JP2005290039A - Modified polyolefin composition, adhesive layer composed of the same and layered product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified polyolefin composition (C) excellent in a total balance of adhesion to a polyamide layer and/or a polar group-containing polymer (D) such as an ethylene-vinyl alcohol copolymer, adhesion to a layer composed of a polymer having a saturated cyclic hydrocarbon residue and suppression of adhesive strength after filling chemicals, and to provide an adhesive layer and a layered product using the composition. <P>SOLUTION: The modified polyolefin composition (C) having specific physical properties contains 15-60 wt% based on the total composition of a polymer (A) having a saturated cyclic hydrocarbon residue, wherein at least a part of the remainder of the composition is a modified ethylene polymer (B) grafted with an unsaturated carboxylic acid and/or a derivative thereof. The adhesive layer and the layered product are obtained from the modified polyolefin composition (C). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a modified polyolefin composition and an adhesive layer and a laminate using the composition. More specifically, it has excellent adhesion to a polyamide layer and / or an ethylene / vinyl alcohol copolymer, and excellent adhesion to a layer made of a polymer having a saturated hydrocarbon residue, and adhesion after chemical filling. The present invention relates to a modified polyolefin composition capable of suppressing a decrease in force, and an adhesive layer and a laminate using the composition.

Conventionally, for the purpose of improving adhesion to a polyamide or an ethylene / vinyl alcohol copolymer layer, a high-pressure low-density polyethylene and a linear ethylene-based polymer and an amorphous or low-crystalline ethylene / α-olefin copolymer are used. It is known to use a modified polyolefin composition obtained by modifying a polymer as an adhesive layer (see Patent Document 1).
In addition, by using an ethylene / vinyl alcohol copolymer layer and a cyclic olefin copolymer layer as each layer of the laminate, it is already possible to form a laminate excellent not only in oxygen barrier properties but also in fragrance retention. As a known adhesive layer of this laminate, a layer made of linear ultra-low density polyethylene or an acid-modified product thereof is used (see Patent Document 2).
On the other hand, it is already known that a modified cyclic olefin polymer obtained by modifying a composition comprising a cyclic olefin resin and a specific polyolefin with an unsaturated carboxylic acid or the like has adhesiveness (see Patent Document 3). ).
Although these adhesive compositions are excellent in adhesiveness to ethylene / vinyl alcohol copolymers, their adhesive strength to cyclic olefin copolymers after chemical filling is still insufficient, and further improvements are desired. Yes.

Japanese Patent Laid-Open No. 08-053584 Japanese Patent Laid-Open No. 10-059344 Japanese Patent Application Laid-Open No. 06-1000074

  The object of the present invention is to adhere to a polyamide layer and / or a polar group-containing polymer such as an ethylene / vinyl alcohol copolymer, to a layer made of a polymer having a saturated hydrocarbon residue, and after filling with a chemical. It is in providing the modified polyolefin composition excellent in all the balance of the adhesive force fall suppression in, the adhesive layer formed by shape | molding the composition, and the laminated body containing the said adhesive layer.

The present inventors have intensively studied, and by using a specific composition, adhesion to a polyamide layer and / or a polar group-containing polymer such as an ethylene / vinyl alcohol copolymer, and a heavy hydrocarbon having a saturated hydrocarbon residue. The present inventors have found that a composition excellent in all the balances of adhesiveness with a layer composed of coalescence and suppression of decrease in adhesive strength after chemical filling can be obtained, and the present invention has been completed.
That is, the present invention contains a polymer (A) having a saturated cyclic hydrocarbon residue in an amount of 15 to 60% by weight based on the total composition, and at least a part of the rest of the composition comprises an unsaturated carboxylic acid and / or Or a modified ethylene polymer (B) graft-polymerized with a derivative thereof, wherein the content of the group derived from the unsaturated carboxylic acid and / or derivative thereof in the total composition is 0.01 to 4% by weight, A modified polyolefin composition (C) having a melt flow rate (190 ° C., 2.16 kg load) of 0.1 to 15 g / 10 min. More specifically, it is an adhesive layer formed by molding the modified polyolefin composition (C), and the dispersed phase composed of the polymer (A) having a saturated cyclic hydrocarbon residue in the composition layer (C) is layered. The ratio of the long side length to the short side length of the polymer (A) phase having a phase-separated structure dispersed in and having a saturated cyclic hydrocarbon residue ((length of long piece) / (length of short piece) The adhesive layer is preferably 3 or more, and further, a laminate comprising the adhesive layer.

  The modified polyolefin composition of the present invention has an adhesive property with a polyamide layer and / or a polar group-containing polymer such as an ethylene / vinyl alcohol copolymer, and an adhesive property with a layer made of a polymer having a saturated cyclic hydrocarbon residue. Excellent balance of adhesive strength reduction after chemical filling. Therefore, when the modified polyolefin composition of the present invention is used as an adhesive layer between a layer made of a polymer having a saturated cyclic hydrocarbon residue and a layer made of a polyethylene resin, the fragrance component is filled and aged. It is possible to obtain a molded article in which the decrease in adhesive strength is effectively eliminated. Further, the composition of the present invention has a saturated cyclic hydrocarbon residue because it is a composition excellent in adhesiveness and moldability with a polar group-containing polymer such as polyamide or ethylene / vinyl alcohol copolymer. By using it as an adhesive layer of a laminate comprising a polar group-containing polymer such as a polymer, polyamide, or ethylene / vinyl copolymer, a molded product having excellent fragrance retention properties can be obtained.

Hereinafter, the present invention will be described in more detail.
The modified polyolefin composition (C) of the present invention contains a polymer (A) having a saturated cyclic hydrocarbon residue, and at least a part of the rest of the composition is grafted with an unsaturated carboxylic acid and / or a derivative thereof. The composition is a modified ethylene polymer (B).

Polymer having saturated cyclic hydrocarbon residue (A)
The polymer (A) having a saturated cyclic hydrocarbon residue used in the present invention has a cyclic structure (alicyclic structure) composed of a carbon-carbon saturated bond. The melt flow rate of the polymer (A) having a saturated cyclic hydrocarbon residue used in the present invention (value measured at 260 ° C. under a load of 2.16 kg according to ASTM D1238) is usually 1 to 40 g / 10 minutes, preferably Is preferably 5 to 40 g / 10 min, more preferably 10 to 40 g / 10 min. When the MFR is in this range, the phase composed of the polymer (A) having a saturated cyclic hydrocarbon residue having low chemical permeability is dispersed in a layer in the composition (C) layer when formed into a molded body. This is preferable because the path through which the chemical permeates through the composition (C) layer becomes long.

  The content of the saturated cyclic hydrocarbon residue in the polymer (A) having a saturated cyclic hydrocarbon residue used in the present invention is usually 10 to 50 mol%, preferably 12 to 40 mol%, more preferably 15 ˜30 mol%. When the content of the saturated cyclic hydrocarbon residue is within this range, bubbles are generated due to the gas derived from the saturated cyclic hydrocarbon group remaining in the polymer (A) having the saturated cyclic hydrocarbon residue at the time of molding. This is preferable because the amount is small and a good appearance can be obtained.

The weight average molecular weight of a polymer having a saturated cyclic hydrocarbon residue (A) used in the present invention is usually 8x10 ⁴ ~25x10 ^4, is preferably 8x10 ⁴ ~20x10 ^4, more preferably at 8x10 ⁴ ~15x10 ^4. When the weight average molecular weight is within this range, the phase composed of the polymer (A) having a saturated cyclic hydrocarbon residue having low chemical permeability is layered in the composition (C) layer when formed into a molded body. Dispersing is preferable because the path through which the chemical permeates the composition (C) layer becomes longer.

Although it does not specifically limit as a polymer (A) which has a saturated cyclic hydrocarbon residue used for this invention, For example, the following resin can be illustrated. The polymer (A) having a saturated cyclic hydrocarbon residue may have a polar group such as a carboxylic acid ester group.
(B) Addition copolymer of α-olefin and cyclic olefin (b) Ring-opening polymer of cyclic olefin and hydrogenated product thereof (c) Vinyl alicyclic hydrocarbon polymer (d) Vinyl aromatic hydrocarbon type Hydrogenated product of polymer (e) Monocyclic cyclic conjugated diene polymer or hydrogenated product thereof

  The α-olefin used in the polymer (A) having a saturated cyclic hydrocarbon residue of the present invention may be linear or branched and is an α-olefin having 2 to 20 carbon atoms. In these, a C2-C4 linear alpha olefin is preferable and ethylene is especially preferable. Moreover, you may use an alpha olefin individually by 1 type or in combination of 2 or more types.

  As the cyclic olefin, for example, those described in paragraphs [0032] to [0054] of JP-A-07-145213 can be used. The cyclic olefin may be used alone or in combination of two or more different cyclic olefins.

  As the vinyl alicyclic hydrocarbon compound, a structure in which a monocyclic cycloalkyl group, an alkyl-substituted cycloalkyl group, an icroalkenyl group, or an alkyl-substituted scroalkenyl group is bonded to a vinyl group or an α-alkyl-substituted vinyl group The compound which has can be mentioned. These can be polymerized singly or in combination of two or more.

  The vinyl aromatic hydrocarbon compound is a compound in which an aromatic hydrocarbon substituent is bonded to a vinyl group or an α-alkyl-substituted vinyl group. These can be used alone or in combination of two or more.

  Examples of the monocyclic conjugated diene compound include monocyclic conjugated dienes which may have a substituent, such as cyclopentadiene, cyclohexadiene, cycloheptadiene, and cyclooctadiene. . These may be used singly or in combination of two or more.

  In addition, the polymer (A) having a saturated cyclic hydrocarbon residue used in the present invention is a structural unit derived from another copolymerizable monomer as necessary, as long as the object of the present invention is not impaired. You may have.

  The production method of the polymer (A) having a saturated cyclic hydrocarbon residue used in the present invention is not particularly limited, and can be produced by a conventionally known method. When obtained by an addition polymerization reaction, it can be obtained by a known method using a conventionally known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst, and when obtained by a ring-opening polymerization reaction, Copolymerization can be carried out in the presence of a ring-opening polymerization catalyst, and further hydrogenation can be carried out in the presence of a conventionally known hydrogenation catalyst. In addition, when obtaining a vinyl alicyclic hydrocarbon polymer or vinyl aromatic hydrocarbon polymer, for example, a known polymerization method such as radical polymerization, coordination anion polymerization, cationic polymerization, anion polymerization or the like can be applied. The aromatic ring can be hydrogenated by a conventionally known method. Similarly, a polymerization method of a polymer of a monocyclic conjugated diene compound can be performed by a conventionally known method, and hydrogenation can be performed by a known method.

  The polymer (A) having a saturated cyclic hydrocarbon residue used in the present invention can be used by mixing polymers having several different saturated cyclic hydrocarbon residues.

Modified ethylene polymer (B)
The modified ethylene polymer (B) used in the present invention is an ethylene polymer graft-modified with an unsaturated carboxylic acid and / or a derivative thereof.

  The ethylene polymer used for graft modification may be a homopolymer of ethylene or a copolymer of ethylene and another olefin. Examples of other olefins copolymerized with ethylene include α-olefins having 2 to 10 carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. These α-olefins may be used alone or in combination of two or more. The content of the other α-olefin is usually 25 mol% or less, preferably 4 to 25 mol%, more preferably 6 to 25 mol%. The ethylene polymer used for graft modification in the present invention is preferably an ethylene / α-olefin copolymer, and the α-olefin copolymerized with ethylene is propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene is particularly preferred.

  The melt flow rate (value measured at 190 ° C. and load 2.16 kg according to ASTM D1238) of the ethylene-based polymer used for graft modification is usually 0.1 to 30 g / 10 minutes, preferably 0.3 to 25 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes. When the MFR is within this range, it is possible to obtain a satisfactory MFR as the modified ethylene polymer (B).

The density of the ethylene-based polymer used for graft modification is usually 0.860 to 0.970 g / cm ³ , preferably 0.860 to 0.930 g / cm ³ , and more preferably 0.860 to 0.905 g. / Cm ³ . Since the polymer (A) having a saturated cyclic hydrocarbon residue used in the present invention has high rigidity, when the modified polyolefin composition (C) is used, a polar group-containing polymer such as an ethylene / vinyl alcohol copolymer is used. There exists a tendency for adhesiveness with a union (D) to be spoiled. However, if the density is within this range, it is preferable because the adhesiveness is excellent. In particular, in the present invention, the lower the density, the better the adhesion with the polar group-containing polymer (D) such as an ethylene / vinyl alcohol copolymer.

The weight average molecular weight of the ethylene-based polymer used for graft modification is usually 3.0 × 10 ^{4 to} 30 × 10 ⁴ , preferably 3.1 × 10 ^{4 to} 25 × 10 ⁴ , and more preferably 3.2 × 10 ^{4 to} 20 × 10 ⁴ . It is preferable for the weight average molecular weight to be in this range since it is possible to obtain a molecular weight that is satisfactory for the modified ethylene polymer (B).

  The method for producing the ethylene polymer used for graft modification is not particularly limited and can be produced by a conventionally known method. For example, known transition metals such as Ziegler catalysts and metallocene catalysts can be used. It can be obtained by a known method using a catalyst, and a commercially available resin can be used as it is.

  Examples of unsaturated carboxylic acids and / or derivatives thereof used as graft monomers include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having carboxylic acid groups and alkyl alcohols, and unsaturated compounds having one or more carboxylic anhydride groups. Examples of the unsaturated group include a vinyl group, vinylene group, and unsaturated cyclic hydrocarbon group. Specific examples of the compound include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endocis-bicyclo [2.2.1] hept Unsaturated carboxylic acids such as -5-ene-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrides, esters and the like. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. These unsaturated carboxylic acids and / or derivatives thereof can be used singly or in combination of two or more. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferably used. The content of the unsaturated carboxylic acid and / or derivative thereof can be easily controlled by, for example, appropriately selecting the grafting conditions.

  The method for grafting a graft monomer selected from an unsaturated carboxylic acid and / or a derivative thereof is not particularly limited, and conventionally known graft polymerization methods such as a solution method and a melt-kneading method can be employed. For example, there are a method in which a polymer is melted and a grafting monomer is added thereto for a grafting reaction, or a solution is prepared by dissolving the polymer in a solvent and a grafting monomer is added thereto for a grafting reaction.

  The content of the unsaturated carboxylic acid or derivative thereof in the modified ethylene polymer (B) used in the present invention is usually 0.01 to 5% by weight with respect to 100% by weight of the modified ethylene polymer (B). Preferably it is 0.01 to 3 weight%, More preferably, it is 0.01 to 1 weight%.

  The melt flow rate (MFR) at a load of 2.16 kg and 190 ° C. according to ASTM D1238 of the modified ethylene polymer (B) used in the present invention is usually 0.1 to 30 g / 10 minutes, preferably 0.1 to 20 g. / 10 minutes, more preferably 0.1 to 10 g / 10 minutes. If the MFR of the modified ethylene polymer (B) is within this range, the polymer (A) having a saturated cyclic hydrocarbon residue with low chemical permeability in the composition (C) layer when formed into a molded body (A) ) Is preferably dispersed in a layered manner because the path through which the chemical permeates the composition (C) layer becomes longer.

The density of the modified ethylene polymer (B) is usually 0.860 to 0.970 g / cm ³ , preferably 0.860 to 0.930 g / cm ³ , and more preferably 0.860 to 0.905 g / cm ³ . cm ³ . Since the polymer (A) having a saturated cyclic hydrocarbon residue used in the present invention has high rigidity, when the modified polyolefin composition (C) is used, a polar group-containing polymer such as an ethylene / vinyl alcohol copolymer is used. There exists a tendency for adhesiveness with a union (D) to be spoiled. However, if the density is within this range, it is preferable because the adhesiveness is excellent. In particular, in the present invention, the lower the density, the better the adhesion with the polar group-containing polymer (D) such as an ethylene / vinyl alcohol copolymer.

The weight average molecular weight of the modified ethylene polymer (A) used in the present invention is usually 3.0 × 10 ^{4 to} 30 × 10 ⁴ , preferably 3.1 × 10 ^{4 to} 30 × 10 ⁴ , more preferably 3.2 × 10 ^{4 to} 30 × 10 ⁴ . . When the weight average molecular weight is in this range, the phase composed of the polymer (A) having a saturated cyclic hydrocarbon residue having low chemical permeability is layered in the composition (C) layer when formed into a molded body. Dispersing is preferable because the path through which the chemical permeates the composition (C) layer becomes longer.

  The modified ethylene polymer (B) used in the present invention may be blended with other resins, elastomers, etc. as long as it has the above physical properties as a whole. Other resins, elastomers and the like may be modified with an unsaturated carboxylic acid and / or a derivative thereof, or may be unmodified. In the present invention, the content in the composition (C) of the polymer (A) having a saturated cyclic hydrocarbon residue in the case of the modified polyolefin composition (C), and the unsaturated carboxylic acid and / or derivative thereof It is an indispensable requirement that both of the contents are specific, and other resins, elastomers and the like may be blended for the purpose of controlling the physical properties of the composition (C).

  Furthermore, it is possible to add a known process stabilizer, heat stabilizer, heat aging agent, filler, etc. to the modified ethylene polymer (B) used in the present invention within a range not to impair the purpose of the present invention. It is.

Modified polyolefin composition (C)
The modified polyolefin composition (C) of the present invention is a composition comprising at least the polymer (A) having the above-mentioned saturated cyclic hydrocarbon residue and the modified ethylene polymer (B).

  In the modified polyolefin composition (C) of the present invention, the polymer (A) component having the saturated cyclic hydrocarbon residue is usually 15 to 60% by weight, preferably 18 to 55% by weight, more preferably 20 to 20%. Contains 50% by weight. Further, it is a composition comprising the above-mentioned modified ethylene polymer (B) usually at most 85% by weight, preferably at most 82% by weight, more preferably at most 80% by weight. When the blending amount is within the above range, the modified polyolefin composition for adhesion of the present invention is a polymer having a saturated cyclic hydrocarbon residue, a polar group-containing polymer such as a polyamide and an ethylene / vinyl alcohol copolymer (D )

  The content of the group derived from the unsaturated carboxylic acid and / or derivative thereof with respect to 100% by weight of the modified polyolefin composition (C) is usually 0.01 to 4% by weight, preferably 0.01 to 2.5% by weight. %, More preferably 0.01 to 0.8% by weight. When the content of the group derived from the unsaturated carboxylic acid and / or derivative thereof is in the above range, the modified polyolefin composition (C) of the present invention contains a polar group such as polyamide or ethylene / vinyl alcohol copolymer. A high adhesive strength is exhibited with respect to the polymer (D). Control of the content of the group derived from the unsaturated carboxylic acid and / or derivative thereof can be easily performed, for example, by appropriately selecting the grafting conditions.

  The melt flow rate of the modified polyolefin composition (C) of the present invention thus obtained under the conditions of 190 ° C. and 2.16 kg is usually 0.1 to 15 g / 10 minutes, preferably 0.3 to 10 g / 10 minutes. More preferably, it is 0.5 to 5 g / 10 min. If the MFR of the modified polyolefin composition (C) is within this range, the composition is excellent in moldability during extrusion molding.

  A conventionally well-known method can be employ | adopted for the manufacturing method of the modified polyolefin composition (C) of this invention. For example, a polymer having a saturated cyclic hydrocarbon residue (A), a modified ethylene-based polymer (B), or other components blended as necessary are collectively or sequentially added to a Henschel mixer, a V-blender. , Ribbon blender, tumbler blender, etc. Or it can obtain by grind | pulverizing the obtained resin lump.

  In addition, the modified polyolefin composition (C) of the present invention can be blended with other resins, elastomers and the like that can be mixed within a range that does not impair the object of the present invention. In the present invention, both the content of the polymer (A) having a saturated cyclic hydrocarbon residue in the modified polyolefin composition (C) and the content of the unsaturated carboxylic acid and / or its derivative are specified. Therefore, in order to control the physical properties of the composition (C), other resins, elastomers and the like may be blended. The amount of other resins, elastomers and the like is usually 80% by weight or less, preferably 78% by weight or less, and more preferably 75% by weight or less with respect to 100% by weight of the modified polyolefin composition (C) of the present invention. Even if the blending of the other resin is the same as the polymer (A) having the above-mentioned saturated cyclic hydrocarbon residue and the modified ethylene polymer (B), the modified polyolefin composition is changed from (A) and (B). It may be a mixture after obtaining the product (C).

  Other resins, elastomers, and the like used in the modified polyolefin composition (C) of the present invention are not particularly limited, and examples thereof include ethylene polymers. The melt flow rate (measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238), density, and weight average molecular weight of the ethylene-based polymer are within the range of the modified ethylene-based polymer (B). Is desirable. When the physical properties of other resins and elastomers to be blended are in the range of the modified ethylene polymer (B), it is possible to have an optimum phase separation structure.

  In the present invention, the modified polyolefin composition (C) is used by adding to a normal polyolefin such as a heat stabilizer, a weather stabilizer, a heat aging agent, an antistatic agent, a filler, a nucleating agent, a pigment, and a dye. The various compounding agents to be used can be blended within a range not impairing the object of the present invention.

Laminate The modified polyolefin composition (C) of the present invention is suitably used as an adhesive layer of a laminate.

  Further, the adhesive layer formed by molding the modified polyolefin composition (C) of the present invention has a phase separation structure in which the polymer (A) phase having a saturated cyclic hydrocarbon residue is dispersed in a layer shape, and a saturated cyclic The ratio of the length of the long side to the length of the short side of the polymer (A) phase having a hydrocarbon residue ((length of long piece) / (length of short piece)) is usually 3 or more, preferably 5 or more It is desirable that When the ratio of the length of the long side to the length of the short side is within this range, the adhesive layer made of the modified polyolefin composition (C) of the present invention is filled with a fragrance component and the like when it is aged. It is possible to maintain and suppress a decrease in adhesive strength.

  In the present invention, in order to obtain a molded body in which the ratio of the length of the long side to the length of the short side is in the above range, the molding speed when molding the molded body is 0.5 m / min or more. There is a need.

  As the resin of the other thermoplastic resin layer constituting the laminate of the present invention, various thermoplastic resins can be used and are not particularly limited. Examples thereof include polar group-containing resins such as polyester, polyamide, and ethylene / vinyl alcohol copolymer, polymers having a saturated hydrocarbon residue such as cyclic olefin copolymer, and ethylene polymers. In the present invention, a laminate having at least a layer composed of the polar group-containing resin (D), an adhesive layer of the present invention, and a layer composed of a polymer having a saturated hydrocarbon residue is a preferred embodiment. Of the polar group-containing resins (D), polyamide or ethylene / vinyl alcohol copolymer is particularly preferably used.

  Examples of the polyamide constituting the laminate of the present invention include nylon 6, nylon 66, MXD nylon (metaxylylenediamine copolymer nylon), and the like.

  As the ethylene / vinyl alcohol copolymer constituting the laminate of the present invention, a copolymer containing 20 to 50 mol%, preferably 25 to 48 mol% of a polymer unit derived from ethylene is desirable. These can be produced by saponifying a corresponding ethylene / vinyl acetate copolymer by a conventional method.

  As the polymer having a saturated hydrocarbon residue constituting the laminate of the present invention, the above-mentioned polymer (A) having a saturated hydrocarbon residue can be used. Specifically, an α-olefin and a cyclic compound can be used. Addition copolymer of olefin, ring-opening polymer of cyclic olefin and hydrogenated product thereof, vinyl alicyclic hydrocarbon polymer, hydrogenated vinyl aromatic hydrocarbon polymer, monocyclic cyclic conjugated diene compound Or a hydrogenated product thereof.

When the laminate of the present invention includes a layer made of an ethylene polymer, the ethylene polymer constituting the laminate has an ethylene content of 70 mol% or more, usually 70 to 100 mol%, preferably It is preferable that it is a homopolymer or copolymer of ethylene which is 80-100 mol%. Specifically, high density polyethylene, linear low density polyethylene, high pressure low density polyethylene, ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate copolymer, ethylene / acrylic acid copolymer, Examples include ionomer resins. Among these, low density polyethylene, EVA, particularly linear low density polyethylene having a density of 0.930 g / cm ³ or less, high pressure method low density polyethylene, or EVA is preferably used.

  The laminate of the present invention is preferably a layer comprising a polymer (A) having a saturated hydrocarbon residue, a layer of the modified polyolefin composition (C) of the present invention, a polyamide or an ethylene / vinyl alcohol copolymer. And the like, which are laminated in the order of layers composed of the polar group-containing polymer (D).

  The laminate of the present invention can be produced by various known methods. For example, it can be produced by a known coextrusion method such as inflation molding, cast molding, tube molding, extrusion coating molding, etc. Also, after forming a single-layer or multi-layer film, etc., dry laminating by heating, etc. It can be illustrated. In the present invention, it is preferable to use coextrusion molding.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all to these Examples, unless the summary is exceeded.

Substances used in Examples and Comparative Examples are shown below. In addition, unless otherwise indicated, all were prepared by polymerization according to a conventional method.
PE-1: Ethylene / Butene Copolymer
(MFR 4.0 g / 10 min at 190 ° C. and 2.16 kg load,
Density 0.885 g / cm ³ ,
(Weight average molecular weight 11 × 10 ⁴ , butene content 10 mol%)
PE-2: Polyethylene homopolymer
(MFR 15.0 g / 10 min at 190 ° C. and 2.16 kg load,
Density 0.965 g / cm ³ , weight average molecular weight 5.0 × 10 ⁴ )
PE-3: Ethylene / propylene copolymer
(MFR 3.0 g / 10 min at 190 ° C., 2.16 kg load,
Density 0.870 g / cm ³ ,
Weight average molecular weight 12 × 10 ⁴ , propylene content 8.6 mol%)
PE-4: Ethylene / hexene copolymer
(MFR 4.0 g / 10 min at 190 ° C. and 2.16 kg load,
Density 0.920 g / cm ³ ,
Weight average molecular weight 9.0 × 10 ⁴ , hexene content 3.0 mol%)
COC-1: ethylene / tetracyclododecene copolymer
(MFR 15.0 g / 10 min at 260 ° C., 2.16 kg load,
Density 1.020 g / cm ³ , weight average molecular weight 12 × 10 ⁴ ,
Tetracyclododecene content 20 mol%)
EVOH: Ethylene / vinyl alcohol copolymer
(Product name EVAL F101A, manufactured by Kuraray Co., Ltd.,
MFR 1.6 g / 10 min at 190 ° C. and 2.16 kg load,
Density 1.190 g / cm ³ , ethylene copolymerization ratio 32 mol%)
LDPE: High-pressure low-density polyethylene
(MFR 3.3 g / 10 min at 190 ° C., 2.16 kg load,
Density 0.921 g / cm ³ )

(Example 1)
<Production of Modified Ethylene / Butene Copolymer (MAH-PE-1)>
An ethylene / butene copolymer (PE-) produced using a transition metal catalyst and having a melt flow rate of 4.0 g / 10 min and a density of 0.885 g / cm ³ measured at 190 ° C. and 2.16 kg. 1) 100% by weight, maleic anhydride 0.05% by weight, and peroxide (trade name Perhexin 25B, manufactured by NOF Corporation) 0.07% by weight were mixed with a Henschel mixer, and the resulting mixture was A modified ethylene / butene copolymer (MAH-PE-1) was obtained by melt graft modification with a 65 mmφ single screw extruder set at 250 ° C. When the graft amount of the modified ethylene / butene copolymer (MAH-PE-1) was measured by IR analysis, the maleic anhydride graft amount was 0.5% by weight. The melt flow rate measured under the conditions of 190 ° C. and 2.16 kg was 2.0 g / 10 min, and the weight average molecular weight measured by GPC analysis was 11 × 10 ⁴ .

<Production of Modified Polyolefin Composition (C)>
70% by weight of the modified ethylene / butene copolymer (MAH-PE-1) obtained as described above, a melt flow rate measured under the conditions of 260 ° C. and 2.16 kg, 15 g / 10 min, and a density of 1 30% by weight of a polymer having a saturated cyclic hydrocarbon residue (COC-1) of 0.020 g / cm ³ , 0.05% by weight of Irganox 1010 (trade name, manufactured by Ciba Geigy, Japan), Irgaphos 168 (Trade name, manufactured by Ciba-Geigy Japan, Stabilizer) and synthetic hydrotalcite (trade name DHT-4A, manufactured by Kyowa Chemical Co., Ltd., stabilizer) 0.03% at 230 ° C. using a single screw extruder By melt-kneading, a modified polyolefin composition (C) was obtained. This composition (C) had a melt flow rate of 1.6 g / 10 min measured at 190 ° C. and 2.16 kg, and a density of 0.920 g / cm 3.
Next, using the resulting modified polyolefin composition (C), the adhesion strength with an ethylene / vinyl alcohol copolymer (EVOH) and a polymer having a saturated cyclic hydrocarbon residue are obtained by the following method. The adhesion strength, the adhesion strength with the polymer having a saturated cyclic hydrocarbon residue after chemical filling, and the dispersion state observation of the polymer (A) having a saturated cyclic hydrocarbon residue in the adhesive layer were tested. The test results are shown in Table 1.

<Adhesive strength with ethylene / vinyl alcohol copolymer (EVOH)>
A three-layer film (film-1) is formed by coextrusion molding under the following molding conditions, and the interlayer adhesion strength (peeling) between the EVOH layer of the obtained three-layer film and the adhesive layer made of the modified polyolefin composition (C) Strength) was obtained by T-peeling at a peeling rate of 300 mm / min.
[Molding condition]
EVOH (outer layer) / modified polyolefin composition (C) (intermediate layer) / high pressure method LDPE (inner layer)
= 40/40/160 μm
T-die forming machine: die diameter 40mmφ extruder (outer layer)
Set temperature ... 220 ° C
Die diameter 40mmφ extruder (intermediate layer)
Set temperature ... 220 ° C
Die diameter 40mmφ extruder (inner layer)
Set temperature ... 220 ° C
Molding speed: 5m / min

<Adhesive strength with polymer (COC-2) having saturated cyclic hydrocarbon residue>
A three-layer film (film-2) is formed by coextrusion molding under the following molding conditions, and the resulting three-layer film comprises a polymer layer having a saturated cyclic hydrocarbon residue and a modified polyolefin composition (C). The interlayer adhesion strength (peeling strength) with the adhesive layer was determined by T-peeling at a peeling rate of 300 mm / min.
The polymer (COC-2) having a saturated cyclic hydrocarbon residue as the outer layer is 100% by weight of the polymer (COC-1) having a saturated cyclic hydrocarbon residue, and Irganox 1010 (trade name, Japan). This is a composition obtained by dry blending 0.05% by weight of Ciba Geigy, stabilizer).
[Molding condition]
COC-2 (outer layer) / modified polyolefin composition (C) (intermediate layer) / high pressure method LDPE (inner layer)
= 20/20/80 μm
T-die forming machine: die diameter 40mmφ extruder (outer layer)
Set temperature ... 230 ℃
Die diameter 40mmφ extruder (intermediate layer)
Set temperature ... 230 ℃
Die diameter 40mmφ extruder (inner layer)
Set temperature ... 220 ° C
Molding speed: 20m / min

<Adhesion strength with polymer (COC-2) having saturated cyclic hydrocarbon residue after chemical filling>
Two three-layer films (film-2) using a polymer (COC-2) having a saturated cyclic hydrocarbon residue obtained under the same conditions as described above were placed with the LDPE side facing each other [COC-2 / The composition / LDPE // LDPE / the composition / COC-2] is superposed and the three sides of the film are heat sealed with an impulse heat sealer, and then octyldodecanol is placed between the two films. (Product name: Calcoal 200GD, manufactured by Kao Corporation) was filled, and one side of the remaining film was heat-sealed with an impulse sealer to obtain a packaged body of a superposed film filled with octyldodecanol. The package filled with the obtained octyldodecanol was allowed to stand in an atmosphere of 50 ° C. for 1 day, and then the polymer (COC-2) layer having a saturated cyclic hydrocarbon residue and a modification of film-2 used as the package The interlayer adhesion strength (peeling strength) with the adhesive layer made of the polyolefin composition (C) was determined by T-type peeling at a peeling rate of 300 mm / min.

<Observation of dispersion state of polymer (COC-1) having saturated cyclic hydrocarbon residue in adhesive layer>
Using the three-layer film (film-2) using the polymer (COC-2) having the saturated cyclic hydrocarbon residue, the saturated cyclic hydrocarbon residue in the adhesive layer made of the modified polyolefin composition (C) The dispersion state in the cross section perpendicular to the extrusion direction of the polymer (A) phase having a group was observed with a transmission electron microscope (H-7000, manufactured by Hitachi, Ltd.).
As a result of observation, the polymer (A) phase having a saturated cyclic hydrocarbon residue is an island phase, and the polymer (A) phase having a saturated cyclic hydrocarbon residue is further dispersed in a layered structure. It was. The length of the long piece and the short side of the polymer (A) phase having a saturated cyclic hydrocarbon residue which is an island phase are measured, and the ratio of the length of the long piece to the length of the short side ((long piece (Length) / (length of short side)) was calculated. The results are shown in Table 1.

(Example 2, Comparative Examples 1-2)
Example 1 except that the polymer (COC-1) having a saturated cyclic hydrocarbon residue and the modified ethylene / butene copolymer (MAH-PE-1) were used in the proportions shown in Table 1 in Example 1. In the same manner as above, a modified polyolefin composition (C) was obtained. Table 1 shows the melt flow rate and density measured under the conditions of 190 ° C. and 2.16 kg of the resulting modified polyolefin composition (C) and the results of various tests conducted in the same manner as in Example 1.

(Example 3)
<Production of modified polyethylene homopolymer (MAH-PE-2)>
A polyethylene homopolymer (PE-2) produced using a transition metal catalyst and having a melt flow rate of 15 g / 10 min and a density of 0.965 g / cm ³ measured at 190 ° C. and 2.16 kg, A modified ethylene homopolymer (MAH-PE-2) was obtained by graft modification with maleic anhydride by a solution modification method in a toluene solvent. When the grafting amount of this modified ethylene homopolymer (MAH-PE-2) was measured by IR analysis, the grafting amount of maleic anhydride was 2.0% by weight. Moreover, the melt flow rate measured on condition of 190 degreeC and 2.16 kg was 4.0 g / 10min. The weight average molecular weight measured by GPC analysis was 5.0 × 10 ⁴ .

<Production of Modified Polyolefin Composition (C)>
5% by weight of the modified ethylene homopolymer (MAH-PE-2) obtained as described above, a melt flow rate measured at 260 ° C. and 2.16 kg, 15 g / 10 minutes, and a density of 1.020 g. The melt flow rate measured under the conditions of 190 ° C. and 2.16 kg produced using 30% by weight of a polymer (COC-1) having a saturated cyclic hydrocarbon residue of / cm ³ and a transition metal catalyst is 3. Modified polyolefin composition in the same manner as in Example 1 except that 65% by weight of unmodified ethylene / propylene copolymer (PE-3) having a density of 0 g / 10 min and a density of 0.870 g / cm ³ was used. (C) was obtained. Table 1 shows the melt flow rate and density measured under the conditions of 190 ° C. and 2.16 kg of the resulting modified polyolefin composition (C) and the results of various tests conducted in the same manner as in Example 1.

Example 4
In Example 3, a polymer (COC-1) having a saturated cyclic hydrocarbon residue, a modified polyethylene homopolymer (MAH-PE-2), and an unmodified ethylene / propylene copolymer (PE-3) were used as the first. A modified polyolefin composition (C) was obtained in the same manner as in Example 3, except that the proportions shown in the table were used. Table 1 shows the melt flow rate and density measured under the conditions of 190 ° C. and 2.16 kg of the resulting modified polyolefin composition (C) and the results of various tests conducted in the same manner as in Example 1.

(Examples 5-6)
In Examples 3 and 4, instead of the unmodified ethylene / propylene copolymer (PE-3), the melt flow rate measured under the conditions of 190 ° C. and 2.16 kg produced using a metallocene catalyst was 4.0 g / A modified polyolefin composition (C) was obtained in the same manner as in Example 3 except that an unmodified ethylene / hexene copolymer (PE-4) having a density of 0.920 g / cm ³ was used for 10 minutes. . Table 1 shows the melt flow rate and density of these modified polyolefin compositions (C) obtained, measured at 190 ° C. and 2.16 kg, and the results of various tests carried out in the same manner as in Example 1.

(Comparative Example 3)
In Example 3, a modified polyethylene homopolymer (MAH-PE-2), an unmodified ethylene / propylene copolymer (PE-3) were used without using a polymer (COC-1) having a saturated cyclic hydrocarbon residue. ) Was used in the same manner as in Example 3 except that the modified polyolefin composition (C) was obtained. Table 1 shows the melt flow rate and density of the obtained composition (C) measured at 190 ° C. and 2.16 kg, and the results of various tests conducted in the same manner as in Example 1.

  The modified polyolefin composition (C) of the present invention is composed of a polymer having a polyamide layer and / or a polar group-containing polymer (D) such as an ethylene / vinyl alcohol copolymer and a saturated cyclic hydrocarbon residue. It is excellent in all the balance of adhesiveness with a layer to be formed and suppression of lowering of adhesive strength after chemical filling. Therefore, by using the modified polyolefin composition (C) of the present invention as an adhesive layer between a layer made of a polymer having a saturated cyclic hydrocarbon residue and a layer made of a polyethylene resin, the aromatic component is filled and Thus, it is possible to obtain a molded product in which the decrease in the adhesive strength is effectively eliminated. In addition, since the composition (C) of the present invention is a composition excellent in adhesiveness and moldability with a polar group-containing polymer (D) such as polyamide or ethylene / vinyl alcohol copolymer, it is saturated cyclic. It has excellent fragrance retention properties when used as an adhesive layer for polymers containing hydrocarbon residues, polar group-containing polymers (D) such as polyamide and ethylene / vinyl copolymers, and laminates made of polyethylene resins. A molded product can be obtained. The use of the laminate using the modified resin composition for adhesion of the present invention is not particularly limited, but a film, sheet, tube, container, etc. when filling a substance having an aroma component, and food packaging It can be preferably used for processing a film, a thermoformed cup, a cosmetic tube and the like.

Claims (6)

 The polymer (A) having a saturated cyclic hydrocarbon residue is contained in an amount of 15 to 60% by weight based on the total composition, and at least a part of the rest of the composition is graft-polymerized with an unsaturated carboxylic acid and / or a derivative thereof. Modified ethylene polymer (B), the content of the group derived from the unsaturated carboxylic acid and / or derivative thereof in the total composition is 0.01 to 4% by weight, and the melt flow rate (190 ° C. , 2.16 kg load) is a modified polyolefin composition (C) of 0.1 to 15 g / 10 min.   An adhesive layer formed by molding the modified polyolefin composition (C) according to claim 1, wherein a dispersed phase composed of a polymer (A) having a saturated cyclic hydrocarbon residue in the composition layer is dispersed in a layer form. Of the long side and the short side of the polymer (A) phase having a phase separation structure and having a saturated cyclic hydrocarbon residue ((long piece length) / (short piece length)) ) Is 3 or more.   A laminate comprising at least a layer comprising a polar group-containing polymer (D), a layer according to claim 2, and a layer comprising a polymer having a saturated hydrocarbon residue.   Three or more layers in which the layer composed of the polar group-containing polymer (D), the layer described in claim 2, and the layer composed of a polymer having a saturated hydrocarbon residue are laminated in this order. body.   The laminate according to claim 3 or 4, wherein the polar group-containing polymer (D) is at least one selected from a polyamide or an ethylene / vinyl alcohol copolymer.   The laminate according to any one of claims 3 to 6, wherein the composition according to claim 1 is coextruded as at least one layer.