JP2000086778A - Heat-shrinkable sheet or film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject sheet or film excellent in shrinkability, moisture resistance or the like and hardly broken in wrapping of a package having sharp corner and useful as several kind of shrink films by orienting a specified composition comprising a specified cyclic olefin-based resin or the like. SOLUTION: This film is obtained by orienting a composition comprising (A) 95-40 pts.wt. at least one resin selected from (i) a random copolymer of ethylene with a cyclic olefin of formula I [(n) and (q) are each 0 or 1; (m) is >=0; and R1 to R18, Ra and Rb are each H or the like] or formula II [(p) and (q) are each >=0; (m) and (n) are each 0 to 2; and R1 to R19 are each H or the like), (ii) a ring-opened polymer or copolymer of a cyclic olefin of formula I or formula II, (iii) a hydride of the component ii and (iv) graft-modified products of components (i) to (iii), (B) 4-40 pts.wt. polar group-containing polymer including at least one functional group such as carboxyl group, an acid anhydride group or an ester group and (C) 1-20 pts.wt. polyamide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin comprising a cyclic olefin resin, a polar group-containing polymer containing at least one functional group selected from a carboxyl group, an acid anhydride group, an ester group and an epoxy group, and a polyamide resin. It relates to a shrinkable sheet or film. More specifically, the present invention is excellent in shrink properties (heat shrinkability), moisture resistance, and chemical resistance,
The present invention relates to a heat-shrinkable sheet or film that is less likely to be perforated or torn when packaging an object to be packaged having a sharp corner.

[0002]

BACKGROUND OF THE INVENTION Applicants have disclosed that a biaxially stretched cyclic olefin polymer sheet or film is transparent,
It has been found that it has excellent moisture proofing properties and heat shrinkage properties.
-1966832, a heat-shrinkable sheet or film has already been proposed.

Further, Japanese Patent Application Laid-Open No. 8-165 by the present applicant
No. 357 discloses that a composition obtained by blending a specific soft polymer with a cyclic olefin resin is biaxially stretched to provide excellent shrink properties, moisture resistance, chemical resistance, easy-openability, transparency, and high rigidity. It is described that a heat-shrinkable sheet or film into which an object can be easily inserted can be provided.

[0004] However, the heat-shrinkable sheet or film as described above may have insufficient toughness depending on the use. In particular, when used for packaging of a package having sharp corners, the sharp corners may be torn or punctured,
Improvement was desired.

[0005]

An object of the present invention is to improve the toughness of a conventional heat-shrinkable sheet or film using a cyclic olefin-based resin, thereby achieving excellent shrink properties (heat-shrinkability), moisture resistance and chemical resistance. It is an object of the present invention to provide a heat-shrinkable sheet or film that is less likely to be perforated or torn when packaging an object to be packaged having a sharp corner.

[0006]

The heat-shrinkable sheet or film according to the present invention is selected from the group consisting of [A] the following [I-1], [I-2], [I-3] and [I-4]. 95-40 parts by weight of at least one kind of cyclic olefin resin and [B] a polar group-containing polymer 4-40 containing at least one functional group selected from a carboxyl group, an acid anhydride group, an ester group and an epoxy group. A heat-shrinkable sheet or film obtained by stretching a composition comprising 1 part by weight and 1 to 20 parts by weight of a polyamide resin (C).

[I-1] An ethylene / cyclic olefin random copolymer obtained by copolymerizing ethylene with a cyclic olefin represented by the following formula [I] or [II]:

[0008]

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(In the formula [I], n is 0 or 1, m
Is 0 or a positive integer; q is 0 or 1;
^{1 to} R ¹⁸ and R ^a and R ^b are each independently
Hydrogen atom, a halogen atom or a hydrocarbon group, R ¹⁵
To R ¹⁸ may combine with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ may be R ¹⁷ and R ¹⁸ may form an alkylidene group. ),

[0010]

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(In the formula [II], p and q are 0 or an integer of 1 or more; m and n are 0, 1 or 2;
R ^{1 to} R ¹⁹ each independently represent a hydrogen atom, a halogen atom,
An aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein R ¹³ or R ¹¹ is bonded to the carbon atom to which R ⁹ (or R ¹⁰ ) is bonded The carbon atom may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other. It may form a monocyclic or polycyclic aromatic ring. ), [I-
2] a ring-opened polymer or copolymer of a cyclic olefin represented by the above formula [I] or [II], [I-3] the above [I-2]
Hydrogenated ring-opened polymer or copolymer of [I-
4] A graft-modified product of the above [I-1], [I-2] or [I-3].

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the heat-shrinkable sheet or film according to the present invention will be specifically described.

[0013] The heat-shrinkable sheet or film according to the present invention comprises the following [A]: [I-1], [I-2], [I-3] and [I].
-4] 95 to 40 parts by weight of at least one kind of cyclic olefin resin (also referred to as cyclic olefin resin [A]) selected from the group consisting of: [B] carboxyl group, acid anhydride group, ester group, epoxy The composition is obtained by stretching a composition comprising 4 to 40 parts by weight of a polar group-containing polymer containing at least one functional group selected from groups and [C] 1 to 20 parts by weight of a polyamide resin.

Here, the cyclic olefin resin [A] will be described. [A] Cyclic olefin resin In the present invention, as the cyclic olefin resin [A], [I-
1]: a random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II], [I-2]: opening of a cyclic olefin represented by the following formula [I] or [II] A ring polymer or copolymer, [I-3]: a hydride of the above [I-2] ring-opening polymer or copolymer, and [I-4]: a above-mentioned [I
At least one selected from graft-modified products of [-1], [I-2] and [I-3] is used.

The cyclic olefin resin [A] used in the present invention is generally amorphous or low-crystalline, and has a crystallinity as measured by an X-ray diffraction method of usually 20% or less,
Preferably, it is not more than 10%.

The cyclic olefin-based resin [A] contains 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.
It is desirably 0.01 to 20 dl / g, preferably 0.03 to 10 dl / g, and more preferably 0.05 to 8 dl / g.

The iodine value of such a cyclic olefin resin [A] is usually 5 or less, and most of them are 1 or less. Also,
For these cyclic olefin-based resins, the melting point is often not observed when the melting point is measured using a differential scanning calorimeter (DSC).

Another property of such a cyclic olefin resin is that it has a high glass transition temperature (Tg) and a high softening temperature (TMA). The glass transition temperature (Tg) is usually 5
It is measured within the range of 0 to 230 ° C. By using such a cyclic olefin-based resin, the softening temperature of the obtained cyclic olefin-based resin composition as described later is usually measured in the range of 60 ° C or higher, preferably 70 to 250 ° C. .

Here, the cyclic olefin represented by the formula [I] or [II] forming the cyclic olefin resin [A] used in the present invention will be described. Cyclic olefin The cyclic olefin used in the present invention is represented by the following formula.

[0020]

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In the above formula [I], n is 0 or 1,
m is 0 or a positive integer, and q is 0 or 1.
When q is 1, R ^a and R ^b are each independently the following atoms or hydrocarbon groups. When q is 0, each bond is bonded to form a 5-membered ring. Form.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the hydrocarbon group independently include an alkyl group usually having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. A cyclohexyl group is mentioned, and a phenyl group, a naphthyl group, etc. are mentioned as an aromatic hydrocarbon group.

These hydrocarbon groups may be substituted with a halogen atom. Further, in the above formula [I], R
^{15 to} R ¹⁸ may be bonded to each other (together with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed has a double bond. Is also good. The monocyclic or polycyclic rings formed here are specifically exemplified below.

[0025]

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In the formula [II], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. Also R
^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom,
It is a hydrocarbon group or an alkoxy group.

The halogen atom has the same meaning as the halogen atom in the above formula [I]. Further, as the hydrocarbon group, each independently an alkyl group having 1 to 20 carbon atoms,
Examples thereof include a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group. More specifically, as the alkyl group,
A methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group; a cycloalkyl group includes a cyclohexyl group; an aromatic hydrocarbon group; Examples thereof include an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group.
These hydrocarbon groups and alkoxy groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or a carbon atom having 1 to 1 carbon atoms.
And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ , or the groups represented by R ¹⁰ and R ¹¹ cooperate with each other, It forms an alkylene group of any one of a methylene group (-CH2-), an ethylene group (-CH2CH2-) or a propylene group (-CH2CH2CH2-).

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. In this case, as the monocyclic or polycyclic aromatic ring, for example, the following n = m = 0
In the above, a group in which R ¹⁵ and R ¹² further form an aromatic ring can be mentioned.

[0031]

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Here, q has the same meaning as q in the formula [II]. The cyclic olefin represented by the above formula [I] or [II] is more specifically exemplified below.

[0033]

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(In the above general formula, the numbers 1 to 7 indicate the position numbers of carbon atoms) and the compound has a hydrocarbon group. Substituted derivatives are mentioned.

The hydrocarbon groups include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5 -Phenyl, 5
-Benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl), 5 , 6-diphenyl.

Still other derivatives include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-
Tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a
-Bicyclo [2.2.1] such as hexahydroanthracene
A 2-heptene derivative can be exemplified.

In addition, tricyclo [4.3.0.1^2,5] -3-de
Sen, 2-methyltricyclo [4.3.0.1 ^2,5] -3-decene, 5
-Methyltricyclo [4.3.0.1^2,5] -3-Decene and other birds
Cyclo [4.3.0.1^2,5] -3-decene derivative, tricyclo
[4.4.0.1^2,5] -3-undecene, 10-methyltricyclo
[4.4.0.1^2,5] -3-undecene and other tricyclo [4.4.
0.1^{Two ,Five}] -3-undecene derivatives,

[0038]

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Tetracyclo [4.4.0.1 ^2,5 .17 represented by [0039],
10] -3-dodecene and derivatives thereof substituted with a hydrocarbon group. As the hydrocarbon group, 8-methyl, 8-
Ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10-dimethyl, 8,9-dimethyl, 8-ethyl-9- Methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl
-9-ethyl, 9-isobutyl-2,7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,1
2-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8
-Ethylidene-9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-
n-propylidene, 8-n-propylidene-9-methyl, 8-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8 -Isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-
Isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-
Fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl,
Examples thereof include 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl), and 5,6-diphenyl.

[0040] Furthermore, - tetracyclo such (cyclopentadiene acenaphthylene adduct) and adduct of cyclopentadiene [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives, pentacyclo [6.5.1.1 ^{3, 6.0 2,7} .0 ^9,13] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 ^2,5 .1
^9,12 .0 ^8,13] -3-pentadecene and its derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene and derivatives thereof, pentacyclo 6.1.1 ^{3, 6.0 2,7.}
0 ^9,14] -4-hexadecene and derivatives thereof, hexacyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] -4- heptadecene and its derivatives, heptacyclo 7.0.1 ^{2 ,} 9.1 ^.4,7 .
1 ^11,17 .0 ^{3 and 8} .0 ^12,16] -5-eicosene and its derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0
^11,16] -4-eicosene and its derivatives, heptacyclo [8.8.0. ^{12, 9} .1 ^4,7 .1 ^11,18 .0 ^3,8 .0 ^12,17] -5-heneicosene and its derivatives, octacyclo [8.8.0. ^{12, 9} .1
^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17] -5-docosene and its derivatives, Nonashikuro [10.9.1.1 ^4,7 .1 ^{13, 20} .1 ^{15 and 18} .0
^2,10 .0 ^3,8 .0 ^12,21 .0 ^14,19] such as 5-pentacosene and derivatives thereof.

Specific examples of the cyclic olefin represented by the above formula [I] or [II] that can be used in the present invention are as described above. Paragraph No. [00] of Japanese Patent Application Laid-Open No. 7-145213 filed by the present applicant.
32] to [0054], and those exemplified herein can be used as the cyclic olefin of the present invention.

The cyclic olefin represented by the above general formula [I] or [II] can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to a Diels-Alder reaction.

These cyclic olefins can be used alone or in combination of two or more. The cyclic olefin resin used in the present invention can be prepared by using the cyclic olefin represented by the formula [I] or [II] as described above, for example, in JP-A-60-168708, JP-A-61-120816 and JP-A-61-120816
-115912, 61-115916, 61-271308, 61-2722
Nos. 16, 62-252406, 62-252407, etc., according to the method proposed by the present applicant, and by appropriately selecting conditions, it can be produced.

[I-1] Ethylene / cyclic olefin lander
Copolymer [I-1] The ethylene / cyclic olefin random copolymer generally contains 20 to 9 structural units derived from ethylene.
It contains 5 mol%, preferably 30 to 90 mol%, of structural units derived from cyclic olefins, usually in an amount of 5 to 80 mol%, preferably 10 to 70 mol%.
The composition ratio of ethylene and cyclic olefin is 13C-
Measured by NMR.

In the [I-1] ethylene / cyclic olefin random copolymer, the structural units derived from ethylene and the structural units derived from the cyclic olefin are randomly arranged and bonded, It has a substantially linear structure. The fact that the copolymer is substantially linear and does not have a substantially gel-like cross-linked structure means that when the copolymer is dissolved in an organic solvent, the solution contains an insoluble component. You can confirm by not having. For example, when the intrinsic viscosity [η] is measured,
It can be confirmed by complete dissolution in decalin at 5 ° C.

In the [I-1] ethylene / cyclic olefin random copolymer used in the present invention, the above-mentioned formula [I]
Or at least a part of the cyclic olefin represented by [II] is considered to constitute a repeating unit represented by the following formula [III] or [IV].

[0047]

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In the formula [III], n, m, q, R ^{1 to} R
¹⁸ and R ^a and R ^b have the same meanings as in formula [I].

[0049]

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In the formula [IV], n, m, p, q and R ^{1 to} R ¹⁹ have the same meaning as in the formula [II]. Further, the [I-1] ethylene / cyclic olefin random copolymer used in the present invention has a structural unit derived from another copolymerizable monomer as needed within a range not to impair the object of the present invention. May be.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic olefin. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, Methyl-1-butene, 3-
Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-
Α- having 3 to 20 carbon atoms such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene
Olefin, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene and cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano Cycloolefins such as -1H-indene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2 Non-conjugated dienes such as -norbornene.

These other monomers can be used alone or in combination. [I-1] Ethylene
In the cyclic olefin random copolymer, structural units derived from other monomers as described above usually have 20 units.
It may be contained in an amount of up to 10 mol%, preferably up to 10 mol%.

The [I-1] ethylene / cyclic olefin random copolymer used in the present invention comprises ethylene and the formula [I]
Alternatively, it can be produced by using the cyclic olefin represented by [II] and the production method disclosed in the above publication. Among these, this copolymerization is carried out in a hydrocarbon solvent, and the [I-1] ethylene / cyclic olefin random copolymer is used as a catalyst using a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent. It is preferred to produce a polymer.

In this copolymerization reaction, a solid group IVB metallocene catalyst can also be used. Where solid IV
The group B metallocene-based catalyst is a catalyst comprising a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organic aluminum oxy compound, and an organic aluminum compound optionally added. Here, the group VI transition metal is zirconium, titanium or hafnium, and these transition metals have at least one ligand having a cyclopentadienyl skeleton. here,
Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group or an indenyl group, a tetrahydroindenyl group and a fluorenyl group which may be substituted by an alkyl group. These groups may be bonded via another group such as an alkylene group. Further, ligands other than the ligand having a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like.

Further, as the organoaluminum oxy compound and the organoaluminum compound, those usually used for producing an olefin resin can be used. Such a solid group IVB metallocene catalyst is described in, for example, JP-A-61-221206, JP-A-64-106, and JP-A-2-173112.

[I-2] Ring Opening Polymer of Cyclic Olefin or
Is a ring-opened polymer or ring-opened copolymer of a copolymer cyclic olefin, wherein at least a part of the cyclic olefin represented by the above formula [I] or [II] is represented by the following formula [V] or [VI] It is considered to constitute the repeating unit represented.

[0057]

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In the formula [V], n, m, q and R ¹
To R ¹⁸ and R ^a and R ^b have the same meanings as in formula [I].

[0059]

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In the formula [VI], n, m, p, q and R ^{1 to} R ¹⁹ have the same meaning as in the formula [II]. Such a ring-opening polymer or a ring-opening copolymer can be produced by the production method disclosed in the above-mentioned gazette. It can be produced by polymerization or copolymerization below.

Examples of such a ring-opening polymerization catalyst include a catalyst comprising a halide, nitrate or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, indium or platinum and a reducing agent; A catalyst comprising a halide or acetylacetone compound of a metal selected from palladium, zirconium or molybdenum and an organoaluminum compound can be used.

[I-3] Hydrogen of ring-opened polymer or copolymer
The hydride of the ring-opening polymer or copolymer [I-3] used in the present invention is obtained by converting the ring-opening polymer or copolymer [I-2] obtained as described above into a conventionally known hydrogen-containing compound. It is obtained by hydrogenation in the presence of an added catalyst.

In the hydride of the ring-opened polymer or copolymer [I-3], at least a part of the cyclic olefin represented by the formula [I] or [II] has the following formula [VII]
Or it is thought that it has the repeating unit represented by [VIII].

[0064]

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In the formula [VII], n, m, q and R ¹
To R ¹⁸ and R ^a and R ^b have the same meanings as in formula [I].

[0066]

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In the formula [VIII], n, m, p, q, R
^{1 to} R ¹⁹ have the same meaning as in formula [II]. [I-4] Graft Modified Product The graft modified product of the cyclic olefin resin is the above-mentioned [I-
1] random copolymer of ethylene and cyclic olefin, [I-
2] A ring-opened polymer or copolymer of a cyclic olefin or [I-3] a graft-modified product of a hydride of a ring-opened polymer or copolymer.

As the modifier, unsaturated carboxylic acids are usually used, and specific examples thereof include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Unsaturated carboxylic acids such as endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid TM), and derivatives of these unsaturated carboxylic acids such as unsaturated carboxylic anhydride and unsaturated carboxylic acid Examples include carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and unsaturated carboxylic acid ester compounds.

Specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, citraconic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

Among these modifiers, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic anhydrides such as maleic acid, nadic acid and anhydrides of these acids are preferably used. These modifiers can be used in combination of two or more.

The modification rate of the graft modified product of the cyclic olefin resin used in the present invention is usually desirably 10 mol% or less. Such a graft modified product of a cyclic olefin-based resin can be produced by blending a modifier with a cyclic olefin-based resin so as to obtain a desired modification rate and graft-polymerizing the same, or a modified product having a high modification rate can be prepared in advance. It can also be produced by preparing and then mixing this modified product with an unmodified cyclic olefin resin.

In order to obtain a graft-modified product of a cyclic olefin resin from a cyclic olefin resin and a modifier, a conventionally known method for modifying a polymer can be widely applied.
For example, a graft-modified product is obtained by a method of adding a modifier to a molten cyclic olefin-based resin and performing graft polymerization (reaction), or a method of adding a modifier to a solvent solution of the cyclic olefin-based resin and performing a graft reaction. be able to.

Such a graft reaction is usually carried out at 60 to 3
It is performed at a temperature of 50 ° C. The graft reaction can be performed in the presence of a radical initiator such as an organic peroxide and an azo compound.

A modified product having the above modification rate can be directly obtained by a graft reaction between a cyclic olefin resin and a modifying agent, and a high modification rate can be previously obtained by a graft reaction between the cyclic olefin resin and a modifying agent. After obtaining the modified product of the above, the modified product can be obtained by diluting the modified product with an unmodified cyclic olefin resin so as to obtain a desired modification ratio.

In the present invention, the cyclic olefin resin [A]
Any of [I-1], [I-2], [I-3] and [I-4] as described above can be used alone, or a combination of these can be used.

Of these, an ethylene / cyclic olefin random copolymer [I-1] is preferably used. In the present invention, a resin composition obtained by further blending another resin with the cyclic olefin resin [A] may be used.

The following [B] carboxyl group, acid anhydride group,
The polar group-containing polymer containing at least one functional group selected from an ester group and an epoxy group will be described. [B] Polar group-containing polymer This polar group-containing polymer [B] has at least one functional group selected from a carboxyl group, an acid anhydride group, an ester group and an epoxy group and a double bond in one molecule. It is obtained by copolymerization of a monomer (hereinafter referred to as a polar group-containing unsaturated compound) and an α-olefin. Specific examples of the polar group-containing unsaturated compound containing a carboxyl group include (meth)
Acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acidTM) And unsaturated carboxylic acids.

Specific examples of the polar group-containing unsaturated compound having an acid anhydride group include maleic anhydride, citraconic anhydride, nadic anhydride and the like.

Of these compounds, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic anhydrides such as maleic acid, nadic acid and anhydrides of these acids are preferably used. Further, these monomers can be used in combination of two or more kinds. Examples of the polar group-containing unsaturated compound containing an ester group include the above-mentioned unsaturated carboxylic acid methyl ester, ethyl ester, butyl ester, propyl ester, isopropyl ester and the like.

Examples of the double bond-containing compound containing an epoxy group include glycidyl acrylate, glycidyl methacrylate and glycidyl maleate.
Monomers used for copolymerization with a polar group-containing unsaturated compound include ethylene, propylene, butene-1, 4
-Methyl-1-pentene, hexene-1, octene-
Α-olefins having 2 to 15 carbon atoms such as 1, decene-1 and the like are used, and among them, ethylene is particularly preferably used. Examples of specific copolymers include ethylene
(Meth) acrylic acid copolymer, ethylene / maleic anhydride copolymer and these copolymers and alkali metal or
Neutralized product with alkaline earth metal, ethylene / methyl (meth) acrylate copolymer, ethylene / ethyl (meth)
Acrylate copolymer, ethylene glycidyl (meth)
An acrylate copolymer can be mentioned.

The polar group-containing polymer [B] can also be obtained by grafting a polar group-containing unsaturated compound to a known polymer by a known method. Here, the following examples can be given as the polymer used for the graft reaction of the polar group-containing unsaturated compound. [Α-olefin-based copolymer (1)] The α-olefin-based copolymer is formed from at least two kinds of α-olefins. Specific examples include an ethylene / α-olefin copolymer and a propylene / α-olefin copolymer.

As the α-olefin constituting the ethylene / α-olefin copolymer, those having 3 to 20 carbon atoms are usually used, and specifically, propylene, 1-butene, 4-methyl
Examples include 1-pentene, 1-hexene, 1-octene, 1-decene, and the like, or a mixture thereof. Of these,
Particularly, α-olefins having 3 to 10 carbon atoms are preferable.

The molar ratio of ethylene / α-olefin copolymer (ethylene / α-olefin) varies depending on the type of α-olefin, but is generally 40/60 to 95/5. The molar ratio is preferably from 40/60 to 90/10 when the α-olefin is propylene, and from 50/50 to 95/5 when the α-olefin has 4 or more carbon atoms. Preferably, there is.

As the α-olefin constituting the propylene / α-olefin copolymer, one having 4 to 20 carbon atoms is usually used, and specifically, 1-butene and 4-methyl-1-
Examples include pentene, 1-hexene, 1-octene and 1-decene, or mixtures thereof. this house,
Particularly, α-olefins having 4 to 10 carbon atoms are preferable.

In the propylene / α-olefin copolymer described above, the molar ratio of propylene to α-olefin (propylene / α-olefin) varies depending on the type of α-olefin, but is generally 50/50. ~ 95
/ 5.

[Α-Olefin / Diene Copolymer (2)] As the α-olefin / diene copolymer,
Examples thereof include an ethylene / α-olefin / diene copolymer rubber and a propylene / α-olefin / diene copolymer rubber. Α constituting these copolymer rubbers
-Olefin is usually 3 to 20 carbon atoms (propylene
4 to 20) α-olefins in the case of α-olefins, for example, propylene, 1-butene, 1-pentene, 4-methyl-1
-Pentene, 1-hexene, 1-octene, 1-decene or mixtures thereof. Among these,
Α-olefins having 3 to 10 carbon atoms are preferred.

The diene components constituting these copolymer rubbers are 1,4-hexadiene, 1,6-octadiene, and 2-diene.
Linear non-conjugated dienes such as methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene and 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene,
Methyltetrahydroindene, 5-vinylnorbornene,
Cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3- Examples include diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

The above ethylene (or propylene) α-
In the olefin-diene copolymer rubber, the molar ratio of ethylene (or propylene) to α-olefin [ethylene (or propylene) / α-olefin] varies depending on the type of α-olefin, but is generally 40 / α. 60
９０90/10.

The content of the repeating unit derived from the diene component in these copolymer rubbers is usually 1 to 20 mol%, preferably 2 to 15 mol%. [Aromatic vinyl hydrocarbon / conjugated diene soft copolymer (3)] The aromatic vinyl hydrocarbon / conjugated diene soft copolymer is a random copolymer of an aromatic vinyl hydrocarbon and a conjugated diene, It is a block copolymer or a hydride thereof. Specifically, styrene / butadiene block copolymer rubber, styrene / butadiene / styrene block copolymer rubber, styrene / isoprene block copolymer rubber, styrene / isoprene / styrene block copolymer rubber, hydrogenated styrene / butadiene / Styrene block copolymer rubber, hydrogenated styrene / isoprene / styrene block copolymer rubber, styrene / butadiene random copolymer rubber, or rubber obtained by graft-polymerizing styrene, methyl acrylate, or the like to these rubbers is used.

In these copolymer rubbers, the molar ratio between the aromatic vinyl hydrocarbon and the conjugated diene (aromatic vinyl hydrocarbon / conjugated diene) is from 10/90 to 70/30.
It is preferred that In these copolymer rubbers, the hydrogenated copolymer rubber is a copolymer rubber in which part or all of the double bonds remaining in the above-mentioned copolymer rubber are hydrogenated.

[Soft polymer or copolymer comprising isobutylene or isobutylene / conjugated diene (4)] The isobutylene-based soft polymer or copolymer is, specifically,
Examples include polyisobutylene rubber, polyisoprene rubber, polybutadiene rubber, and isobutylene / isoprene copolymer rubber.

Incidentally, 135 of the copolymer (1) to (4) was used.
The intrinsic viscosity [η] measured in decalin at 0 ° C is usually in the range of 0.01 to 10 dl / g, preferably 0.08 to 7 dl / g, and the glass transition temperature (Tg) is usually 0 ° C or less. , Preferably -10 ° C or lower, particularly preferably -20 ° C or lower. The crystallinity measured by the X-ray diffraction method is usually in the range of 0 to 30%, preferably 0 to 20%, particularly preferably 0 to 10%. [B] used in the present invention
As the polar group-containing polymer, an ethylene / α-olefin copolymer obtained by grafting an unsaturated group-containing carboxylic acid or its anhydride is preferably used.

Next, the polyamide resin [C] used in the present invention will be described. [C] Polyamide Resin The polyamide resin used in the present invention is a polyamide or copolyamide derived from a polycondensation reaction of a diamine component and a dicarboxylic acid component or an aminocarboxylic acid or a corresponding lactam. 6,
Nylon 66, nylon 610, nylon 11, nylon 612, nylon 12, copolymerized nylon formed from caprolactam and a nylon salt, nylon MXD6 formed from metaxylene diamine and adipic acid, nylon 46 and methoxymethylated polyamide; Examples thereof include polyhexamethylenediamine terephthalamide and polyhexamethylenediamine isophthalamide.

[Other Additives] The heat-shrinkable sheet or film according to the present invention may be any of known heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents and the like as long as the object of the invention is not impaired.
A slip agent, an anti-blocking agent, an anti-fogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax and the like may be blended.

For example, stabilizers to be blended as optional components include tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane,
β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenol antioxidants such as propionate, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 1,2-hydroxystearate, glycerin monostearate, glycerin distearate, and pentaerythritol Polyhydric alcohol fatty acid esters such as rumonostearate, pentaerythritol distearate, and pentaerythritol tristearate can be exemplified. These may be blended alone or in combination. For example, tetrakis [methylene-3
-(3.5-di-t-butyl-4-hydroxyphenyl) propionate] A combination of methane, zinc stearate and glycerin monostearate can be exemplified. These stabilizers can be used alone or in combination of two or more.

Examples of the organic and inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, Calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica,
Asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide,
Examples thereof include boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.

[Production of heat-shrinkable sheet or film]
The heat-shrinkable sheet or film of the present invention comprises the cyclic olefin resin [A] (or the resin composition containing the resin [A]) in an amount of 95 to 40 parts by weight, preferably 90 to 50 parts by weight, and more preferably 80 to 50 parts by weight. To 60 parts by weight and 4 to 40 parts by weight of the polar group-containing polymer [B], preferably 10 to 30 parts by weight.
Parts by weight, more preferably 20 to 30 parts by weight, and 1 to 20 parts by weight, preferably 2 to 10 parts by weight, more preferably 2 to 8 parts by weight of the polyamide resin [C] are previously mixed by an extruder, a kneader or the like. After that, it can be formed into a sheet or film using a known method. Also, a sheet or film can be formed while kneading these raw materials with a sheet or film forming machine. As a method for forming a sheet or film, T-die method, inflation method, press molding method, and the like, using a method known per se, to form a sheet or film, and then uniaxially or biaxially stretched The heat-shrinkable sheet or film of the present invention can be obtained. The thickness of the heat-shrinkable sheet or film according to the present invention can be appropriately set in consideration of its use.

In the case where the unstretched sheet or film is uniaxially or biaxially stretched, a method of stretching the unstretched sheet or film by heating it to a temperature equal to or higher than the glass transition temperature (Tg) is employed. In the present invention, the stretching ratio can be appropriately set in consideration of, for example, required properties such as strength and shrinkage. As the stretching method, a commonly used stretching method such as a roll stretching method, a tenter stretching method, an inflation method, a tubular biaxial stretching method, or the like can be employed.

The preferred embodiment of the method for producing a heat-shrinkable sheet or film according to the present invention will be described in further detail with reference to specific examples. The composition of the present invention is prepared by utilizing a T-die molding method or an inflation molding method. For example, a sheet or film having a thickness of 0.01 to 2 mm is prepared.

Next, the sheet or film prepared as described above was used as the glass transition temperature of the cyclic olefin resin [A] forming the sheet or film.
(Tg) is heated to a temperature higher by 0 to 60C, preferably 10 to 40C. Subsequently, the sheet or film heated to such a temperature is stretched 1.5 to 10 times sequentially in the machine direction and / or the transverse direction, or simultaneously in both directions, for example, to a thickness of 1 to 100 μm, Preferably, a stretched film or sheet of about 10 to 50 μm can be obtained. The heat shrinkage rate (%) of the heat-shrinkable sheet or film thus obtained is determined by the used cyclic olefin resin [A] or the resin [A].
When the resin composition containing the cyclic olefin-based resin [A] is heat-treated at a temperature of, for example, about 80 to 120 ° C., depending on the type of the resin composition containing the resin and the heat treatment temperature (° C.). , Usually about 20 to 100%.

The heat-shrinkable sheet or film according to the present invention thus obtained has excellent shrink properties, moisture resistance, chemical resistance, and easy-openability. Also impact strength,
It is excellent in piercing strength and the like, and is less likely to be torn or perforated even when used for a packaged article having a sharp corner.

The heat-shrinkable sheet or film of the present invention is a heat-shrinkable packaging material for storing and transporting foods, medicines, utensils, notebooks, etc .; a seal packaging material for preventing opening of caps and stoppers; bottles, containers, etc. Heat-shrinkable label material; suitable for battery packaging material.

[0103]

As described above, the heat-shrinkable sheet or film according to the present invention has a shrink property, a moisture-proof property,
Excellent toughness, especially resistant to tearing and puncturing.
Due to such properties, the heat-shrinkable sheet or film of the present invention is useful, for example, as various shrink films. In addition, since a chlorine-containing material is not used, there is no need to generate dioxin during incineration.

[0104]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The methods for measuring and evaluating various physical properties according to the present invention are described below. (1) Melt flow index (MFR): Measured under a load of 2.16 kg according to ASTM-D1238. (2) Softening temperature (TMA): Dupont Thermal Mechani
It measured by the thermal deformation behavior of a sheet having a thickness of 1 mm using a cal Analyzer. A quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5 ° C./min.
The temperature at which 5 mm entered was defined as TMA. (3) Glass transition temperature (Tg): Measured at a heating rate of 10 ° C./min using DSC-20 manufactured by SEIKO Electronic Industries. (4) Tensile test: An ASTM TYPEIV dumbbell-type test piece was punched out of a molded product, and measured at a test temperature of 23 ° C according to the method of ASTM-D638. (5) Film impact: 100 × 10 from molded product
A test piece of 0 mm was cut out and measured using a film impact tester manufactured by Toyo Seiki. Impact head diameter 1 inch (6) Tear strength: Measured by Elmendorf tear method according to ASTM-D1922. The measurement temperature is 23 ° C. (7) Break-through strength: A molded product attached to a jig having a receiving diameter of 50 mm is pierced by a rod having a tip R of 1/2 inch.
It was pressed at a speed of mm / min, and the stress and deformation when the molded product was torn were measured. (8) Shrink property: A test piece is cut from a molded product into a strip having a length of 150 mm in the measurement direction and a width of 20 mm, and marked lines having a distance of 100 mm are drawn in the length direction. Next, the test piece is placed at a predetermined temperature as shown in Table 1 for 5 minutes, and the length of the marked line after contraction is measured. From the length between the marked lines before and after the test, the shrinkage ratio is determined using the following equation. Shrinkage (%) = (length of mark before test−length of mark after test) × 100 / length of mark before test

[0106]

REFERENCE EXAMPLE 1 1 part by weight of maleic anhydride, 100 parts by weight of ethylene / propylene random copolymer having an MFR of 0.4 g / 10 min. (Nippon Oil & Fat, Perhexin 2
5B) A mixture of 0.2 parts by weight and 3 parts by weight of acetone was blended and thoroughly mixed. Next, the mixture was kneaded with a twin-screw extruder in which the cylinder temperature was set at 270 ° C. to obtain pellets. The pellet was dissolved in xylene and reaggregated with acetone to remove unreacted maleic anhydride.
As a result, it was found that 0.95% by weight of maleic anhydride was grafted.

[0107]

REFERENCE EXAMPLE 2 Instead of the ethylene / propylene random copolymer of Reference Example 1, an ethylene content of 85 mol%, 190 ° C
The graft reaction was carried out in the same manner as in Reference Example 1 except that an ethylene / butene-1 random copolymer having an MFR of 3.6 g / 10 min as measured in Example 1 was used, and the grafting amount of maleic anhydride was 0.97% by weight. A graft was obtained.

[0108]

Reference Example 3 A graft reaction was carried out in the same manner as in Reference Example 1, except that glycidyl methacrylate was used instead of maleic anhydride. The graft amount was 0.60% by weight.

[0109]

Example 1 As a cyclic olefin copolymer, ethylene and 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene {in other words, tetracyclo [ 4.4.0.12,5.1
7,10] -3-dodecene｝ (structural formula;

[0110]

Embedded image

A random copolymer (hereinafter abbreviated as “TCD”) (ethylene content 68 mol% measured by 13 C-NMR)
, Intrinsic viscosity [η] measured in decalin at 135 ° C.
80dl / g, softening temperature (TMA) 80 ° C, glass transition temperature (T
g: 70 ° C.)) 77% by weight and 19% by weight of the polymer of Reference Example 1
And nylon 6 (Unitika, A1020BRL) 4
% By weight and pelletized on a twin screw extruder set at 270 ° C. Then, the pellets are press-formed (temperature 2).
At 70 ° C), a 200 μm press sheet was prepared, and a batch-type biaxial stretching device was used at an ambient temperature of 100 ° C and a draw ratio of 2 × 2.
And a biaxially stretched film having a thickness of 50 μm was obtained. Table 1 shows the physical properties of this film.

[0112]

Example 2 A film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the polymer of Reference Example 2 was used instead of the polymer of Reference Example 1 used in Example 1. Was. Table 1 shows the physical properties.

[0113]

Example 3 A film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the polymer of Reference Example 3 was used instead of the polymer of Reference Example 1 used in Example 1. Was. Table 1 shows the physical properties.

[0114]

Comparative Example 1 The MF measured at 190 ° C. and an ethylene content of 80 mol% instead of the polymer of Reference Example 1 used in Example 1
Molding was performed in the same manner as in Example 1 except that the ethylene / propylene random copolymer 100 having an R of 0.4 g / 10 min was used, to obtain a film having a thickness of 70 μm. Table 1 shows the physical properties.

[0115]

Comparative Example 2 The MF measured at 190 ° C. and an ethylene content of 85 mol% instead of the polymer of Reference Example 1 used in Example 1
Molding was performed in the same manner as in Example 1 except that a random copolymer of ethylene and butene-1 having an R of 3.6 g / 10 min was used to obtain a film having a thickness of 70 μm. Table 1 shows physical properties
Shown in

[0116]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) // (C08L 45/00 51:00 77:00) (C08L 65/00 51:00 77:00) F Terms (reference) 4F071 AA15X AA20X AA39X AA54 AA69 AA77 AA78 AF61 AH04 BA01 BB03 BB07 BB08 BC01 4J002 BB011 BB042 BB072 BB082 BB092 BB101 BB142 BB162 BB201 BB211 BB212 03003 BB212 BB03 CL013

Claims (2)

[Claims] 1. [A] at least one type of cyclic olefin resin 95 to 40 selected from the group consisting of the following [I-1], [I-2], [I-3] and [I-4] Parts by weight, [B] 4 to 40 parts by weight of a polar group-containing polymer containing at least one functional group selected from a carboxyl group, an acid anhydride group, an ester group and an epoxy group, and [C] a polyamide resin 1-2.
A heat-shrinkable sheet or film obtained by stretching a composition comprising 0 parts by weight; [I-1] copolymerizing ethylene with a cyclic olefin represented by the following formula [I] or [II]. An ethylene / cyclic olefin random copolymer obtained by the reaction: (In the formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently: A hydrogen atom, a halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond; R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.), In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon. Group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁹ (or R ¹⁰ ) is bonded and the carbon atom to which R ¹³ or R ¹¹ is bonded are They may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic ring. The ring may form an aromatic ring. ), [I-2] the ring-opening polymer or copolymer of the cyclic olefin represented by the above formula [I] or [II], [I-3] the ring-opening polymer or copolymer of the above [I-2]. Hydride of the polymer, and [I-4] [I-
[1] A graft-modified product of [I-2] or [I-3]. 2. The heat-shrinkable sheet according to claim 1, wherein the polar group-containing polymer is an ethylene / α-olefin copolymer grafted with an unsaturated group-containing carboxylic acid or an anhydride thereof. the film.