JP2007203689A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate excellent in heat resistance and flexibility. <P>SOLUTION: The laminate is composed of at least one surface layer, at least one intemediate layer and at least one base material layer. The surface layer contains a thermoplastic layer. The intemediate layer contains a resin composition containing 95-5 wt.% of an amorphous or a low crystalline olefinic polymer satisfying the following requirements (a), (b) and (c) and 5-95 wt.% of a thermoplastic resin excluding the amorphous or the low crystalline olefinic polymer. The base material layer is composed of paper or metal. (a): The heat of crystal fusion as determined by differential scanning calorimetry based on JIS K 7122 at the temperature range of -50°C to 200°C is ≤30 J/g. (b): The limiting viscosity is 0.1-10 dl/g. (c): The content of a monomer unit derived from a 3-20C α-olefin contained in the amorphous or the low crystalline olefinic polymer is 50-100 mole%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminate excellent in heat resistance and flexibility.

Laminated bodies made of thermoplastic resins are widely used for applications such as industrial and factory materials, containers and packaging, for example, as transparent or flexible sheets or films.
For example, Patent Document 1 includes an inner surface layer and an outer surface layer containing a crystalline polyolefin-based polymer, and an intermediate layer composed of a crystalline polyolefin-based polymer and an amorphous polyolefin-based polymer, A laminate having excellent transparency and flexibility is described.

JP 2004-167905 A

However, even in the laminate described in Patent Document 1, when the temperature of the environment in which the laminate is used exceeds the melting temperature of the crystalline polyolefin used in the laminate, the heat resistance is not necessarily sufficient, Further improvements were sought.
Under such circumstances, a problem to be solved by the present invention, that is, an object of the present invention is to provide a laminate having excellent heat resistance and flexibility.

That is, the present invention is a laminate having at least one surface layer (I), at least one intermediate layer (II) and at least one substrate layer (III), wherein the surface layer (I) A layer containing a plastic resin, and the intermediate layer (II) comprises 95 to 5% by weight of an amorphous or low crystalline olefin polymer satisfying the following requirements (a), (b) and (c): A resin composition comprising 5 to 95% by weight of a thermoplastic resin excluding a crystalline or low crystalline olefin polymer (however, the total of the amorphous or low crystalline olefin polymer and the thermoplastic resin is 100% by weight) The base material layer (III) is a layer made of paper or metal.
(A) In the differential scanning calorimetry according to JIS K 7122, the heat of crystal melting obtained by measuring in the range of −50 ° C. to 200 ° C. is 30 J / g or less.
(B) The intrinsic viscosity is 0.1 to 10 dl / g.
(C) The content of the monomer unit derived from the α-olefin having 3 to 20 carbon atoms contained in the amorphous or low-crystalline olefin polymer is 50 to 100 mol% (however, the amorphous Or the whole of the low crystalline olefin polymer is 100 mol%).

  According to the present invention, a laminate having excellent heat resistance and flexibility is provided.

  The surface layer (I) of the laminate of the present invention is a layer containing a thermoplastic resin. Examples of the thermoplastic resin include polyethylene resins such as high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. , Ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-acrylic acid ester-glycidyl methacrylate copolymer, polypropylene Resin, polybutene resin, poly (4-methyl-1-pentene) resin, polystyrene resin, polyester resin, polymethacrylic acid resin, polyamide resin, polyphenylene ether resin, polyacetal resin, polycarbonate resin , D Len - and cyclic olefin copolymer. Preferably, it is an olefin resin such as polyethylene resin, polypropylene resin, polybutene resin, poly (4-methyl-1-pentene) resin, more preferably a single monomer derived from an aliphatic olefin having 2 or more carbon atoms. It is an olefin resin having a monomer unit as a main unit, and more preferably an olefin resin having a monomer unit derived from an aliphatic olefin having 3 or more carbon atoms as a main unit. From the viewpoint of improving the heat resistance of the laminate of the present invention, a polypropylene resin is particularly preferable. A plurality of different types of thermoplastic resins may be used in combination.

  As a general method for producing a polypropylene resin, for example, a Ziegler-Natta type catalyst comprising a titanium-containing solid transition metal component and an organometallic component, or a periodic table having at least one cyclopentadienyl skeleton A slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, or a polymerization method combining these, using a metallocene catalyst comprising a transition metal compound of Group 4 to Group 6 and a promoter component as a polymerization catalyst And a method of producing a propylene homopolymer by polymerizing propylene by a single-stage polymerization method or a multi-stage polymerization method, or at least one olefin selected from the group consisting of propylene and an olefin having 2 to 12 carbon atoms (propylene And a method of producing a copolymer by copolymerization. Moreover, you may use a commercial item as a polypropylene resin.

  The crystallinity of the polyolefin-based resin is preferably 80 to 176 ° C. as the melting point, more preferably 120 to 176 ° C., and preferably 30 as the heat of crystal melting, from the viewpoint of enhancing the heat resistance of the laminate of the present invention. It is -120 J / g, More preferably, it is 60-120 J / g.

  The number average molecular weight of the polyolefin resin is preferably 10,000 to 1,000,000. The number average molecular weight is measured by gel permeation chromatograph (GPC).

The intermediate layer (II) of the laminate of the present invention comprises an amorphous or low crystalline olefin polymer that satisfies the following requirements (a), (b), and (c), and the amorphous or low crystalline olefin type. It is a layer containing a resin composition made of a thermoplastic resin excluding a polymer.
(A) In the differential scanning calorimetry according to JIS K 7122, the heat of crystal melting obtained by measuring in the range of −50 ° C. to 200 ° C. is 30 J / g or less.
(B) The intrinsic viscosity is 0.1 to 10 dl / g.
(C) The content of the monomer unit derived from the α-olefin having 3 to 20 carbon atoms contained in the amorphous or low-crystalline olefin polymer is 50 to 100 mol% (however, the amorphous Or the whole of the low crystalline olefin polymer is 100 mol%).

  As the thermoplastic resin, the thermoplastic resin exemplified in the surface layer (I) can be used. Preferred are polyolefin resins such as polyethylene resins, polypropylene resins, polybutene resins, poly (4-methyl-1-pentene) resins, and more preferably single resins derived from aliphatic olefins having 2 or more carbon atoms. A polyolefin resin having a monomer unit as a main unit, and more preferably a polyolefin resin having a monomer unit derived from an aliphatic olefin having 3 or more carbon atoms as a main unit. From the viewpoint of improving the heat resistance of the laminate of the present invention, a polypropylene resin is particularly preferable. A plurality of different types of thermoplastic resins may be used in combination.

  The amorphous or low-crystalline olefin polymer used for the intermediate layer (II) of the laminate of the present invention is preferably at least selected from the group consisting of ethylene, propylene and α-olefins having 4 to 20 carbon atoms. It is an amorphous or low crystalline olefin polymer obtained by copolymerizing two kinds of olefins. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Linear olefins such as dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3- Examples thereof include chain olefins such as branched olefins such as methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene.

  A specific combination of at least two olefins selected from the group consisting of α-olefins having 4 to 20 carbon atoms is preferable, from the viewpoint of obtaining heat resistance and flexibility of the laminate of the present invention. A combination in which the total number of atoms is 6 or more. Specific combinations of two or more of the olefins include, for example, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and 4-methyl-1-pentene, ethylene and propylene and 1- Butene, ethylene and propylene and 1-hexene, ethylene and 1-butene and 1-hexene, propylene and 1-butene, propylene and 1-hexene, propylene and 1-octene, propylene and 4-methyl-1-pentene, propylene Examples include 1-butene and 1-hexene, 1-butene and 1-hexene, 1-butene and 1-octene, 1-hexene and 1-octene, and the like.

  The amorphous or low-crystalline olefin polymer used for the intermediate layer (II) of the laminate of the present invention is ethylene, propylene, and α- of 4 to 20 carbon atoms within a range not impairing the object of the present invention. Copolymers obtained by further copolymerizing monomers other than olefins may be used. Examples of the monomers include cyclic olefins, vinyl aromatic compounds, and polyene compounds, preferably cyclic olefins. is there.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1, 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphth 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methylsic Examples include lohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, and vinylcyclohexane.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, Examples include vinyl naphthalene.

  Examples of the polyene compound include conjugated polyene compounds and non-conjugated polyene compounds. Examples of the conjugated polyene compound include aliphatic conjugated polyene compounds such as linear aliphatic conjugated polyene compounds and branched aliphatic conjugated polyene compounds, and alicyclic conjugated polyene compounds. Non-conjugated polyene compounds include Examples thereof include an aliphatic nonconjugated polyene compound, an alicyclic nonconjugated polyene compound, and an aromatic nonconjugated polyene compound. These may have an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, and the like.

  Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2- Hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3- Hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3- Examples include dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene.

  Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2,3- Dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene, and the like.

  Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9 -Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4 -Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4 -Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4- Octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5- Octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6- Octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1 4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1, 5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1, 7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1, 5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1, 6-decadiene, 7-methyl -1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl -1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl -1,8-undecadiene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,13-trimethyl-1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7 , 14-Hexadeca Lien, 4-ethylidene-12-methyl-1,11-penta decadiene, and the like.

  Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, and cyclohexadiene. , Dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene -3-Isopropylidene-5-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5- Divinylcyclooctane, 1-allyl-4- Nylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1- Examples thereof include isopropenyl-3-vinylcyclopentane and methyltetrahydroindene.

  Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

  From the viewpoint of enhancing the flexibility of the laminate of the present invention, the amorphous or low-crystalline olefin polymer used for the intermediate layer (II) of the laminate of the present invention, in the differential scanning calorimetry according to JIS K 7122, It is a polymer having a heat of crystal fusion of 30 J / g or less obtained by measurement in the range of −50 ° C. to 200 ° C. The crystal melting heat quantity is preferably 10 J / g or less, more preferably 5 J / g or less, and still more preferably a peak with a crystal melting heat quantity of 1 J / g or more and a crystallization heat quantity of 1 J / g or more. None of the peaks are observed.

  The content of the monomer unit derived from the α-olefin having 3 to 20 carbon atoms contained in the amorphous or low-crystalline olefin polymer is the viewpoint of heat resistance and flexibility of the laminate of the present invention. From 50 to 100 mol% (however, the whole amorphous or low-crystalline olefin polymer is 100 mol%).

When the amorphous or low crystalline olefin polymer contains a monomer unit derived from ethylene, it is preferable to satisfy the following relational expression from the viewpoint of heat resistance and flexibility of the laminate of the present invention.
[Y / (x + y)] ≧ 0.5
More preferably,
[Y / (x + y)] ≧ 0.6,
More preferably,
[Y / (x + y)] ≧ 0.8.
In the above relational expression, x is the content (mol%) of monomer units derived from ethylene contained in the amorphous or low crystalline olefin polymer, and y is amorphous or low crystalline. It is content (mol%) of the monomer unit derived from a C4-C20 alpha olefin contained in a functional olefin polymer.

  The molecular weight distribution (Mw / Mn) of the amorphous or low-crystalline olefin polymer is preferably 1 to 4, more preferably 1 to 3, from the viewpoint of reducing the stickiness of the laminate of the present invention. . The molecular weight distribution is measured by gel permeation chromatograph (GPC).

  The intrinsic viscosity of the amorphous or low-crystalline olefin polymer is 0.1 dl / g or more, preferably 0.3 dl / g or more, from the viewpoint of improving the workability at the time of molding of the laminate of the present invention. More preferably, it is 0.5 dl / g or more, More preferably, it is 0.7 dl / g or more. In addition, the intrinsic viscosity is 10 dl / g or less, preferably 7 dl / g or less, more preferably 5 dl / g or less, from the viewpoint of improving the workability at the time of forming the laminate of the present invention. More preferably, it is 4 dl / g or less. The intrinsic viscosity is measured using an Ubbelohde viscometer in 135 ° C. tetralin.

The amorphous or low crystalline olefin polymer can be produced using a known Ziegler-Natta type catalyst or a known single site catalyst (metallocene type, etc.), but the thermoplastic resin composition of the present invention From the viewpoint of enhancing the heat resistance, known single site catalysts (metallocene series and the like) are preferable. Examples of such single site catalysts include Japanese Patent Application Laid-Open Nos. 58-19309, 60-35005, and JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, JP-A-61-130314, JP-A-3-16388, JP-A-4-268307, Described in Kaihei 9-12790, JP-A-9-87313, JP-A-11-80233, JP 10-508055, etc. Metallocene catalysts, JP-A-10-316710, JP-A-11-1000039, JP-A-11-80228, JP-A-11-80227, JP-T-10-513289, JP-A-10-338706 And non-metallocene complex catalysts described in JP-A-11-71420 and the like. Among these, from the viewpoint of availability, it is preferably a metallocene catalyst, more preferably at least one cyclopentadiene-type anion skeleton, and a periodic table group 3 to group 12 having a C ₁ antipodal structure. The transition metal complex. Moreover, as a manufacturing method using a metallocene catalyst, the method of the European Patent Publication No. 12111287 is mentioned, for example.

The resin composition constituting the intermediate layer (II) of the present invention comprises 95 to 5% by weight of an amorphous or low crystalline olefin polymer that satisfies the following requirements (a), (b), and (c): It is a resin composition comprising 5 to 95% by weight of a thermoplastic resin excluding a crystalline or low crystalline olefin polymer.
(A) In the differential scanning calorimetry according to JIS K 7122, the heat of crystal melting obtained by measuring in the range of −50 ° C. to 200 ° C. is 30 J / g or less.
(B) The intrinsic viscosity is 0.1 to 10 dl / g.
(C) The content of the monomer unit derived from the α-olefin having 3 to 20 carbon atoms contained in the amorphous or low-crystalline olefin polymer is 50 to 100 mol% (however, the amorphous Or the whole of the low crystalline olefin polymer is 100 mol%).

  The content of the thermoplastic resin in the resin composition is 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight from the viewpoint of increasing the heat resistance and strength of the laminate of the present invention. That's it. Further, the content of the thermoplastic resin in the resin composition is 95% by weight or less, more preferably 90% by weight or less, and still more preferably 80% by weight from the viewpoint of enhancing the flexibility of the laminate of the present invention. % Or less.

  The content of the amorphous or low crystalline olefin polymer in the resin composition is 5% by weight or more, preferably 10% by weight or more from the viewpoint of enhancing the flexibility of the laminate of the present invention, More preferably, it is 20% by weight or more. In addition, the content of the amorphous or low crystalline olefin polymer in the resin composition is 95% by weight or less, preferably 90% by weight from the viewpoint of increasing the heat resistance and strength of the laminate of the present invention. Or less, more preferably 80% by weight or less.

  The resin composition may contain a known resin other than the non-crystalline or low-crystalline olefin polymer and thermoplastic resin exemplified above, for example, an elastomer, as long as the object of the present invention is not impaired. You may mix | blend.

  Examples of the elastomer include natural rubber, polybutadiene, liquid polybutadiene, styrene-butadiene random copolymer, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, and styrene. -Isoprene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene-styrene block copolymer, polyacrylonitrile rubber, acrylonitrile-butadiene copolymer, partially hydrogenated acrylonitrile-butadiene Copolymer, butyl rubber, chloroprene rubber, fluoro rubber, chlorosulfonated polyethylene, silicone rubber, urethane rubber, isobutylene-isoprene copolymer, halogenated isobutylene-i Puren copolymer.

  The resin composition is, for example, a rosin resin, a polyterpene resin, a synthetic petroleum resin, a coumarone resin, a phenol resin, a xylene resin, and a styrene resin as long as the object of the present invention is not impaired. Other resins such as isoprene-based resins can be blended.

  Examples of the rosin resin include natural rosin, polymerized rosin, partially hydrogenated rosin, fully hydrogenated rosin, esterified products of these rosins (for example, glycerin ester, pentaerythritol ester, ethylene glycol ester, methyl ester), rosin derivatives ( Examples thereof include disproportionated rosin, fumarized rosin, and lime rosin).

  Examples of polyterpene resins include homopolymers of cyclic terpenes such as α-pinene, β-pinene, and dipentene, copolymers of cyclic terpenes, and copolymers of cyclic terpenes and phenolic compounds such as phenol and bisphenol. (For example, terpene-phenol resins such as α-pinene-phenol resin, dipentene-phenol resin, terpene-bisphenol resin, etc.), aromatic modified terpene resins that are copolymers of cyclic terpenes and aromatic monomers.

The synthetic petroleum resins, for example, C ₅ fraction naphtha cracked oil, C ₆ -C ₁₁ fraction, other olefinic fractions homopolymer or a copolymer, the water of these homopolymers and copolymers Examples thereof include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, and aliphatic-alicyclic copolymer resins that are additives. Examples of the synthetic petroleum resin further include a copolymer of naphtha cracked oil and the above terpene, and a copolymer petroleum resin that is a hydrogenated product of the copolymer.

Preferably the C ₅ fraction of naphtha cracked oil, isoprene, cyclopentadiene, 1,3-pentadiene, 2-methyl-1-butene, methylbutene such as 2-methyl-2-butene, 1-pentene, 2-pentene And pentenes such as dicyclopentadiene. As the C _{6 to} C ₁₁ fraction, preferably, indene, styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, methylstyrenes such as α-methylstyrene, β-methylstyrene, methylindene, ethylindene Vinyl xylene and propenylbenzene. Other preferred olefinic fractions are butene, hexene, heptene, octene, butadiene, and octadiene.

  Examples of the phenolic resin include alkylphenol resins, alkylphenol-acetylene resins obtained by condensation of alkylphenol and acetylene, and modified products of these resins. Here, the phenolic resin may be any of a novolac resin obtained by methylolation of phenol with an acid catalyst and a resol resin obtained by methylolation of an alkali catalyst.

  Examples of the xylene-based resin include a xylene-formaldehyde resin composed of m-xylene and formaldehyde, and a modified resin obtained by adding and reacting a third component thereto.

  Examples of the styrene resin include a low molecular weight polymer of styrene, a copolymer of α-methylstyrene and vinyltoluene, a copolymer of styrene, acrylonitrile, and indene.

The isoprene-based resin, for example, resins obtained by copolymerizing a C ₁₀ alicyclic compound and C ₁₀ chain compound is a dimerization of isoprene.

  If necessary, the resin composition comprises an anti-aging agent, an antioxidant, an anti-ozone degradation agent, an ultraviolet absorber, a stabilizer such as a light stabilizer, an antistatic agent, a slip agent, an internal release agent, a colorant, You may mix | blend additives, such as a dispersing agent, an antiblocking agent, a lubricant agent, an antifogging agent, organic fillers, such as carbon fiber and an aramid fiber, and mineral oil type softeners, such as naphthene oil and paraffinic mineral oil.

  The resin composition may be blended with a flame retardant, if necessary, as long as the object of the present invention is not impaired. Examples of the flame retardant include inorganic compounds such as antimony flame retardant, zinc borate, guanidine flame retardant, zirconium flame retardant, ammonium polyphosphate, ethylenebistris (2-cyanoethyl) phosphonium chloride, tris (tribromo Phenyl) phosphates, tris (tribromophenyl) phosphates, phosphate esters and compounds such as tris (3-hydroxypropyl) phosphine oxide, chlorinated paraffins, chlorinated polyolefins, chlorinated flame retardants such as perchlorocyclopentadecane, hexa Odors such as bromobenzene, ethylenebisdibromonorbornanedicarboximide, ethylenebistetrabromophthalimide, tetrabromobisphenol A derivatives, tetrabromobisphenol S, tetrabromodipentaerythritol System flame retardant, and the like. These flame retardants may be used alone or in combination of two or more.

  The resin composition may be a foam obtained by blending a foaming agent as necessary. Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, ammonium bicarbonate and ammonium carbonate, nitroso compounds such as N, N′-dinitrosopentamethylenetetramine, azo compounds such as azocarbonamide and azoisobutyronitrile, Examples thereof include sulfonyl hydrazides such as benzenesulfonyl hydrazine, p, p′-oxybis (benzenesulfonyl hydrazide), toluenesulfonyl hydrazide, and toluenesulfonyl hydrazide derivatives. The foaming agent may be used in combination with a foaming aid such as salicylic acid, urea, urea derivatives and the like.

  The resin composition may contain a high-frequency processing aid such as a polar group-containing polymer, if necessary. Examples of the high-frequency processing aid include a copolymer of ethylene and at least one comonomer. Examples of the comonomer include monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid, monoesters of the above dicarboxylic acids, and methyl methacrylate. Examples thereof include acrylic acid esters such as methacrylic acid esters, methyl acrylate and ethyl acrylate, vinyl esters of saturated carboxylic acids such as vinyl acetate and vinyl propionate, and ionomers of these acids and esters.

  The resin composition may contain a tackifier as necessary. Examples of the tackifier include natural rosin resins such as rosin and dammar, modified rosin and derivatives thereof, terpene resins and modified products thereof, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, alkylphenol resins, coumarone- Examples thereof include resins such as indene resins. Among these, terpenes such as terpene phenol and α-polyterpene are preferable. As terpenes, “YS Resin TO-105” and “Clearon” (trade names manufactured by Yashara Chemical Co., Ltd.), “Arcon”, “Esthegam” and “Pencel” (trade names manufactured by Arakawa Chemical Industries, Ltd.) Is mentioned.

The resin composition may be a resin composition subjected to crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, silane crosslinking, resin crosslinking, electron beam crosslinking, or the like, if necessary, by a known method. Good. Examples of the crosslinking agent include sulfur, phenol resin, metal oxide, metal hydroxide, metal chloride, p-quinonedioxime, and bismaleimide-based crosslinking agent. The crosslinking agent can be used in combination with a crosslinking accelerator in order to adjust the crosslinking rate. Examples of the crosslinking accelerator include oxidizing agents such as red lead and dibenzothiazoyl sulfide. The crosslinking agent can be used in combination with a dispersing agent such as a metal oxide or stearic acid. Examples of the metal oxide include zinc oxide, magnesium oxide, lead oxide, calcium oxide and the like, preferably zinc oxide and magnesium oxide. The thermoplastic composition may be dynamically crosslinked in the presence of a crosslinking agent.
The resin composition may be a resin composition subjected to crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, silane crosslinking, resin crosslinking, electron beam crosslinking, or the like, if necessary, by a known method. Good. Examples of the crosslinking agent include sulfur, organic peroxides, phenol resins, metal oxides, metal hydroxides, metal chlorides, p-quinone dioxime, and bismaleimide-based crosslinking agents.

  Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-bis ( t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl -4,4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate , Diacetyl peroxide, lauroyl peroxide, t-butyl peroxide, etc. It is below.

  The method for producing the resin composition is not particularly limited. Examples of the production method include a method in which each component is kneaded by an ordinary kneading apparatus such as a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a single screw or a twin screw extruder. The kneading apparatus may be either a closed type or an open type, but is preferably a closed type apparatus that can be replaced with an inert gas. The kneading temperature is usually 120 to 250 ° C, preferably 140 to 240 ° C. The kneading time depends on the type and amount of the components used and the type of the kneading apparatus, but is usually about 3 to 10 minutes when a kneading apparatus such as a pressure kneader or a Banbury mixer is used. In the kneading step, a method of kneading each component in a lump may be adopted, or a multistage division kneading method in which a part of each component is kneaded and then the remainder is added to continue kneading may be adopted. Good.

  The surface layer (III) of the present invention is a layer made of paper or metal. Examples of the metal include aluminum and iron. From the viewpoint of increasing the flexibility of the laminate of the present invention, paper is preferred.

  The laminate of the present invention may have at least one surface layer (I), at least one intermediate layer (II), and at least one base material layer (III). It may be a three-layer structure of I) / intermediate layer (II) / base layer (III), or 4 such as surface layer (I) / intermediate layer (II) / layer (IV) / base layer (III) A layer structure may be used. Here, the layer (IV) represents a recycled layer or the like.

  The total thickness of the laminate of the present invention is usually from 30 to 2000 μm, preferably from 50 to 1000 μm, more preferably from 100 to 500 μm, from the viewpoint of further improving flexibility. The thickness of each layer is usually surface layer (I) / intermediate layer (II) / base material layer (III) = 5 to 500 μm / 5 to 500 μm / 20 to 1000 μm, and more flexible and heat resistant. From the viewpoint of enhancing, preferably, surface layer (I) / intermediate layer (II) / base material layer (III) = 10 to 100 μm / 10 to 400 μm / 30 to 500 μm, more preferably surface layer (I) / Intermediate layer (II) / base material layer (III) = 10-50 μm / 40-150 μm / 50-300 μm.

  As a method for producing the laminate of the present invention, a known extrusion laminating method is used. For example, the surface layer (I) and the intermediate layer (II) are formed into a multilayer coextruded film or sheet by extrusion molding such as T-die casting, and then the multilayer film or multilayer sheet is subjected to an extrusion coating method or The method of laminating | stacking with base-material layer (III) by the sandwich lamination method etc. can be mentioned.

  The laminated body of the present invention utilizes, for example, its excellent characteristics, for example, vehicle parts, electrical / electronic equipment parts, electric wires, building materials, agriculture / fishery / horticultural supplies, chemical industry supplies, civil engineering materials, industrial / industrial materials. , Furniture, stationery, clothes, containers / packaging supplies, toys, leisure goods, medical supplies, display materials, release / process paper, waterproof / moisture-proof paper, etc.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[Example 1]
[1] Measurement of physical properties The physical properties of the present invention were measured by the following methods.
(1) Monomer unit content of amorphous propylene-1-butene copolymer ¹ H-NMR spectrum, ¹³ C-NMR spectrum using a nuclear magnetic resonance apparatus (trade name AC-250 manufactured by Bruker). It calculated based on the measurement result. Specifically, in the ¹³ C-NMR spectrum, from the ratio of the spectral intensity of methyl carbon derived from the propylene monomer unit to the spectral intensity of methyl carbon derived from the 1-butene monomer unit, the propylene monomer unit and 1 -The composition ratio of the butene monomer unit was calculated, and then in the ¹ H-NMR spectrum, the ethylene unit amount was determined from the ratio between the spectral intensity of hydrogen derived from the methine unit and the methylene unit and the spectral intensity of hydrogen derived from the methyl unit. The composition ratio of the body unit, the propylene monomer unit and the 1-butene monomer unit was calculated.
(2) Intrinsic viscosity [η]
The measurement was performed at 135 ° C. using an Ubbelohde viscometer. Tetralin solution of amorphous propylene-1-butene copolymer in which the concentration c of amorphous propylene-1-butene copolymer per unit volume of tetralin is 0.6, 1.0, 1.5 mg / ml The intrinsic viscosity at 135 ° C. was measured. The measurement was repeated three times at each concentration, the average value of the three values obtained was taken as the specific viscosity (η _sp ) at that concentration, and the value obtained by extrapolating c of η _sp / c to zero was used as the intrinsic viscosity [η ]
(3) Molecular weight distribution It measured by the gel permeation chromatograph (GPC) method on the following conditions.
Equipment: 150C ALC / GPC manufactured by Waters
Column: Shodex Packed Column A-80M manufactured by Showa Denko KK Temperature: 140 ° C
Solvent: o-dichlorobenzene elution solvent flow rate: 1.0 ml / min Sample concentration: 1 mg / ml
Measurement injection volume: 400 μl
Molecular weight standard substance: Standard polystyrene detector: Differential refraction (4) Crystal melting peak and crystallization peak Measurement was performed under the following conditions using a differential scanning calorimeter (DSC220C: input compensation DSC manufactured by Seiko Denshi Kogyo Co., Ltd.).
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after completion of the temperature increase.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed. The peak observed in (ii) was a crystallization peak, and the presence or absence of a crystallization peak having a peak area of 1 J / g or more was confirmed.
(Iii) Next, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. The peak observed in (iii) was a crystal melting peak, and the presence or absence of a melting peak with a peak area of 1 J / g or more was confirmed.
(5) Melt flow rate (MFR)
According to JIS K 7210, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 230 ° C.
(6) The flexibility of the flexible laminate was evaluated under the following conditions.
(I) The laminate was cut into a rectangular shape of 9 cm in the parallel direction of extrusion and 1 cm in the vertical direction of extrusion.
(Ii) Extrusion A cylindrical sample having a height of 1 cm and a circumference of 8 cm was prepared with 1 cm from one end in the vertical direction being glued.
(Iii) Using a Tensilon universal testing machine (manufactured by A & D), compress the cylindrical sample in the direction of compression from the side at a speed of 20 mm / min in an atmosphere of 23 ° C. and 50% humidity, When the minor axis of the ellipse on the bottom surface of the compressed cylindrical sample reaches 50% of the diameter of the bottom surface of the cylindrical sample before compression, that is, the stress at the time of 50% compression is measured, and this is compressed by 50%. Stress was used. The smaller the 50% compressive stress, the more flexible the laminate.
(7) Heat resistance Measured under the following conditions using a heat / application / strain measuring device (TMA manufactured by Seiko Denshi Kogyo Co., Ltd.).
(I) Using a probe having a 1 mmφ cylindrical tip, a load of 412 mN was applied to the surface layer (I) of the laminate.
(Ii) Next, the penetration depth in the process of raising the temperature of the sample from room temperature to 190 ° C. at a rate of temperature rise of 5 ° C./min was measured, and this was designated as 170 ° C. penetration depth. The smaller the 170 ° C. penetration depth, the more heat-resistant the laminate.
(8) The surface tackiness of the surface layer (I) of the surface tacky laminate was evaluated according to the following criteria.
○: Adhesiveness is not recognized even if the sheet surface is touched by hand.
X: Adhesiveness is recognized on the sheet surface.

[2] Material (1) Crystalline polypropylene resin PP-1 Homopolypropylene Sumitomo Nobrene Z101S (manufactured by Sumitomo Chemical Co., Ltd., MFR = 25 g / 10 min, hereinafter referred to as PP-1)
PP-2 homopolypropylene Sumitomo Nobrene FS2011DG3 (manufactured by Sumitomo Chemical Co., Ltd., MFR = 2.5 g / 10 min, hereinafter referred to as PP-2)
PP-3 homopolypropylene Sumitomo Nobrene H501 (manufactured by Sumitomo Chemical Co., Ltd., MFR = 3 g / 10 min, hereinafter referred to as PP-3)

(2) Amorphous propylene-1-butene copolymer In a 100-L SUS polymerizer equipped with a stirrer, hydrogen was used as a molecular weight regulator, and propylene and 1-butene were continuously copolymerized by the following method. Thus, an amorphous propylene-1-butene copolymer corresponding to the amorphous or low crystalline olefin polymer of the present invention was obtained.
From the lower part of the polymerization vessel, hexane as a polymerization solvent was continuously supplied at a supply rate of 100 L / hour, propylene was supplied at a supply rate of 24.00 kg / hour, and 1-butene was supplied at a supply rate of 1.81 kg / hour. Supplied to.
From the top of the polymerization vessel, the reaction mixture was continuously withdrawn so that the reaction mixture in the polymerization vessel maintained an amount of 100 L.
From the lower part of the polymerization vessel, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a component of the polymerization catalyst was fed at a feed rate of 0.005 g / hour. Triphenylmethyltetrakis (pentafluorophenyl) borate was continuously fed at a feed rate of 0.298 g / hr and triisobutylaluminum was fed at a feed rate of 2.315 g / hr.
The copolymerization reaction was carried out at 45 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel.
By adding ethanol to the reaction mixture continuously withdrawn from the top of the polymerization vessel to stop the polymerization reaction, followed by demonomer and water washing, and then removing the solvent with steam in a large amount of water, Amorphous propylene-1-butene copolymer was obtained and dried under reduced pressure at 80 ° C. for 1 day. The production rate of the copolymer was 7.10 kg / hour.
Table 1 shows the physical property evaluation results of the obtained amorphous propylene-1-butene copolymer (hereinafter referred to as PB).

(3) Paper A 180 μm-thick kraft paper (manufactured by Nippon Paper Industries Co., Ltd., basis weight 129.5 kg / m ² ) was used.

(4) Preparation of Resin Composition-1 Amorphous propylene-1-butene copolymer PB 85 parts by weight, PP-2 15 parts by weight, hindered phenol antioxidant (Irganox manufactured by Ciba Specialty Chemicals) 1010) 0.12 part by weight, 0.12 part by weight of an aromatic phosphite antioxidant (Irgaphos 168 manufactured by Ciba Specialty Chemicals) and 1,3-bis (t-butylperoxyisopropyl) benzene By kneading using an axial kneader, pellets of an amorphous propylene-1-butene copolymer composition were obtained. The MFR of the copolymer composition was 10 g / 10 minutes. Furthermore, 41 parts by weight of PP-1 and 59 parts by weight of pellets of an amorphous propylene-1-butene copolymer composition were pellet-blended to obtain a resin composition-1.
(4) Preparation of Resin Composition-2 PP-1 50 parts by weight and ethylene-1-butene copolymer (1-butene monomer unit content 22% by weight, MFR = 12 g / 10 min, according to JIS K 7122 In differential scanning calorimetry, the amount of heat of crystal fusion obtained by measurement in the range of −50 ° C. to 200 ° C. is 51 J / g) (hereinafter referred to as EB). Got.
[3] Preparation of Laminate Using a 30mmφ coextrusion laminator, PP-1 and resin composition-1 are coextruded under the conditions of a processing speed of 6m / min and an extrusion temperature of 280 ° C. Extrusion lamination was performed on paper to obtain a laminate having a thickness of PP-1 / resin composition-1 / both kraft paper = 50 μm / 100 μm / 180 μm. Table 2 shows the evaluation results of the obtained laminate.

[Comparative Example 1]
In Example 1, the same procedure as in Example 1 was performed except that the thickness of the surface layer (I) of the laminate was changed from 50 μm to 150 μm and the intermediate layer (II) was not used.

[Comparative Example 2]
In Example 1, it carried out similarly to Example 1 except having changed the intermediate | middle layer (II) of the laminated body from the resin composition-1 to the resin composition-2.

[Comparative Example 3]
In Example 1, the surface layer (I) of the laminate was changed from PP-1 to a resin composition-1 having a thickness of 150 μm, and the intermediate layer (II) was not used. I did it.

[Comparative Example 4]
In Example 1, it carried out similarly to Example 1 except having changed the base material layer (III) of the laminated body from PP paper to PP-1.

Claims (4)

A laminate having at least one surface layer (I), at least one intermediate layer (II) and at least one base layer (III), wherein the surface layer (I) contains a thermoplastic resin. And an intermediate layer (II) is 95 to 5% by weight of an amorphous or low crystalline olefin polymer satisfying the following requirements (a), (b) and (c) and the amorphous or low crystalline A resin composition comprising 5 to 95% by weight of a thermoplastic resin excluding the crystalline olefin polymer (however, the total of the amorphous or low crystalline olefin polymer and the thermoplastic resin is 100% by weight). A laminate in which the base layer (III) is a layer made of paper or metal.
(A) In the differential scanning calorimetry according to JIS K 7122, the heat of crystal melting obtained by measuring in the range of −50 ° C. to 200 ° C. is 30 J / g or less.
(B) The intrinsic viscosity is 0.1 to 10 dl / g.
(C) The content of the monomer unit derived from the α-olefin having 3 to 20 carbon atoms contained in the amorphous or low-crystalline olefin polymer is 50 to 100 mol% (however, the amorphous Or the whole of the low crystalline olefin polymer is 100 mol%). The amorphous or low crystalline olefin polymer contained in the resin composition of the intermediate layer (II) has a total number of carbon atoms of olefins contained in the olefin polymer of 6 or more, and The laminate according to claim 1, wherein the laminate satisfies the relational expression.
[Y / (x + y)] ≧ 0.5
(In the above relational expression, x represents the content (mol%) of monomer units derived from ethylene contained in the amorphous or low crystalline olefin polymer, and y is amorphous or low crystalline. Represents the content (mol%) of monomer units derived from an α-olefin having 4 to 20 carbon atoms contained in the olefin polymer, provided that the entire amorphous or low crystalline olefin polymer. Is 100 mol%.)   An amorphous or low crystalline olefin polymer contained in the resin composition of the intermediate layer (II) is obtained by measuring in the range of −50 ° C. to 200 ° C. in the differential scanning calorimetry according to JIS K 7122. The laminate according to claim 1, which is a polymer in which neither a peak with a heat of crystal melting of 1 J / g or more nor a peak with a heat of crystallization of 1 J / g or more is observed. The laminate according to claim 1, wherein the substrate layer (III) is a layer made of paper having a thickness of 20 to 1000 µm.