10 [0113]
[Glossiness of inorganic layer (111) (%)I
Glossiness: Specular gloss of a gloss surface at an incident
angle of 20 degrees was measured by a gloss meter (manufactured by
Murakami Color Research laboratory Co., Ltd., GM-26D) in accordance
15 with the method of JIS P 8142. In Table 1, glossiness is referred
to as gloss.
[0114]
(Polyolefins used)
(1) Modified PP-1: modified isotactic random polypropylene
(MFR=12 9/10 min, density=O. 91 g/cm3, maleic anhydride graft
quantity=0.4 wt%, melting point=138"C, Mw/Mn=4.5)
(2) Modified PP-2: modified isotactic homopropylene
(MFR=10 9/10 min, density=O. 90 g/cm3, maleic anhydride graft
quantity=0.3 wt%, Melting point=158"C, Mw/Mn=4.1)
(3) PP-1: random polypropylene
(MFR=7 9/10 min, density=O .91 g/cm3, melting point=141 'C,
ethylene content=3.5 mol%, Mw/Mn=7.5)
(4) PP-2: homopolypropylene
5 (MFR=3.0 9/10 min, density=O. 91 g/cm3, melting point=162'C,
Mw/Mn=7.2)
(5) PER-1: propylene/ethylene random copolymer
(MFR=2O 9/10 min, density=O. 86 g/cm3, ethylene content=2Omol%,
melting point=109'C, Mw/Mn=2.1)
(6) PBR-1: propylene/butene random copolymer
(MFR=7 9/10 min, density=O .86 g/cm3, butene content=25 mol%,
melting point=7S0C, Mw/Mn=2.2)
(7) PEBR-1: propylene/ethylene/butene random copolymer
(MFR=3 9/10 min, density=O. 86 g/cm3, ethylene content=13 mol%,
15 butene content=19 mol%, melting point=45"C, Mw/Mn=2.0)
(8) EPR-1: ethylene/propylene copolymer
(MFR measured at 190'C under a load of 2.16 kg in accordance
with ASTM Dl238 = 1 9/10 min, density=O. 87 g/cm3, propylene content=19
mol%, melting point = not detected)
(9) Ethylene-based copolymer: ethylene/methyl methacrylate
(MFR measured at 190 "C under a load of 2.16 kg in accordance
with ASTM Dl238 = 20 9/10 min, density=O. 94 g/cm3, methyl methacrylate
content=20 wt%)
[Example 11

Using a single screw extruder, 50% by weight of modified
isotactic homopolypropylene (A) (modified PP-1) and 50% by weight
ofapropylene/ethylenerandomcopolymer (B) (PER-1)weremelt-kneaded
5 at 230°C to obtain a composition (P) for a layer for deposition.

Layers ofthe following constitutionwere coextrudedunderthe
following conditions to produce a two-layer laminated film.
10 [0116]
For the polyolefin-based resin layer (I), the random
polypropylene (PP-1) was used. For the layer (11) for deposition,
a blend of the composition (P) for a layer for deposition prepared
bytheaboveprocess andthepolypropylene (PP-1) (weight of component
15 (P) :weight of component (PP-1)= 4O: 60)w as used. Thepolyolefi n-based
layer (I) and the layer (11) for deposition were extruded by a T-die
extruder and laminated in this order in a feed block. The die
temperature was 230°C. The thus coextruded laminate having a
thickness of about 50 pm was cooled by a chill roll, subjected to
20 ozone treatment and then taken off at a rate of 20 m/min. The thickness
ofthelayer (11) fordeposition/thethicknessofthepolyolefin-based
resin layer (I) was set to 5/45 pm. The wetting index of the layer
for deposition was adjusted to 42 dyn/cm by the ozone treatment.
Usingabatchtypealuminumdepositionapparatus (ShowaVacuum
SIP-600), aluminum deposition was carried out on the layer for
deposition of the laminated film obtained above in such a manner that
the thickness became 50 nm.

Depositionstrengthofthelaminateobtainedintheaboveexample
and gloss of the inorganic layer (deposited surface) were measured
inaccordancewiththeaforesaiddepositionstrengthmeasuringmethod
10 and gloss measuring method. The results are set forth in Table 1.
(Examples 2 to 8, Comparative Examples 1 to 4)
Two-layer laminated films were produced in the same manner as
inExample1, exceptthatthecomposition (P) foralayerfordeposition
15 or the layer (11) for deposition was prepared in accordance with the
formulation shown in Table 1 or 2.
Performance of the resulting laminates is set forth in Table
1 or 2.
20 [0121]
(Comparative Example 5)
Instead of the composition (P) for a layer for deposition
described in Example 1, a composition was obtained by melt-kneading
60% by weight of random polypropylene (PP-1) and 40% by weight of
anethylene-basedcopolymer (ethylene/methylmethacrylate) at 230'C
by the use of a single screw extruder.
[0122]
A two-layer laminated film was produced in the same manner as
5 inExample1, except that the above compositionwas used forthe layer
(11) for deposition.
[0123]
Performance of the resulting laminate is set forth in Table
2.
10 [0124]
(Reference Example)
Using a single screw extruder, 90% by weight of modified
isotactic homopolypropylene (modified PP-1) and 10% by weight of a
propylene/ethylene random copolymer (PER-1) were melt-kneaded at
15 230°C to obtain a composition for a layer for deposition.
[0125]
A two-layer laminated film was produced in the same manner as
inExample 1, except that the above compositionwas used forthe layer
(11) for deposition.
20 [0126]
Performance of the resulting laminate is set forth in Table
2.
101271
The resultinglaminate exhibited a deposition strength of 1.5
N/15 min, but surface roughening took place a t t h e i n t e r f a c e of the
polyolefin-basedresinlayer ( I ) , s o t h a t gloss couldnot bemeasured
stably.
[0128] [Table 11
Table 1
Composition for
Ethylene-based
copolymer
EAAmethoddeposition
strength
Gloss
N/15m
%
1.5
450
1.2
470
1 . 3
440
1 . 3
450
0.9
450
1.6
440
0.7
450
1.2
420
[0129] [Table 21
Table 2
Composition for
layer for
deposition
Layer for
deposition
Modified PP-1
Modified PP-2
PP-1
PER-1
PBR-1
PEBR-1
EPR-1
Composition for layer
for deposition
PP-1
PP-2
Ethylene-based
copolymer
EAAmethoddeposition
strength
Gloss
Comp .
Ex. 1
100
4 0
60
0.3
450
wt%
wt%
N/15mm
%
Comp .
Ex. 2
90
10
4 0
60
0.4
450
comp .
Ex. 3
50
50
4 0
60
0.3
440
Comp .
Ex. 4
50
50
4 0
~~~~~~
60
1.3
220
comp .
Ex. 5
60
4 0
0.9
55
Ref. Ex.
90
10
100
1.5
immeasurable
53
Claims
[Claim 11
A laminate having at least a polyolefin-based resin layer (I),
alayer (11) fordepositionandaninorganiclayer (111) inthisorder,
5 wherein:
the layer (11) for deposition comprises a composition (P) for
a layer for deposition and polypropylene (D) and is different from
the polyolefin-based resin layer (I),
the composition (P) for a layer for deposition is obtained by
10 melt-kneading 30 to 85% by weight of isotactic polypropylene (A),
70 to 15% by weight of a propylene-based copolymer (B) (with the proviso
that the total of (A) and (B) is 100% by weight), and if necessary,
an additive, and a part or all of the isotactic polypropylene (A)
and/orthepropylene-basedcopolymer (B) hasbeengraft-modifiedwith
15 a graft monomer (C) , and
the propylene-based copolymer (B) is different from the
isotactic polypropylene (A) and (i) contains 45 to 89% by mol of
constituent units (U3) derived from propylene and 11 to 55% by mol
of constituent units (Uo) derivedfromatleastonea-olefin selected
20 from ethylene and a-olefins of 4 to 20 carbon atoms (with the proviso
that the total of the constituent units (U3) derived from propylene
and the constituent units (Uo) derived from the a-olefin is 100% by
mol) .
[Claim 21
The laminate as claimedinclaiml, whereinthepropylene-based
copolymer (B) further satisfies the following requirements (ii) and
(iii) :
5 (ii) ameltingpoint (Tm) asmeasuredbyadifferentialscanning
calorimeter is not higher than 120°C or is not observed, and
(iii) a molecular weight distribution (Mw/Mn) as determined
by gel permeation chromatography. (GPC) is in the range of 1.0 to 3.0.
10 [Claim 31
The laminate as claimed in claim1 or 2, wherein the graft quantity
of the graft monomer (C) is 0.001 to 5 parts by weight based on 100
weight of the total of the isotactic polypropylene (A) and the
propylene-based copolymer (B).
[Claim 41
The laminate as claimed in any one of claims 1 to 3, wherein
a weight ratio between the composition (P) for a layer for deposition
and the polypropylene (D) is (P) : (D) =95: 5 to 5: 95.
[Claim 51
The laminate as claimed in any one of claims 1 to 4, wherein
apartorallofat leastthepolypropylene (A) hasbeengraft-modified
with a graft monomer (C).
[Claim 63
The laminate as claimed in any one of claims 1 to 5, wherein
the graftmonomer (C) comprises anunsaturatedcarboxylicacidand/or
5 i t s derivative.
[Claim 71
Thelaminateasclaimedinanyoneofclaims1to 6,whichfurther
has a transparent sealant layer ( I V ) , and
has the polyolefin-based resln layer ( I ) , the layer (11) for
deposition, the inorganic layer (111) and the transparent sealant
layer ( I V ) in t h i s order.
[Claim 81
15 The laminate as claimed in any one of claims 1 to 7, wherein
the inorganic layer (111) contains aluminum.
[Claim 91
Apackagingmaterialcomprisingthelaminate as claimedin any
20 one of claims 1 to 8.
[Claim 101
A laminate having a t l e a s t a layer for deposition, wherein:
thelayerfordepositioncomprisesacomposition (P) f o r a l a y e r
for deposition and polypropylene (D),
the composition (P) for a layer for deposition is obtained by
melt-kneading 30 to 85% by weight of i s o t a c t i c polypropylene ( A ) ,
70 to 15% by weight of a propylene-based copolymer (B) (with the proviso
5 that the t o t a l of (A) and (B) is 100% by weight), and i f necessary,
an additive, and a part or a l l of t h e i s o t a c t i c polypropylene (A)
and/orthepropylene-basedcopolymer (B) hasbeengraft-modifiedwith
a graft monomer ( C ) , and
the propylene-based copolymer (B) is different from the
10 i s o t a c t i c polypropylene (A) and (i) contains 45 to 89% by mol of
constituent units (U3) derived from propylene and 11 t o 55% by mol
of constituent units (Uo) derived f r o m a t l e a s t o n e a - o l e f i n selected
fromethylene anda-olefins of 4 t o 20 carbon atoms (with the proviso
that the t o t a l of the constituent units (U3) derived from propylene
15 and the constituent units (Uo) derived from the a-olefin is 100% by
mol) .
[Claim 111
A production process for a laminate having a t l e a s t a layer
20 for deposition, comprising:
a step (1) of melt-kneading 30 to 85% by weight of i s o t a c t i c
polypropylene (A), 70to15%byweightofapropylene-basedcopolymer
(B) (with the proviso that the t o t a l of (A) and (B) is 100% by weight),
andifnecessary, anadditive toproduceacomposition (P) f o r a l a y e r
f o r deposition, and
a s t e p ( 2 ) of producing a layer f o r deposition comprising the
composition (P) f o r a layer f o r deposition and polypropylene (D),
w h e r e i n a p a r t o r a l l o f t h e i s o t a c t ~ c p o l y p r o p y l e n e (A) and/or
5 thepropylene-basedcopolymer (B) hasbeengraft-mod~fiedwithagraft
monomer (C) , and
the propylene-based copolymer (B) is d i f f e r e n t from the
i s o t a c t i c polypropylene (A) and (i) contains 45 t o 89% by mol of
c o n s t i t u e n t u n i t s (U3) derived from propylene and 11 t o 55% by mol
10 of c o n s t i t u e n t u n i t s (Uo) derived fromat l e a s t one a - o l e f i n s e l e c t e d
fromethylene a n d a - o l e f i n s of 4 t o 20 carbon atoms (with the proviso
t h a t the t o t a l of the c o n s t i t u e n t u n i t s (U3) derived from propylene
and the c o n s t i t u e n t u n i t s (Uo) derived from the a - o l e f i n is 100% by
mol) .