JP2010194983A - Laminated structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated structure which is laminated through a hot melt adhesive for strongly bonding base materials of various types and a base material such as olefin resin. <P>SOLUTION: Provided is the laminated structure, wherein a part of the laminated structure has at least such a structure that a layer (A), a layer (B) and a layer (C) are laminated in this order, wherein (A) is a layer consisting essentially of polyolefin, (B) is a layer containing hybrid polymer [P] having a polyolefin segment [S<SB>1</SB>] and a polar polymer segment [S<SB>2</SB>], and (C) is a layer composed of at least one selected from polar vinyl plastic, aromatic vinyl polymer, polyester, and the like. The [S<SB>2</SB>] is obtained through radial (co) polymerization of one or more kinds of monomers that contain radical polymerizable monomer having a reactive group. The number average molecular weight of [S<SB>2</SB>] section is 300 to <3,000, and also the number average molecular weight of [S<SB>1</SB>] section is 7,000 to <40,000. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminated structure in which a plurality of organic polymer layers or inorganic material layers are laminated. Specifically, it consists of at least one selected from polar vinyl plastics, aromatic vinyl polymers, polyesters, polyamides, polycarbonates, engineering plastics, biological polymers, thermoplastic elastomers, natural or artificial fibers, inorganic glass and metals. The present invention relates to a laminated structure having at least a part of a laminated structure in which a layer and a layer containing a specific hybrid polymer are bonded.

  Polyester film is excellent in mechanical properties and chemical resistance. Utilizing these properties, it is used for various purposes alone or in the form of laminates with polyethylene, polypropylene, and other olefin resin films. Yes. Polycarbonate film is excellent in transparency and impact resistance, and polymethylmethacrylate film is excellent in transparency, weather resistance, printability, etc., making use of these properties and laminating with various plastic films. Yes. Saponified ethylene / vinyl acetate copolymer films, polyvinylidene chloride films, and polyamide films have excellent gas barrier properties. By taking advantage of their high gas barrier properties, heat sealability and other properties such as polyethylene and polypropylene can be achieved. Laminated with excellent plastic film, etc., it is widely used in packaging materials and other fields. Polyvinyl chloride films are excellent in transparency, chemical resistance, printability, mechanical properties, and the like, and therefore, useful films in many industries are provided by laminating with general-purpose plastic films.

  Conventionally, styrene-conjugated diene-styrene-based adhesives for laminating substrates such as polycarbonate resins, acrylic resins, polyester resins, and other polar group-containing resins, or metals such as aluminum on substrates such as olefin resins A modified block copolymer obtained by graft polymerization of maleic anhydride to a hydrogenated block copolymer or an adhesive comprising the polymer and a solvent is known (Patent Documents 1 and 2). A method of using a mixture of thermoplastic polyurethane and an aromatic vinyl compound / conjugated diene polymer block hydrogenated product as an adhesive is also disclosed (Patent Document 3). However, since the adhesive strength of these adhesives is not sufficient, there is a demand for an adhesive that can more strongly bond a base material of a polar group-containing resin and a base material such as an olefin resin.

  In general, the production of laminated films as described above is roughly divided into a method of bonding and laminating between plastic films using a solvent-type adhesive and a method of laminating using a hot-melt adhesive. Is done. When laminating polyester film, polycarbonate film, acrylic polymer film, ethylene-vinyl acetate copolymer saponified film, polyvinylidene chloride film, polyvinyl chloride film, etc. with other polymer films, solvent-based adhesive However, there has been a problem in terms of natural environmental pollution due to the use of organic solvents, work environment deterioration and safety, and a lamination technique that does not use a solvent-type adhesive has been demanded. Further, among the polar group-containing resin base materials, polycarbonate films, acrylic polymer films, and the like have poor solvent resistance, and therefore selectable solvents are limited.

Japanese Examined Patent Publication No. 4-45532 Japanese Patent Publication No. 63-65116 Japanese Patent Laid-Open No. 10-202799

  In view of the above prior art, the present invention is a hot-melt adhesive that can be easily handled without using a solvent, and can strongly bond various types of polar group-containing resin substrates and substrates such as olefinic resins. It is an object of the present invention to provide a laminated structure laminated via an agent.

  As a result of intensive studies to solve the above problems, the present inventors have found that a layer containing an olefin polymer as a main component and a layer made of various materials each include a specific hybrid polymer. It has been found that strong adhesion is achieved by adopting a laminated structure through an adhesive layer, and the present invention has been achieved.

That is, the present invention
(A) a layer containing an olefin polymer as a main constituent,
(B) a layer comprising a hybrid polymer [P] having a polyolefin segment [S ₁ ] and a polar polymer segment [S ₂ ],
(C) At least one selected from polar vinyl plastic, aromatic vinyl polymer, polyester, polyamide, polycarbonate, engineering plastic, biological polymer, thermoplastic elastomer, natural or artificial fiber, inorganic glass and metal Layer
Having at least part of a structure in which layers (A) / layers (B) / layers (C) are laminated in this order,
The polar polymer segment [S ₂ ] is obtained by radical (co) polymerizing one or more monomers including a radical polymerizable monomer having a reactive group,
The number average molecular weight of the polar polymer segment [S ₂ ] part calculated from ¹ H-NMR measurement of the hybrid polymer [P] is 300 or more and less than 3,000, and
The polyolefin segment [S ₁ ] has a polypropylene-converted number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of from 7,000 to less than 40,000 (hereinafter referred to as a laminated structure [ I]).

In a preferred embodiment of the laminated structure in the present invention, the hybrid polymer [P] is a laminated structure (hereinafter, referred to as a structure in which a polyolefin segment [S ₁ ] and a polar polymer segment [S ₂ ] are linked by a covalent bond). It may be referred to as a laminated structure [II]).

In the laminated structures [I] and [II] of the present invention, the reactive group of the polar polymer segment [S ₂ ] is an isocyanate group, a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, an oxazoline group, It is preferably at least one group selected from the group consisting of a maleimide group and an amino group.

The polar polymer segment [S ₂ ] preferably has a solubility parameter of 18.0 to 25.0 ((J / cm ³ ) ^1/2 ), and was measured with a differential scanning calorimeter (DSC). The glass transition temperature (Tg) is preferably 25 ° C. or lower. In the laminated structures [I] and [II] of the present invention, the polyolefin segment [S ₁ ] has an endothermic peak position temperature of 50 caused by the melting point (Tm) measured by a differential scanning calorimeter (DSC). It is preferably a crystalline polyolefin residue having a temperature equal to or higher than ° C., and particularly preferably a propylene-based polymer residue.

  According to the present invention, from at least one selected from polar vinyl plastics, aromatic vinyl polymers, polyesters, polyamides, polycarbonates, engineering plastics, biological polymers, thermoplastic elastomers, natural or artificial fibers, inorganic glasses and metals. A laminated structure excellent in adhesive force between the layer and the layer containing an olefin polymer as a main constituent is provided.

  In particular, in the present invention, since a layer containing a hybrid polymer having a specific molecular weight range and a reactive group is used as an adhesive layer, it can be bonded more strongly than the conventional one, so that it can be suitably used for a wide range of applications. A laminated structure can be provided.

Hereinafter, the laminated structure of the present invention will be specifically described.
The present invention comprises (A) a layer containing an olefin polymer as a main component,
(B) a layer comprising a hybrid polymer [P] having a polyolefin segment [S ₁ ] and a polar polymer segment [S ₂ ],
(C) At least one selected from polar vinyl plastic, aromatic vinyl polymer, polyester, polyamide, polycarbonate, engineering plastic, biological polymer, thermoplastic elastomer, natural or artificial fiber, inorganic glass and metal Layer
Having at least part of a structure in which layers (A) / layers (B) / layers (C) are laminated in this order,
The polar polymer segment [S ₂ ] is obtained by radical (co) polymerizing one or more monomers including a radical polymerizable monomer having a reactive group,
The number average molecular weight of the polar polymer segment [S ₂ ] part calculated from ¹ H-NMR measurement of the hybrid polymer [P] is 300 or more and less than 3,000, and
The polyolefin segment _{[S 1],} polypropylene reduced number average molecular weight measured by gel permeation chromatography (GPC) (Mn) is less than 7,000 to 40,000, a laminated structure [I].

  Hereinafter, the components constituting the layer (A), the layer (B) and the layer (C) will be described in detail in this order, and then the layer (A) / layer (B) / layer (C) are stacked in this order. The laminated structure [I] having at least a part thereof will be described.

<Layer (A)>
The layer (A) is a layer containing an olefin polymer as a main constituent component. In the present invention, “main” means that the weight ratio of the whole is 70% by weight or more. The content of the olefin polymer in the layer (A) is 70% by weight or more, preferably 80% by weight or more, more preferably 90% or more.

  In the present invention, the olefin polymer is a polymer obtained by (co) polymerization using at least one olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms. The α-olefin having 3 to 20 carbon atoms may be linear or branched. For example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, Examples include 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. .

  Specific examples of olefin polymers include homopolyolefins such as polyethylene, polypropylene, poly (4-methyl-1-pentene), and poly (1-hexene), block polypropylenes such as ethylene / propylene block copolymers, ethylene Examples thereof include olefin copolymers such as propylene copolymers, ethylene / butene copolymers, ethylene / propylene / butene copolymers, and compositions composed of two or more of these. In addition, when an olefin polymer has stereoregularity, any of a syndiotactic polyolefin and an isotactic polyolefin may be sufficient.

  In addition, the layer (A) contains, as necessary, known additives usually added to the olefin resin, for example, inorganic fillers such as talc, silica, mica, clay, glass fiber, dyes and pigments, antioxidants. , Processing stabilizers, weathering agents, heat stabilizers, light stabilizers, nucleating agents, lubricants, mold release agents, flame retardants, antistatic agents, colorants, ultraviolet absorbers, and the like.

  Furthermore, the layer (A) can contain a resin component other than the olefin-based resin as necessary.

<Layer (B)>
The layer (B) is a polymer layer that functions as an adhesive layer for bonding the layer (A) and the layer (C). The layer (B) is a hybrid having a polyolefin segment [S ₁ ] and a polar polymer segment [S ₂ ] obtained by radical (co) polymerizing one or more monomers including a radical polymerizable monomer having a reactive group. It is a layer comprising polymer [P].

Hybrid polymer [P] is a hybrid polymer having a polar polymer segment _{[S 2]} and the polyolefin segment _{[S 1],} the binding mode of _{[S 1]} and _{[S 2],} the hybrid polymer _[P 1] And hybrid polymer [P ₂ ]. The hybrid polymer [P ₁ ] is a hybrid polymer having a skeleton represented by the following image formula (i) and having a structure in which a carbon atom in [S ₁ ] and a carbon atom in [S ₂ ] are directly covalently bonded. is there. The hybrid polymer [P ₂ ] has a structure (image formula (ii)) in which the carbon atom in [S ₁ ] and the carbon atom in [S ₂ ] are covalently bonded by a hetero atom or a bonding group containing a hetero atom. . The two structures are shown schematically below. Hereinafter, the characteristics of the hybrid polymer [P ₁ ] and the hybrid polymer [P ₂ ] will be described mainly from the viewpoint of the constituent elements and the production method.

(In formula (ii), Q represents a linking group containing a hetero atom.)

Hybrid polymer [P ₁ ]
◆ Polyolefin segment [S ₁ ]
In the hybrid polymer [P ₁ ], the polyolefin segment [S ₁ ] has a chemical structural formula in which the halogen radical is removed from the halogen-modified polyolefin [S ₁ ′] obtained by halogenating the polyolefin on the chemical structural formula. A segment is preferred. The halogen-modified polyolefin [S ₁ ′] is usually obtained by halogenating a polyolefin [S ₁ ″] having a molecular weight distribution (Mw / Mn) of 1.5 or more.

The polyolefin [S ₁ ″] is a polyolefin composed of repeating units derived from an olefin having 2 to 20 carbon atoms, specifically, an olefin homopolymer selected from olefins having 2 to 20 carbon atoms. Or it is a random copolymer. When this polyolefin has stereoregularity, it may be either isotactic polyolefin or syndiotactic polyolefin. Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, and aromatic vinyl compounds.

  Specific examples of the linear α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Examples thereof include those having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as 1-octadecene and 1-eicosene.

  Specific examples of the branched α-olefin include 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, and 4,4-dimethyl. 4-20, preferably 5 carbon atoms such as -1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene Can be exemplified.

  Examples of the cyclic olefin include those having 3 to 20, preferably 3 to 10, carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.

The GPC molecular weight profile of the polyolefin [S ₁ ″] is substantially the same as the GPC molecular weight profile of the polyolefin segment [S ₁ ], and the number average molecular weight (Mn) in terms of polypropylene is usually from 7,000 to 40,000. Less than, More preferably, it is 8,000 or more and less than 30,000, More preferably, it exists in the range of 10,000 or more and less than 25,000. The polyolefin _{[S 1} ''] and polyolefin segments _{[S 1],} the molecular weight determined by GPC distribution (Mw / Mn) of 1 to 10, preferably 1.5 to 8, more preferably from 1.6 to 7, More preferably, it is 1.7-6, Most preferably, it is 1.8-5.

The polyolefin segment [S ₁ ] is preferably a homopolymer or copolymer containing at least one α-olefin having 3 or more carbon atoms, or a copolymer of ethylene and a cyclic olefin. Furthermore, it is more preferable that stereoregularity due to the α-olefin component having 3 or more carbon atoms is observed, and it is particularly preferable that isotacticity having high stereoregularity is exhibited. Among these segments, the polyolefin segment [S ₁ ] has an endothermic peak position temperature of 50 ° C. or higher, preferably 60 to 200 ° C., more preferably 70 to 180 ° C., due to the melting point (Tm) measured by DSC. Particularly preferred is a crystalline polyolefin residue having a temperature of 100 to 180 ° C.

  The crystalline polyolefin having such properties is polyethylene or a polyolefin exhibiting high stereoregularity. Among polyethylene, those having a copolymerization amount of an α-olefin component having 3 or more carbon atoms are preferably 0 to 10 mol%, more preferably 0 to 7 mol%. Among the highly crystalline and highly stereoregular polyolefins, a propylene polymer is preferable, and a high stereoregular propylene polymer having an α-olefin copolymerization amount of 0 to 10 mol% is particularly preferable, and an α-olefin copolymer is preferable. A highly stereoregular propylene polymer having a polymerization amount of 0 to 7 mol% is preferred, and a highly stereoregular propylene homopolymer is more preferred.

Production of polyolefin [S ₁ ″], which is a precursor of polyolefin segment [S ₁ ], is carried out in the presence of a conventionally known olefin polymerization catalyst. Conventionally known olefin polymerization catalysts include TiCl ₃ -based catalysts, MgCl ₂ -supported TiCl ₄ -based catalysts, chromium-based catalysts, metallocene-based catalysts, post-metallocene-based catalysts, etc., and MgCl ₂ -supported TiCl ₄ -based catalysts or metallocenes. It is preferable that the catalyst is produced using a system catalyst.

The halogen-modified polyolefin [S ₁ ′] can be produced by a halogenation method using the above-mentioned polyolefin [S ₁ ″] using a known halogenating agent. Examples of halogenating agents include chlorine, bromine, iodine, phosphorus trichloride, phosphorus tribromide, phosphorus triiodide, phosphorus pentachloride, phosphorus pentabromide, phosphorus pentaiodide, thionyl chloride, sulfuryl chloride, thionyl bromide, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N-bromoglutarimide, N, N'- Dibromoisocyanuric acid, N-bromoacetamide, N-bromocarbamic acid ester, dioxane dibromide, phenyltrimethylammonium tribromide, pyridinium hydrobromide perbromide, pyrrolidone hydrotribromide, tert-butyl hypochlorite, tert hypobromite -Butyl, copper (II) chloride, copper bromide (II), iron (III) chloride, oxalyl chloride, IBr and the like can be mentioned. Of these, chlorine, bromine, N-chlorosuccinimide, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N-chloroglutarimide, N -Bromoglutarimide, N, N'-dibromoisocyanuric acid, more preferably bromine, N-bromosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5,5-dimethylhydantoin, N -A compound having an N-Br bond such as bromoglutarimide and N, N'-dibromoisocyanuric acid. In the reaction with the halogenating agent, benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, cumene hydro hydride as necessary to accelerate the reaction. Add an initiator typified by peroxide, tert-butyl hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobisisobutyric acid dimethyl radical, etc. You can also.

The halogen content of the halogen-modified polyolefin [S ₁ ′] thus obtained is usually 0.01 to 70% by weight, preferably 0.02 to 50% by weight, more preferably 0.05 to 30% by weight. It is. The halogen atom content present in the halogen-modified polyolefin [S ₁ ′] of the present invention can be measured by a method such as elemental analysis or ion chromatography. The carbon-carbon double bond content present in the halogen-modified polyolefin [S ₁ ′] can be measured by a method such as infrared spectroscopy or nuclear magnetic resonance (NMR). Furthermore, the halogen atom present at the allylic position of the carbon-carbon double bond can be confirmed and quantified by, for example, NMR. As a specific example of confirmation of the halogen atom existing at the allylic position, for example, in proton NMR using deuterated orthodichlorobenzene of brominated polypropylene as a solvent, a signal based on a carbon-carbon double bond is usually δ4.5-6. The allylic methylene group and methine group to which a bromine atom is bonded are usually observed at δ 3.5 to 4.5 ppm. Since the signal position when a bromine atom is introduced into a methylene group and a methine group other than the allylic position is usually δ 3.0 to 3.5 ppm, it is easy to determine whether the bromine atom is present at the allylic position or not. Be identifiable. In addition, for example, by using proton-proton two-dimensional NMR (HH-COSY), the correlation between the signal based on the carbon-carbon double bond and the signals of the methylene group and methine group to which a bromine atom is bonded has been confirmed. It is also possible to do.

In the halogen-modified polyolefin [S ₁ ′] thus obtained, at least one structural unit selected from structural units represented by the following general formulas (I) to (III) is connected to the terminal of the polymer main chain. And / or a structure in which at least one structural unit selected from structural units represented by the following general formulas (IV) to (VII) is inserted in the polymer main chain.

In the general formulas (I) to (VII), X represents a halogen atom, and R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , R ^3c , R ^4a , R ^5a , R ^5b , R ^6a , R ^6b , R ^7a and R ^7b represent a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with one or more halogen atoms, an oxygen-containing group or a nitrogen-containing group, and may be the same or different from each other; Also good.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.

  Specifically, the hydrocarbon group has 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, preferably 1-20 linear or branched alkyl groups, vinyl, allyl, isopropenyl, etc., 2-30, preferably 2-20 linear or branched alkenyl groups such as ethynyl, propargyl, etc. A straight or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc. 6-20 aryl groups, tolyl, iso-propylphenyl, tert-butylphenyl, dimethylphenyl Alkenyl, such as alkyl-substituted aryl group such as di -tert- butylphenyl and the like. In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, chlorophenyl and the like. Can be mentioned. Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as benzyl and cumyl, etc. are mentioned.

  Furthermore, the hydrocarbon group includes a heterocyclic compound residue, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic acid anhydride group, and the like. Oxygen-containing groups, amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, amino groups are ammonium salts It may be substituted with a nitrogen-containing group or the like.

  Of these, the hydrocarbon group is particularly preferably 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. Is a linear or branched alkyl group having 1 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, and the like, preferably 6 to 20 aryl groups, and these aryl groups. 1 to 5 substituents such as halogen atom, alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl group or aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms are substituted. And substituted aryl groups are preferred.

  The oxygen-containing group is a group containing 1 to 5 oxygen atoms in the group. Specifically, for example, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxyl group Peroxy group, carboxylic acid anhydride group and the like, and alkoxy group, aryloxy group, acetoxy group, carbonyl group, hydroxyl group and the like are preferable. When the oxygen-containing group contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 30, preferably 1 to 20. Among these oxygen-containing groups, the alkoxy group includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and the like, and the aryloxy group includes phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like are acyl groups such as formyl, acetyl, benzoyl, p-chlorobenzoyl and p-methoxybenzoyl, and ester groups are acetyloxy, benzoyloxy, methoxycarbonyl and phenoxycarbonyl. , P-chlorophenoxycarbonyl and the like are preferably exemplified.

  The nitrogen-containing group is a group containing 1 to 5 nitrogen atoms in the group. Specifically, for example, an amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group , A cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, an amino group converted to an ammonium salt, and the like. An amino group, an imino group, an amide group, an imide group, a nitro group, and a cyano group preferable. In addition, when a nitrogen-containing group contains a carbon atom, it is desirable that the number of carbon atoms is in the range of 1 to 30, preferably 1 to 20. Among these nitrogen-containing groups, as amide groups, acetamido, N-methylacetamide, N-methylbenzamide, etc., and as amino groups, methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, etc. An alkylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, and the like, an imide group such as acetimide and benzimide, and an imino group such as methylimino. , Ethylimino, propylimino, butylimino, phenylimino and the like are preferred.

In the halogen-modified polyolefin [S ₁ ′], a carbon-halogen bond existing at the α-position of the carbon-carbon double bond, or a structure in which a plurality of halogens are added on one carbon atom is used as an initiator structure. The polar polymer segment [S ₂ ] can be introduced by radical (co) polymerizing one or more monomers including a radically polymerizable monomer having a reactive group. From the viewpoint of fluidity and adhesive performance, the average number of halogen atoms introduced in the halogen-modified polyolefin [S ₁ ′] is preferably 0.3 to 10, more preferably 0.5 to 8, and further preferably 0.7 to 5. preferable.

The average number N of halogen atoms introduced per polymer chain of the halogen-modified polyolefin [S ₁ '] was determined as follows. The number average molecular weight of [S ₁ ′] determined from GPC is Mn, the average molecular weight of the monomer constituting [S ₁ ′] determined from ¹ H-NMR is Fw (ave), and the halogen in [S ₁ ′] When the molar content of the group with respect to all monomer chain units is n (mol%), the average number N of halogen atoms introduced per polymer chain of the halogen-modified polyolefin [S ₁ '] (lines / chain) is It is calculated by.

    N = n × Mn / [Fw (ave) × 100]

◆ Polar polymer segment [S ₂ ]
The polar polymer segment [S ₂ ] constituting the hybrid polymer is a polymer or copolymer obtained by radical polymerization of one or more monomers including a radical polymerizable monomer having a reactive group.

In the present invention, the “reactive group” means that at least a part of functional groups and at least a part of the constituent material of the layer (A) and / or the layer (C) are produced under the production conditions of the laminated structure of the present invention described later. Says a reactive group. In the present invention, such a reactive group is preferably an isocyanate group, a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, an oxazoline group, a maleimide group or an amino group. When the polar polymer segment [S ₂ ] in the hybrid polymer [P ₁ ] contains the reactive group, the adhesive force with the layer (A) and / or the layer (C) increases.

In addition, the polar polymer segment [S ₂ ] in the hybrid polymer [P ₁ ] has a glass transition temperature (Tg) of 25 ° C. or less as measured by a differential scanning calorimeter (DSC) in terms of adhesive strength. Preferably, it is -60-25 degreeC, More preferably, it is -50-20 degreeC.

  The following are mentioned as a radically polymerizable monomer which has the said reactive group.

  Examples of the radical polymerization monomer containing an isocyanate group include (meth) acryloyl isocyanate, crotoyl isocyanate, crotonic acid isocyanate ethyl ester, crotonic acid isocyanate butyl ester, crotonic acid isocyanate ethyl ethylene glycol, crotonic acid isocyanate ethyl diethylene glycol, and crotonic acid isocyanate ethyl. Triethylene glycol, (meth) acrylic acid isocyanate ethyl ester, (meth) acrylic acid isocyanate butyl ester, (meth) acrylic acid isocyanate hexyl ester, (meth) acrylic acid isocyanate octyl ester, (meth) acrylic acid isocyanate lauryl ester, ( (Meth) acrylic acid isocyanate hexadecyl ester, (meth) acrylic Le acid isocyanate ethylene glycol, (meth) acrylic acid-isocyanate ethyl glycol, and (meth) acrylic acid-isocyanate ethyl triethylene glycol.

  Examples of the radical polymerizable monomer containing a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo [2.2. 1] Hept-2-ene-5,6-dicarboxylic acid and the like, and derivatives of the carboxyl group-containing radical polymerizable monomer include derivatives of these acid anhydrides and these acid halides. Specifically, maleyl chloride, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, and maleic Examples thereof include monomethyl acid.

  Examples of the radical polymerizable monomer containing a hydroxyl group include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate. , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (Meth) acrylates such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10- Ndecene-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin mono Examples include allyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, and glycerin monoalcohol.

  The radical polymerizable monomer containing an epoxy group is a monomer having at least one unsaturated bond and epoxy group polymerizable in one molecule. Specifically, as such an epoxy group-containing radical polymerizable monomer, Glycidyl acrylate, glycidyl methacrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrophthalic acid, mono and glycidyl esters of itaconic acid Mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid) And diglycidyl esters, mono- and diglycidyl esters of endo-cis-bicyclo [2.2.1] hept-5-en-2-methyl-2,3-dicarboxylic acid (methylnadic acid), mono- and allysuccinic acid Dicarboxylic acid mono- and alkyl glycidyl esters such as glycidyl ester (in the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms), alkyl glycidyl ester of p-styrene carboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl Ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3 -Methyl-1-pentene, 5,6-epoxy-1-hexene, Such alkenyl cyclohexene monoxide and the like.

  Examples of the radical polymerizable monomer containing an oxazoline group include vinyl oxazoline, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4 , 4-Dimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 2 -Isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, etc. are mentioned.

  Examples of the radically polymerizable monomer containing a maleimide group include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearyl. Maleimides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and derivatives thereof are mentioned.

  Examples of the radically polymerizable monomer containing an amino group include an amino group-containing ethylenically unsaturated compound having an ethylenic double bond and an amino group. As the amino group-containing ethylenically unsaturated compound, specifically, Of acrylic acid or methacrylic acid such as aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate Aminoalkyl ester derivatives; vinylamine derivatives such as N-vinyldiethylamine; allylamine derivatives such as allylamine, methallylamine, N-methylmethallylamine; aminostyrenes such as p-aminostyrene; Hexyl succinimide, such as 2-aminoethyl succinimide is used.

  In the present invention, other radical polymerizable monomers listed below can be used together with the radical polymerizable monomer having the reactive group. Specific examples of the radical polymerizable monomer used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, (meth ) Acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid Cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic Dodecyl acid, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 2-methoxyethyl oxalate, 3-methoxybutyl (meth) acrylate, stearyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, trifluoromethylmethyl (meth) acrylate, (meth) Acrylic acid-2-trifluoromethylethyl, (meth) acrylic acid-2-perfluoroethylethyl, (meth) acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, perfluoroethyl (meth) acrylate Perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2-methacrylic acid-2-perfluoromethyl-2-perfluoroethyl ethyl, (meth) acrylic acid-2-perfluoro Hexylethyl, (meth) acrylic acid-2-perfluorodecylethyl (Meth) acrylic acid monomers such as (meth) acrylic acid-2-perfluorohexadecylethyl, styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof, Fluorine-containing vinyl monomers such as fluoroethylene, perfluoropropylene, vinylidene fluoride, silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane, dialkyl esters of maleic acid, dialkyl esters of fumaric acid, acrylonitrile, methacrylo Nitrile group-containing vinyl monomers such as nitriles, vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, and olefins such as ethylene, propylene, and butene Nomar, butadiene, a diene monomer such as isoprene, vinyl chloride, vinylidene chloride, allyl chloride, vinyl ethyl ether, ethylene glycol dimethacrylate dicyclopentenyl ether, acrylic acid ethylene glycol dicyclopentenyl ether. These radically polymerizable monomers may be used alone or in combination of two or more.

The polar polymer segment [S ₂ ] used in the present invention is a polymer or copolymer obtained by radical polymerization of one or more monomers including a radical polymerizable monomer having the above reactive group. The use amount of the radically polymerizable monomer having a reactive group in all monomers constituting the polar polymer segment [S ₂ ] is not particularly limited, but is usually 10 to 100% by weight, preferably 15 to 100% by weight. It is a range.

The polar polymer segment [S ₂ ] has (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, (meth) acrylamide and derivatives thereof, maleic acid and derivatives thereof, maleimide and derivatives thereof as a main chain structure. It preferably contains a polymer chain obtained by (co) polymerizing one or more monomers selected from derivatives, vinyl esters, conjugated dienes, and halogen-containing olefins. In particular, it is more preferable to include a polymer chain obtained by (co) polymerizing one or more monomers selected from (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, and styrene and derivatives thereof. It is more preferable to include a polymer chain obtained by (co) polymerizing one or more monomers selected from an acrylate ester, styrene, (meth) acrylamide, (meth) acrylonitrile, and (meth) acrylic acid. Such a main chain structure can be obtained by appropriately selecting a monomer from a radical polymerizable monomer having the above reactive group as a monomer and, if necessary, the above other radical polymerizable monomer. .

In the present invention, the polar polymer segment [S ₂ ] in the hybrid polymer [P ₁ ] preferably has a number average molecular weight of 300 or more and less than 3,000, more preferably 500 or more and less than 2,000. . When the molecular weight is higher than this range, aggregation between polar polymers tends to occur. When it is lower than this range, the adhesive performance may be lowered.

In the laminated structure of the present invention, the polar polymer segment [S ₂ ] in the hybrid polymer [P ₁ ] improves the adhesion between the layer (B) and the layer (C) and improves the plasticizer retention. Alternatively, the solubility parameter is 18.0 to 25.0 ((J / cm ³ ) ^1/2 because of good solubility and dispersibility in components other than the hybrid polymer [P] in the layer (B). ² ), preferably 18.2 to 22.0 ((J / cm ³ ) ^1/2 ), more preferably 18.4 to 20.0 ((J / cm ³ ) ^{1. / 2} ).

The solubility parameter of the polar polymer segment [S _2] can be calculated from the composition of the copolymer constituting the polar polymer segment [S _2]. In the present invention, the solubility parameter was calculated by inputting the composition of the polar polymer segment [S ₂ ] into CHEOPSV Ver. 4.0 manufactured by Million Zillion Software, Inc.

The hybrid polymer [P ₁ ] is produced by radical (co) polymerizing one or more monomers including the above-described radical polymerizable monomer having a reactive group using the halogen-modified polyolefin [S ₁ ′] as a macroinitiator. Is done. The radical (co) polymerization method is not particularly limited, but usually an atom transfer radical (co) polymerization method is preferably used. The macroinitiator is a polymer having the ability of initiating atom transfer radical (co) polymerization, and represents a polymer having a site that can serve as an initiation point for atom transfer radical (co) polymerization in the molecular chain.

The atom transfer radical (co) polymerization in the present invention is one of living radical (co) polymerizations, and radicals are prepared by using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. This is a method of radically (co) polymerizing a polymerizable monomer. For example, Matyjaszewski et al., Chem. Rev., 1012921 (2001), WO96 / 30421 pamphlet, WO97 / 18247 pamphlet, WO98 / 01480 pamphlet, WO98 / 40415 pamphlet, WO00 / 157695 pamphlet, etc. Has been. Examples of the initiator used include organic halides and sulfonyl halide compounds, and in particular, a carbon-halogen bond present at the α-position of a carbon-carbon double bond or a carbon-oxygen double bond, or a single carbon. A structure in which a plurality of halogen atoms are added on an atom is suitable as the initiator structure. In the halogen-modified polyolefin [S ₁ ′] according to the present invention, the initiator structure has a carbon-halogen bond existing at the α-position of the carbon-carbon double bond, or a structure in which a plurality of halogens are added on one carbon atom. Can be used as

A method for producing a hybrid polymer [P ₁ ] using a halogen-modified polyolefin [S ₁ ′] as a macroinitiator is basically a metal complex having a transition metal as a central metal in the presence of the modified polyolefin [S ₁ ′]. A radically polymerizable monomer is atom-transferred (co) polymerized using the polymerization catalyst as a polymerization catalyst.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table 7th group, 8th group, 9th group, 10th group, or 11th group element as a central metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl, or a derivative thereof, 1,10-phenanthroline, or a derivative thereof, or tetramethylethylenediamine, pentamethyldiethylenetriamine, or hexamethyltris (2-aminoethyl) Polyamines such as amines are added as ligands. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₃ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  The atom transfer radical (co) polymerization method is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied. As the solvent that can be used in the radical (co) polymerization of the present invention, any solvent that does not inhibit the reaction can be used. For example, aromatic hydrocarbons such as benzene, toluene, and xylene are used as specific examples. Solvents, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, chloride Chlorinated hydrocarbon solvents such as methylene, chloroform, carbon tetrachloride and tetrachloroethylene, alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, Ketone solvents such as seton, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole be able to. Further, suspension polymerization and emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

  The reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and is not uniform depending on the degree of polymerization of the desired polymer, the type and amount of the radical polymerization initiator and the solvent used, but is usually −100 to 250 ° C. Preferably it is -50-180 degreeC, More preferably, it is 0-160 degreeC. In some cases, the reaction can be carried out under reduced pressure, normal pressure or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

The proportion of the polar polymer segment [S ₂ ] in the hybrid polymer [P ₁ ], [S ₂ ] / ([S ₁ ] + [S ₂ ]) is preferably 1 to 60% by weight, more preferably 2 to 30% by weight. Preferably, 3 to 15% by weight is particularly preferable. When the proportion of the polar polymer segment [S ₂ ] is within this range, the solubility of the hybrid polymer [P ₁ ] in the layer (B) increases, and the solubility and reactivity in the layer (C) are high. The adhesive strength between the layer (B) and the layer (C) is increased.

The hybrid polymer [P ₁ ] produced by the above method is isolated by using a known method such as distillation of the solvent used for polymerization or removal of unreacted monomers or reprecipitation with a poor solvent. Furthermore, by treating the obtained polymer with a polar solvent such as acetone or THF using a Soxhlet extraction apparatus, it is possible to remove the by-product homoradical polymer.

Hybrid polymer [P ₂ ]
In the hybrid polymer [P ₂ ] represented by the image formula (ii), the constituent components of the polyolefin segment [S ₁ ] and the polar polymer segment [S ₂ ] are respectively contained in the hybrid polymer [P ₁ ] described above. Same as [S ₁ ] and [S ₂ ]. The aspect of Q in the image formula (ii) and a typical method for producing a hybrid polymer [P ₂ ] composed of [S ₁ ], [S ₂ ] and Q have been filed by the present applicant and have already been published. The method disclosed in JP 2004-131620 A can be used without limitation. Typically, the hybrid polymer [P ₂ ] includes a structural unit represented by the following general formula [C-1], a structural unit represented by the following general formula [C-2], and the following general formula [C-3]. ] At least 1 type of structural unit chosen from the structural unit represented by this is included.

R ¹ in the general formula [C-1] represents a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms. The general formula [C-2] and the general formula [C- R ² in 3 represents a linear or branched aliphatic or aromatic hydrocarbon radical having 1 to 18 carbon atoms, F ¹ in the general formula [C-3] is a group containing a hetero atom or hetero atom F ² in the general formulas [C-2] and [C-3] represents a group containing an unsaturated group, Z represents a polymer segment obtained by radical polymerization, W represents an alcoholic hydroxyl group, A group selected from a phenolic hydroxyl group, a carboxylic acid group, a carboxylic acid ester group, an acid anhydride group, an amino group, an epoxy group, a siloxy group and a mercapto group, n is an integer of 1 to 3, and m is 0, 1 or 2 and n is 2 Alternatively, when Z is 3, Z may be the same or different, and when m is 2, W may be the same or different, and W may be bonded to the same or different atom of R ^{1 by} a cyclic structure. good. In a virtual case where the hybrid polymer [P ₂ ] is composed only of the above [C-2], the main chain portion (—CH ₂ —CH—) in the skeleton [C-2] is as described above. It corresponds to [S ₁ ] in the image formula (ii) represented, Z in the skeleton [C-2] corresponds to [S ₂ ] in the image formula (ii), and the remaining part (−R ² ( Wm) -F ^2- ) corresponds to Q in the image formula.

In hybrid polymer _{[P 2],} the number-average molecular weight of the number average molecular weight and polar polymer segment _{[S 2]} of polyolefin segments _{[S 1],} like each hybrid polymer _{[P 1],} of 7,000 to 40,000 The range is in the range of 300 to 3,000. The hybrid polymers [P ₁ ] and [P ₂ ] have been described in detail above.

The layer (B) constituting the laminated structure of the present invention is a layer comprising the hybrid polymer [P], preferably the hybrid polymer [P ₁ ] and / or the hybrid polymer [P ₂ ]. Usually, the hybrid polymer [P] is an essential constituent, and further selected from the polyolefin [R] of the same quality as the polyolefin segment [S ₁ ] and the polar polymer [Q] of the same quality as the polar polymer segment [S ₂ ]. One or more of them. Note that the "homogeneous" in the present invention, in the polyolefin segment [S _1], polar polymer segment carbon atoms are bonded with [S _2] or a polar polymer segment [S _2] in, polyolefin segment [ S ₁ ] is defined as a polyolefin or a polar polyolefin, each having a chemical structure in which the carbon atom bonded to S ₁ ] is replaced by a hydrogen atom. However, in the present invention, the polyolefin [R] includes not only a polyolefin having a chemical structure in which the carbon atom bonded to the polyolefin segment [S ₂ ] is replaced by a hydrogen atom, but also those having a varied molecular weight or α- Polyolefins having different olefin introduction rates are also targets of [R], and the olefin polymers exemplified as the olefin polymers constituting the layer (A) can be used without limitation. On the other hand, as the polar polyolefin [Q], not only the polar polyolefin having a chemical structure in which the carbon atom bonded to the polyolefin segment [S ₁ ] is substituted with a hydrogen atom, but also those having a varied molecular weight, the introduction rate of the polar monomer All items with different values are also subject to [Q].

The weight ratio of the hybrid polymer [P] in the total of [P], [Q] and [R] in the layer (B) is usually 1 to 100% by weight, preferably 1 to 50% by weight, more preferably 1 to 30% by weight. When the layer (B) includes the hybrid polymer [P] and the polar polymer [Q] and does not include the polyolefin [R], [Q] / [S ₂ ] (weight ratio), that is, the component [ Q] By satisfying the requirement that the value obtained by dividing the weight by the polar polymer segment [S ₂ ] weight in component [P] is less than 0.5, preferably less than 0.4, more preferably less than 0.3 The layer (B) and the layer (C) exhibit strong adhesive force.

  Further, the layer (B) does not exclude any coexistence of components other than [P], [Q], and [R]. You may add resin and additives other than [P], [Q], and [R] in the range which does not inhibit the objective of this invention. In the resin composition constituting the layer (B), when resins are added as constituents other than [P], [Q] and [R], the sum of [P], [Q] and [R] Is 1 to 100% by weight of the layer (B), preferably 50 to 100% by weight, and more preferably 70 to 100% by weight. Additive components added to the layer (B) include inorganic fillers such as talc, silica, mica, clay, glass fiber, dyes and pigments, antioxidants, processing stabilizers, weathering agents, heat stabilizers, light Stabilizers, nucleating agents, lubricants, mold release agents, flame retardants, antistatic agents, coloring agents, ultraviolet absorbers and the like.

  A conventionally well-known method can be employ | adopted for the manufacturing method of the resin composition which comprises a layer (B). For example, a method of mixing each component in a batch or sequentially with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender or the like, or a mixture obtained by mixing by such a method, a single screw extruder, After melt-kneading with a twin screw extruder, kneader, Banbury mixer or the like, it can be obtained by granulation or pulverization of the obtained resin mass.

<Layer (C)>
The layer (C) is at least one selected from polar vinyl plastics, aromatic vinyl polymers, polyesters, polyamides, polycarbonates, engineering plastics, biological polymers, thermoplastic elastomers, natural or artificial fibers, inorganic glasses and metals. A layer of seeds. The layer (C) exhibits excellent adhesion performance by forming a chemical bond particularly with the layer (B). Therefore, the material used for the layer (C) is desirably a material containing a polar group having reactivity with the layer (B). In the present invention, when the layer (C) is composed of a polar vinyl-based plastic, an aromatic vinyl-based polymer, or a polyester, excellent adhesive performance is exhibited particularly between the layers (B).

  Specific examples of the polar vinyl plastic used in the layer (C) include acrylic polymers, vinyl chloride polymers, vinylidene chloride polymers, saponified ethylene-vinyl acetate copolymers, and the like. .

  Examples of the acrylic polymer used in the layer (C) include an acrylic polymer mainly composed of a structural unit derived from a (meth) acrylic acid ester. In that case, the ratio of the structural unit derived from the (meth) acrylic acid ester in the acrylic polymer is preferably 50% by weight or more, and more preferably 80% by weight or more. Examples of the (meth) acrylic acid ester constituting the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Examples include alkyl esters of (meth) acrylic acid such as 2-ethylhexyl acid, and the acrylic polymer has a structural unit derived from one or more of these (meth) acrylic acid esters. Can be. Moreover, the acrylic polymer may have 1 type (s) or 2 or more types of the structural unit induced | guided | derived from unsaturated monomers other than (meth) acrylic acid ester as needed. For example, the methacrylic resin may have a structural unit derived from a vinyl cyanide monomer such as (meth) acrylonitrile, preferably in a proportion of 50% by weight or less, and styrene, o-methylstyrene, m -It has a structural unit derived from an aromatic vinyl compound such as methyl styrene, p-methyl styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, etc., preferably in a proportion of 10% by weight or less. Also good.

  The vinyl chloride polymer used in the layer (C) includes a vinyl chloride homopolymer, a copolymer of vinyl chloride having a structural unit derived from vinyl chloride in a proportion of 70% by weight or more and other copolymerizable monomers. One or two or more of coalesced and chlorinated compounds thereof are preferably used. When the vinyl chloride polymer is a vinyl chloride copolymer, one or more of vinyl chloride and copolymerizable monomers such as ethylene, propylene, vinyl acetate, vinyl bromide, vinylidene chloride, acrylonitrile, maleimide, etc. These copolymers are preferably used. The degree of polymerization of the vinyl chloride polymer is not particularly limited, but generally, those having a degree of polymerization of 100 to 10,000 are preferably used, and those having a degree of polymerization of 500 to 6,000 are more preferably used.

  As the vinylidene chloride polymer used in the layer (C), a thermoplastic polymer having a structural unit derived from vinylidene chloride in a proportion of 50% by weight or more is preferably used, and in a proportion of 70% by weight or more. The thermoplastic polymer it has is more preferably used. When the vinylidene chloride polymer is a copolymer of vinylidene chloride and other monomers, one or two of vinylidene chloride and other unsaturated monomers such as vinyl chloride, acrylonitrile, acrylic acid ester and acrylic acid Copolymers with more than one species are preferably used. The degree of polymerization of the vinylidene chloride polymer is not particularly limited, but generally, those having a degree of polymerization of 100 to 10,000 are preferably used, and those having a degree of polymerization of 500 to 5,000 are more preferably used.

  As the saponified ethylene-vinyl acetate copolymer used in the layer (C), those having an ethylene content of 20 to 60 mol%, preferably 25 to 60 mol% and a saponification degree of 95% or more are preferably used. . The saponified ethylene-vinyl acetate copolymer has a melt index measured in accordance with ASTM D-1238-65T of 0.1 to 25 g / 10 min (measured at 190 ° C. under a load of 2.16 kg). However, it is preferable from the point of a moldability, and it is more preferable that it is 0.3-20 g / 10min.

  The aromatic vinyl polymer used in the layer (C) is a polymer obtained by polymerizing a monomer containing an aromatic vinyl monomer as a component. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene and the like. Examples of aromatic vinyl polymers include not only aromatic vinyl homopolymers, but also various rubbers such as butadiene rubber, styrene-butadiene copolymer, ethylene-propylene copolymer, and ethylene-propylene-diene copolymer. Aromatic vinyl polymer containing styrene polymer, styrene-maleic anhydride copolymer, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-acrylonitrile -An acrylic ester copolymer etc. can be illustrated.

  The polyester used in the layer (C) is not particularly limited as long as it has an ester bond in the polymer main chain and can be melted by heating. Examples of polyesters that can be used in the present invention include polycondensation of polyesters obtained by reaction of dicarboxylic acid components with diol components, polyesters obtained by ring-opening polymerization of lactones (polylactones), hydroxycarboxylic acids or ester-forming derivatives thereof. The polyester obtained by doing this can be mentioned, 1 type, or 2 or more types of these polyesters can be used. Among these, in the present invention, a polyester substantially formed from a dicarboxylic acid component and a diol component is preferably used. Specific examples of the above-mentioned dicarboxylic acid component which is a raw material of polyester include terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid. , Aromatic dicarboxylic acids such as sodium 5-sulfoisophthalate; aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, dodecanedioic acid; alicyclic such as cyclohexanedicarboxylic acid And dicarboxylic acids; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; halogen-containing dicarboxylic acids such as tetrabromophthalic acid; and ester-forming derivatives thereof.

  Specific examples of the above-described diol component that is a raw material of polyester include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, Fats such as 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol Aliphatic diols such as cyclohexanedimethanol and cyclohexanediol; derived from polyalkylene glycols having a molecular weight of 6,000 or less such as diethylene glycol, polyethylene glycol, poly-1,3-propylene glycol and polytetramethylene glycol Geo And the like.

  In addition, the polyester may contain a small amount of one or more structural units derived from a trifunctional or higher functional compound such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, or pyromellitic acid. If so, you may have.

  The polyamide used in the layer (C) is not particularly limited as long as it has an amide bond in the polymer main chain and can be heated and melted. Examples of polyamides that can be used in the present invention include polyamides obtained by ring-opening polymerization of lactams having three or more members (polylactams), polyamides obtained by polycondensation of ω-amino acids, and polycondensation of dibasic acids and diamines. Can be used, and one or more of these polyamides can be used.

  Specific examples of the above-mentioned lactam which is a raw material for polyamide include ε-caprolactam, enatoractam, capryllactam, lauryllactam, α-pyrrolidone and the like. Specific examples of the above-mentioned ω-amino acid that is a raw material of polyamide include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and the like. Specific examples of the dibasic acid include fats such as malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, sebacic acid, and suberic acid. Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, Aromatic dicarboxylic acids such as diphenylsulfone-4,4′-dicarboxylic acid and 4,4′-diphenyldicarboxylic acid And so on. Specific examples of the diamine include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, , 12-dodecanediamine, 2-methyl-1,5-pentanediamine, aliphatic diamines such as 3-methyl-1,5-pentanediamine; cycloaliphatic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine; p Examples include aromatic diamines such as -phenylenediamine, m-phenylenediamine, xylylenediamine, xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl ether. .

  Examples of the polycarbonate used in the layer (C) include polycarbonates obtained by reacting a substantial dihydroxy compound with phosgene, a carbonic acid diester, or a halogen formate. In this case, examples of the dihydroxy compound as a raw material include 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as “bisphenol A”), tetramethylbisphenol A, tetrabromobisphenol A, and bis. Aromatic dihydroxy compounds such as (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol and 4,4′-dihydroxydiphenyl can be mentioned, and among these, bisphenol A is preferred. Further, the polycarbonate may have a small amount of one or more structural units derived from a trifunctional or higher polyhydroxy compound as required.

  Typical examples of the engineering plastic used in the layer (C) include polyacetal (POM), polyphenylene ether (including modified polyphenylene ether), polysulfone (PSF), polyethersulfone (PES), polyphenylene sulfide, polyarylate (U Polymer), polyamideimide, polyetherketone (PEK), polyetheretherketone (PEEK), polyimide (PI), and super engineering plastics such as liquid crystal polyester.

  The biological polymer used in the layer (C) is a biological polymer produced from “biomass” which is a raw material of biological origin such as plants and animals. A typical example thereof is poly-3-hydroxybutyric acid (PHB). ), Polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxybutyrate, or copolymers thereof, starch, cellulose, chitin / chitosan, kenaf, natural rubber, etc., which are components of crab and shrimp shells, etc. .

  The thermoplastic elastomer used in the layer (C) is generally a flexible elastic body having a tensile modulus of 300 MPa or less at room temperature, and examples include olefin elastomers, styrene elastomers, acrylic elastomers, urethane elastomers, and the like. Is done.

  Examples of natural fibers or artificial fibers used in the layer (C) include glass fibers, carbon fibers, metal fibers, aromatic polyamide fibers, polyaramid fibers, alumina fibers, silicon carbide fibers, boron fibers, and basalt fibers.

  The inorganic glass used in the layer (C) is a glass mainly composed of silicate. The metal used in the layer (C) typically includes a metal material obtained by subjecting aluminum, iron, magnesium, titanium, an alloy thereof, or the like to a heat-adhesive surface treatment.

<Laminated structure>
In the laminated structure of the present invention, the thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer or material constituting each layer, the total number of layers in the laminated structure, the use of the laminated structure, and the like. However, in general, the thickness of the polymer layer (A) is 10 μm to 5 mm, the thickness of the polymer layer (B) is 1 μm to 1 mm, and the thickness of the polymer layer (C) is 10 μm to 5 mm. However, it is preferable from the viewpoints of the ease of manufacturing the laminated structure and the interlayer adhesion.

  Further, the total number of layers in the multilayer structure of the present invention is not particularly limited, and is a multilayer structure having at least a part of a structure in which layers (A) / layers (B) / layers (C) are laminated in this order. Any may be used as long as it exists. Moreover, even if the laminated structure of this invention is formed only from three layers, a layer (A), a layer (B), and a layer (C), or those three types of layers, a layer (A)-layer ( It may have one or more layers made of other materials than the material constituting C).

  Examples of the laminated structure of the present invention include a three-layer structure composed of layer (A) / layer (B) / layer (C); layer (C) / layer (A) / layer (B) / layer (C A five-layer structure consisting of layer (A) / layer (B) / layer (C) / layer (B) / layer (A); layer (C) / layer (B) / layer 5-layer structure consisting of (A) / layer (B) / layer (C); layer (C) / layer (A) / layer (B) / layer (C) / layer (B) / layer (A) / Examples thereof include a seven-layer structure composed of the layer (C).

As a manufacturing method of the laminated structure of the present invention, for example,
(1) Using at least a polymer for layer (A), a polymer for layer (B), and a polymer or material for layer (C), melt coextrusion into a film, sheet, or plate A method for producing a laminated structure by molding and laminating simultaneously with extrusion molding of each layer;
(2) A molded product such as a film, a sheet, or a plate constituting the layer (A) and / or the layer (C) is manufactured in advance, and the polymer layer (B) is melt-extruded and the layer (A ) And layer (C), if one of them is not pre-molded, the molded product for layer (A) and / or the molding for layer (C), which is also prepared by melt extrusion molding A method of manufacturing a laminated structure by stacking and integrating with a product;
(3) A molded product such as a film, sheet, or plate constituting the layer (A) and a molded product such as a film, sheet, or plate constituting the layer (C) are manufactured in advance, and further for the layer (B). The polymer is also formed into a film or sheet in advance, and the film or sheet for layer (B) is sandwiched between the molded product for layer (A) and the molded product for layer (C) and heated. A method of producing a laminated structure by melting a film or sheet for layer (B) and bonding and integrating layers (A) and (C) via layer (B);
(4) Using at least the polymer for the layer (A), the polymer for the layer (B), and the polymer or material for the layer (C), the timing of injection of the three types of polymers or materials is shifted. A method of producing a laminated molded body by injecting into a mold;
And so on.

  In any of the above methods (1) to (4), the layer (A) and the layer (C) are bonded via the molten layer (B), and the adhesive layer does not contain an organic solvent. Thus, the desired laminated structure can be obtained without causing problems and troubles such as destruction of the natural environment by the organic solvent, deterioration of the working environment, and recovery of the solvent. Among them, the above-described method by coextrusion molding (1) has few steps and high productivity, and the adhesive strength between the layers (A), (B) and (C) is high, It is preferable because a laminated structure without peeling can be obtained.

  When the laminated structure of the present invention is produced by the coextrusion molding method, for example, three or more extruders are bonded to one die according to the number of layers of the laminated structure, and a plurality of polymers are bonded to the die. Can be manufactured by laminating and integrating them inside or outside. As the die in that case, a T die, an annular die or the like can be used, and the shape and structure of the extruder and the die are not particularly limited.

  The laminated structure of the present invention can be used for various purposes depending on the properties of the layer (A), layer (B), layer (C) constituting the layered structure, for example, for food and medical use. Pharmaceutical packaging materials; Clothing packaging materials; Packaging materials for other products; Building materials such as wallpaper and decorative boards; Electrical insulation films; Adhesive films and tape substrates; Marking films; Agricultural films; Tables It can be used in various applications such as cloths, raincoats, umbrellas, curtains, covers, etc .; laminating with metal plates and other materials.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The analysis method and raw materials used in the present invention are as follows.

[M1] Molecular weight and molecular weight distribution (GPC) of polyolefin segment [S ₁ ]
The molecular weight and molecular weight distribution of the polyolefin segment [S _1], the measurement samples of gel-using permeation chromatography (GPC), substantially identical to the polyolefin molecular weight profile as the polyolefin segment _{[S 1] [S 1 '} '] And asked. GPC was measured under the following conditions.
GPC: Waters 2000 type column: Tosoh TSKgel GMH6-HT × 2, TSKgel GMH6-HTL × 2 Injection amount: 500 μl (polymer concentration 1.5 g / L)
Flow rate: 1 ml / min
Column temperature: 140 ° C
Solvent: A standard curve of elution volume and molecular weight was prepared using standard polystyrene manufactured by o-dichlorobenzene Tosoh Corporation. Using the calibration curve, the polystyrene-equivalent weight average molecular weight (Mw) and number-average molecular weight (Mn) of the specimen were obtained and converted into polypropylene equivalents by the general calibration method.

[M2] Number of introduced halogen atoms ( ¹ H-NMR)
The amount of halogen atoms introduced in the halogen-modified polyolefin [S ₁ ′] was identified from the peak integration ratio of the ¹ H-NMR spectrum chart of the polymer. ¹ H-NMR spectrum measurement was performed using a GSX400 type apparatus manufactured by JEOL Ltd. at a measurement solvent o-dichlorobenzene-d ₄ and a measurement temperature of 120 ° C.

[M3] Molecular weight of the polar polymer segment [S ₂ ] ( ¹ H-NMR)
The content of the polar polymer segment [S ₂ ] in the hybrid polymer was identified from the peak integration ratio of the ¹ H-NMR spectrum chart. Content R (S ₂ ) of the obtained polar polymer segment [S ₂ ] = [S ₂ ] / ([S ₁ ] + [S ₂ ]) (% by weight) and introduction of halogen atom determined by [m ₂ ] From the number N (lines / chain) (= starting amount of the polymer segment [S ₂ ]) and the number average molecular weight Mn (S ₁ ′) of the halogen-modified polyolefin [S ₁ ′], the number average of the polar polymer segment [S ₂ ] The molecular weight Mn (S ₂ ) was calculated as follows.

Mn (S ₂ ) = Mn (S ₁ ′) × R (S ₂ ) / ((100−R (S ₂ )) × N)

[M4] Melting point (DSC)
The melting point of the polymer was measured using DSC-7 manufactured by Perkin-Elmer Co., Ltd., under the condition that a sample obtained by accurately weighing 5.0 mg was heated to 200 ° C. at 10 ° C./min.

[M5] Interfacial Adhesive Strength Determined by T-type peeling under conditions of a peeling atmosphere temperature of 23 ° C., a peeling speed of 300 mm / min, and a peel width of 15 mm.

[Raw materials]
Polyolefin B-1
Prime polymer random polypropylene F327D
MFR = 7.2 g / 10 min, density = 900 kg / m ³
Polyolefin B-2
Mitsui Chemicals Co., Ltd. ethylene propylene random polymer Toughmer P-0680
MFR = 3.6 g / 10 min, density 870 kg / m ³
Polyolefin B-3
Mitsui Chemicals, Inc. Nanocrystal Structure Control Elastomer Notio PN-2070
MFR = 7.0 g / 10 min, density = 870 kg / m ³
Polyolefin B-4
Mitsui Chemicals Co., Ltd. Ethylene Butene Random Polymer Toughmer A-4050
MFR = 3.6 g / 10 min, density 862 kg / m ³

[Production Example 1] Hybrid polymer (P-1)
(1) Production of halogen-modified polypropylene (S1-1) While putting 1700 mL of toluene into a 2 L glass polymerizer and circulating propylene gas (100 L / h), 3.6 mL (18.0 mmol) of 10-undecenol, TIBAL 5 .53 ml (22.0 mmol) was added sequentially, and at 37 ° C. and 600 rpm stirring speed, 8.37 mg (0.02 mmol) of ethylenebis (indenyl) zirconium dichloride prepared in another nitrogen-substituted Schlenk and methylalumoxane (Japan) 2.85 ml of a premixed toluene solution having an aluminum content of 4.0 mmol manufactured by Alkyl Aluminum Co. was placed in a polymerization vessel and polymerized at a stirring speed of 600 rpm for 80 minutes while maintaining 40 ° C. The polymerization solution was poured into 1.5 L of methanol containing 5 mL of 1N hydrochloric acid to precipitate a polymer. The white polymer filtered off with the Kiriyama funnel was dried at 80 ° C. under reduced pressure (50 Torr) overnight to obtain 187.5 g of a propylene / 10-undecenol copolymer having a hydroxyl group. From the GPC measurement, it was Mw = 29000 and Mn = 15300 as the molecular weight in terms of polypropylene, and from ¹ H-NMR measurement, the hydroxyl group content was 0.072 mmol / g. The obtained propylene / 10-undecenol copolymer was put into a glass reaction group, and hexane was added to form a slurry so that the polymer concentration was 100 g / L. 5-fold equivalent 2-bromoisobutyric acid bromide was added to the amount of hydroxyl groups present in the polymer, heated to 60 ° C., and heated and stirred for 3 hours. The reaction solution was cooled to 20 ° C. at a cooling rate of 20 ° C./h, and the polymer was filtered off. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again. The obtained white polymer was dried under reduced pressure conditions of 50 ° C. and 1.3 × 10 ⁻³ MPa for 10 hours to obtain halogen-modified polypropylene (S1-1). As a result of the high temperature GPC analysis, the number average molecular weight Mn in terms of polypropylene was 15,000, the melting point was 128 ° C. from the DSC measurement result, and bromine derived from 2-bromoisobutyric acid bromide was introduced from ¹ H-NMR analysis. The average number of introduced ends was 1.2 / chain. The melting point of the polymer measured by DSC was 129.5 ° C.

(2) Production of hybrid polymer (P-1) The above halogen-modified polypropylene (S1-1) is put in a glass polymerizer, and a monomer mixed solution of styrene: maleic anhydride = 83: 17 (molar ratio) is polymerized. In addition to the concentration of 189 g / L, a deoxygenation operation by nitrogen bubbling was performed. Thereafter, a 1: 2 (molar ratio) toluene solution of copper (I) bromide: N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (hereinafter abbreviated as “PMDETA”) was halogenated. To the halogen content of the modified polypropylene (S1-1), 1.5 equivalents of copper (I) bromide was added and heated and stirred. When polymerized at 100 ° C. for 5 hours, the mixture was cooled in an ice bath to precipitate a polymer, and then filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (1.3 × 10 ⁻³ MPa) to obtain a hybrid polymer (P-1) as a white polymer. The solubility parameter of the [S ₂ ] segment in the hybrid polymer (P-1) was 19.4 ((J / cm ³ ) ^1/2 ), Tg = 85 ° C., and Mn = 1500.

[Production Example 2] Hybrid polymer (P-2)
(1) Production of halogen-modified polypropylene (S1-2) 1700 mL of toluene was placed in a 2 L glass polymerization vessel, and 4.8 mL (24 mmol) of 10-undecenol and TIBAL 7.1 mL were allowed to flow through propylene gas (100 L / h). (28 mmol) was added sequentially, and at 50 ° C. and a stirring rate of 600 rpm, 8.37 mg (0.02 mmol) of ethylenebis (indenyl) zirconium dichloride and methylalumoxane (manufactured by Nippon Alkyl Aluminum Co., Ltd.) prepared in another nitrogen-substituted Schlenk 2.85 ml of a premixed toluene solution having an aluminum content of 4.0 mmol) was placed in a polymerization vessel and polymerized for 60 minutes at a stirring speed of 600 rpm while maintaining 50 ° C. The polymerization solution was poured into 1.5 L of methanol containing 5 mL of 1N hydrochloric acid to precipitate a polymer. The white polymer filtered off with the Kiriyama funnel is dried at 80 ° C. under reduced pressure (6.7 × 10 ⁻³ MPa) overnight to obtain 150.8 g of a propylene / 10-undecenol copolymer having a hydroxyl group. It was. The obtained propylene / 10-undecenol copolymer was put into a glass reactive group, and hexane was added to form a slurry so that the polymer concentration was 100 g / L. 5-fold equivalent 2-bromoisobutyric acid bromide was added to the amount of hydroxyl groups present in the polymer, heated to 60 ° C., and stirred for 2 hours. The reaction solution was cooled to 20 ° C. at a cooling rate of 20 ° C./h, and the polymer was filtered off. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again. The obtained white polymer was dried under reduced pressure conditions of 50 ° C. and 1.3 × 10 ⁻³ MPa for 10 hours to obtain halogen-modified polypropylene (S1-2). The number average molecular weight Mn in terms of polypropylene was Mn = 12,600, and the number of bromine introduced terminals was 0.5 / chain as the average number introduced. The melting point of the polymer measured by DSC was 127.2 ° C.

(2) Production of hybrid polymer (P-2) The above halogen-modified polypropylene (S1-2) was placed in a glass polymerizer, and a toluene solution prepared so that glycidyl methacrylate (GMA) was 3.0 M, In addition to the polymer concentration being 93 g / L, a deoxygenation operation by nitrogen bubbling was performed. Thereafter, a 1: 2 (molar ratio) toluene solution of copper (I) bromide: PMDETA was adjusted to 2 equivalents of copper (I) bromide with respect to the halogen content of the halogen-modified polypropylene (S1-2). In addition, it was heated and stirred. Upon polymerization at 75 ° C. for 20 minutes, the mixture was cooled in an ice bath, and the polymer was filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (1.3 × 10 ⁻³ MPa) to obtain a hybrid polymer (P-2) as a white polymer. The solubility parameter of the [S ₂ ] segment in the hybrid polymer (P-2) was 19.4 ((J / cm ³ ) ^1/2 ), and Tg = −21 ° C. and Mn = 650.

[Production Example 3] Hybrid polymer (P-3)
(1) Production of halogen-modified polypropylene (S1-3) In propylene / 10-undecenol copolymerization operation, as a olefin gas to be circulated, a mixed gas of propylene gas (100 L / h) and hydrogen gas (4 L / h) is used for polymerization. A halogen-modified polypropylene (S1-3) was obtained according to the method described in Production Example 1 except that the time was 120 minutes. The number average molecular weight Mn in terms of polypropylene was Mn = 5,900, and the terminal into which bromine was introduced was 0.5 / chain as the average number of introduction. The melting point of the polymer measured by DSC was 132.0 ° C.
(2) Production of hybrid polymer (P-3) The above halogen-modified polypropylene (S1-3) was put in a glass polymerizer, and a toluene solution prepared so that glycidyl methacrylate (GMA) was 3.0 M, In addition to the polymer concentration being 93 g / L, a deoxygenation operation by nitrogen bubbling was performed. Thereafter, a 1: 2 (molar ratio) toluene solution of copper (I) bromide: PMDETA was adjusted to 2 equivalents of copper (I) bromide with respect to the halogen content of the halogen-modified polypropylene (S1-3). In addition, it was heated and stirred. Upon polymerization at 75 ° C. for 20 minutes, the mixture was cooled in an ice bath, and the polymer was filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (1.3 × 10 ⁻³ MPa) to obtain a hybrid polymer (P-3) as a white polymer. The solubility parameter of the [S ₂ ] segment in the hybrid polymer (P-3) was 19.4 ((J / cm ³ ) ^1/2 ), and Tg = −21 ° C. and Mn = 680.

[Production Example 4] Hybrid polymer (P-4)
(1) Production of halogen-modified polypropylene (S1-4) In the propylene / 10-undecenol copolymerization operation, the olefin gas to be circulated conforms to the method described in Production Example 1 except that propylene gas (150 L / h) is used. Thus, a halogen-modified polypropylene (S1-4) was obtained. The number average molecular weight Mn in terms of polypropylene was Mn = 45,500, and the number of bromine introduced terminals was 0.8 / chain as the average number of introduction. The melting point of the polymer measured by DSC was 135.0 ° C.
(2) Production of hybrid polymer (P-4) The above halogen-modified polypropylene (S1-4) was put in a glass polymerizer, and a toluene solution prepared so that glycidyl methacrylate (GMA) was 3.0 M, In addition to the polymer concentration being 93 g / L, a deoxygenation operation by nitrogen bubbling was performed. Thereafter, a 1: 2 (molar ratio) toluene solution of copper (I) bromide: PMDETA was adjusted to 2 equivalents of copper (I) bromide with respect to the halogen content of the halogen-modified polypropylene (S1-4). In addition, it was heated and stirred. Upon polymerization at 75 ° C. for 20 minutes, the mixture was cooled in an ice bath, and the polymer was filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (1.3 × 10 ⁻³ MPa) to obtain a hybrid polymer (P-3) as a white polymer. The solubility parameter of the S2 segment in the hybrid polymer (P-4) was 19.4 ((J / cm ³ ) ^1/2 ), Tg = -21 ° C., and Mn = 520.

[Example 1]
(1) Preparation of polymer composition 65 parts by weight of polyolefin B-1, 25 parts by weight of polyolefin B-2, and 10 parts by weight of the hybrid polymer (P-1) obtained in Production Example 1 were premixed and stocked Using a twin screw extruder KZW-15G (die diameter: 15 mmφ, L / D = 30) manufactured by Technobel Co., Ltd., melt-kneaded at a temperature of 200 ° C., extruded into strands, and cut to produce pellets. The pellet was heated overnight in a vacuum dryer at 80 ° C. to obtain a polymer composition of polyolefin B-1, polyolefin B-2, and hybrid polymer (P-1).
(2) Manufacture of Laminated Structure Using an extrusion molding apparatus in which three extruders are bonded to one die, each extruder is supplied with a Kuraray Co., Ltd. ethylene-vinyl alcohol copolymer (grade F101A; MFR = 1) 0.6 g / 10 min, density = 1.19 g / cm 3), supplied by Prime Polymer Co., Ltd., random polypropylene F327D, and the polymer composition obtained in (1) above, and the maximum temperature during extrusion is 220 ° C. 3 were laminated in the order of T-die (die width is 130 mm) of the extrusion molding apparatus, random polypropylene (60 μm) / polymer composition (30 μm) / ethylene-vinyl alcohol copolymer (60 μm). Co-extrusion molding is performed so as to form a layer structure, (A) layer is a random polypropylene layer, (B) layer is a layer containing a hybrid polymer (C) layer is ethylene - to produce a laminated structure consisting of three layers is a vinyl alcohol copolymer layer.

  The laminated structure obtained above was measured for the interfacial adhesive strength between the (B) layer and the (C) layer, and showed a peel strength of 4 N / 15 mm.

[Example 2]
(1) Preparation of polymer composition 65 parts by weight of polyolefin B-3, 25 parts by weight of polyolefin B-4, and 10 parts by weight of the hybrid polymer (P-2) obtained in Production Example 2 were premixed to obtain a stock. Using a twin screw extruder KZW-15G (die diameter: 15 mmφ, L / D = 30) manufactured by Technobel Co., Ltd., melt-kneaded at a temperature of 200 ° C., extruded into strands, and cut to produce pellets. The pellet was heated overnight in a vacuum dryer at 80 ° C. to obtain a polymer composition of polyolefin B-3, polyolefin B-4, and hybrid polymer (P-2).
(2) Manufacture of a laminated structure Using an extrusion molding apparatus in which three extruders are combined into one die, each extruder is made of polyethylene terephthalate (grade J125) manufactured by Mitsui Chemicals, Inc. Polypropylene F327D, the polymer composition obtained in the above (1) is supplied, and the maximum temperature during extrusion is set to be 275 ° C., and from the T die of the extrusion molding apparatus (die width is 130 mm), Random polypropylene (60 μm) / polymer composition (30 μm) / polyethylene terephthalate (60 μm) were laminated in this order to form a three-layer structure, and (A) layer was a random polypropylene layer, (B) A layered structure composed of three layers in which the layer includes a hybrid polymer and (C) the layer is a polyethylene terephthalate layer. Manufactured.

  About the laminated structure obtained above, when the interface bond strength between the (B) layer and the (C) layer was measured, a peel strength of 15 N / 15 mm was shown.

[Comparative Example 1]
(1) Preparation of polymer composition 65 parts by weight of polyolefin B-3, 25 parts by weight of polyolefin B-4, and 10 parts by weight of the hybrid polymer (P-3) obtained in Production Example 2 were premixed to obtain a stock. Using a twin screw extruder KZW-15G (die diameter: 15 mmφ, L / D = 30) manufactured by Technobel Co., Ltd., melt-kneaded at a temperature of 200 ° C., extruded into strands, and cut to produce pellets. This pellet was heated overnight in a vacuum dryer at 80 ° C. to obtain a polymer composition of polyolefin B-3, polyolefin B-4, and hybrid polymer (P-3).
(2) Manufacture of a laminated structure Using an extrusion molding apparatus in which three extruders are combined into one die, each extruder is made of polyethylene terephthalate (grade J125) manufactured by Mitsui Chemicals, Inc. Polypropylene F327D, the polymer composition obtained in the above (1) is supplied, and the maximum temperature during extrusion is set to be 275 ° C., and from the T die of the extrusion molding apparatus (die width is 130 mm), Random polypropylene (60 μm) / polymer composition (30 μm) / polyethylene terephthalate (60 μm) were laminated in this order to form a three-layer structure, and (A) layer was a random polypropylene layer, (B) A layered structure composed of three layers in which the layer includes a hybrid polymer and (C) the layer is a polyethylene terephthalate layer. Manufactured.

  About the laminated structure obtained above, when the interface adhesive strength of the (B) layer and the (C) layer was measured, no adhesive force was expressed.

[Comparative Example 2]
(1) Preparation of polymer composition 65 parts by weight of polyolefin B-3, 25 parts by weight of polyolefin B-4, and 10 parts by weight of the hybrid polymer (P-4) obtained in Production Example 2 were premixed to obtain a stock. Using a twin screw extruder KZW-15G (die diameter: 15 mmφ, L / D = 30) manufactured by Technobel Co., Ltd., melt-kneaded at a temperature of 200 ° C., extruded into strands, and cut to produce pellets. This pellet was heated overnight in a vacuum dryer at 80 ° C. to obtain a polymer composition of polyolefin B-3, polyolefin B-4, and hybrid polymer (P-4).
(2) Manufacture of a laminated structure Using an extrusion molding apparatus in which three extruders are combined into one die, each extruder is made of polyethylene terephthalate (grade J125) manufactured by Mitsui Chemicals, Inc. Polypropylene F327D, the polymer composition obtained in the above (1) is supplied, and the maximum temperature during extrusion is set to be 275 ° C., and from the T die of the extrusion molding apparatus (die width is 130 mm), Random polypropylene (60 μm) / polymer composition (30 μm) / polyethylene terephthalate (60 μm) were laminated in this order to form a three-layer structure, and (A) layer was a random polypropylene layer, (B) A layered structure composed of three layers in which the layer includes a hybrid polymer and (C) the layer is a polyethylene terephthalate layer. Manufactured.

  About the laminated structure obtained above, when the interface adhesive strength of the (B) layer and the (C) layer was measured, no adhesive force was expressed.

  The laminated structure of the present invention has extremely high adhesion strength between layers and hardly peels between layers. Therefore, packaging materials for food and medical drugs, packaging materials for clothing, packaging materials for other products, wallpaper, decorative plates, etc. For building materials, such as electrical insulation film, adhesive film and tape substrate, marking film, agricultural film, table cloth, raincoat, umbrella, curtain, covers, etc., metal plates and other materials and It can be effectively used for various applications such as laminating.

Claims (7)

(A) a layer containing an olefin polymer as a main constituent,
(B) a layer comprising a hybrid polymer [P] having a polyolefin segment [S ₁ ] and a polar polymer segment [S ₂ ],
(C) At least one selected from polar vinyl plastic, aromatic vinyl polymer, polyester, polyamide, polycarbonate, engineering plastic, biological polymer, thermoplastic elastomer, natural or artificial fiber, inorganic glass and metal Layer
Having at least part of a structure in which layers (A) / layers (B) / layers (C) are laminated in this order,
The polar polymer segment [S ₂ ] is obtained by radical (co) polymerizing one or more monomers including a radical polymerizable monomer having a reactive group,
The number average molecular weight of the polar polymer segment [S ₂ ] part calculated from ¹ H-NMR measurement of the hybrid polymer [P] is 300 or more and less than 3,000, and
The polyolefin segment [S ₁ ] has a polypropylene equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of from 7,000 to less than 40,000.
A laminated structure characterized by that. The hybrid polymer [P] is
The laminated structure according to claim 1, wherein the polyolefin segment [S ₁ ] and the polar polymer segment [S ₂ ] have a structure linked by a covalent bond. The reactive group of the polar polymer segment [S ₂ ] is at least one group selected from the group consisting of an isocyanate group, a carboxyl group, a hydroxyl group, an acid anhydride group, an epoxy group, an oxazoline group, a maleimide group, and an amino group. The laminated structure according to claim 1 or 2, wherein The solubility parameter of the polar polymer segment [S ₂ ] is 18.0 to 25.0 ((J / cm ³ ) ^1/2 ), The multilayer structure according to any one of claims 1 to 3 body. 5. The laminate according to claim 1, wherein the polar polymer segment [S ₂ ] has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 25 ° C. or less. Structure. The polyolefin segment [S ₁ ] is a crystalline polyolefin residue having a temperature at an endothermic peak position due to a melting point (Tm) measured by a differential scanning calorimeter (DSC) of 50 ° C. or higher. The laminated structure according to any one of claims 1 to 5. The laminated structure according to claim 6, wherein the polyolefin segment [S ₁ ] is a propylene-based polymer residue.