JP2003064334A - Adhesive polymer composition and laminate using the same - Google Patents

Abstract

[PROBLEMS] To provide an adhesive polymer composition suitable as a laminating agent of a polyolefin resin and a gas barrier resin such as a polyamide resin, and to use the adhesive polymer composition. Provided is a laminate of a polyolefin resin and a gas barrier resin. An adhesive polymer composition containing the following components (A) and (B), and a laminate obtained by laminating the adhesive polyolefin-based resin layer and a gas barrier resin layer. (A) The content [M] (% by weight) of the unsaturated carboxylic acid unit determined from the peak area at a wave number of 1791 cm in the infrared absorption spectrum, and the wave number 1791c of the peak area at a wave number of 1785 cm separated by a curve fitting method
The ratio [X] to the peak area of m is expressed by the following formula (I)
And a modified ethylene polymer satisfying the relationship of (II): 5 to 95% by weight 0.50 ≦ 1-X (I);
25% by weight ≦ (1-X) M ≦ 10% by weight (II) (B) an ethylene polymer other than the component (A);
5% by weight

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various laminates containing layers of gas barrier resin such as polyamide resin, saponified ethylene-vinyl acetate copolymer, and polyester resin, particularly polyolefin resin and gas barriers thereof. TECHNICAL FIELD The present invention relates to an adhesive polymer composition suitable as an adhesive in the production of a laminate with a hydrophilic resin, and a laminate of a polyolefin resin using the adhesive polymer composition and these gas barrier resins.

[0002]

2. Description of the Related Art Conventionally, polyolefin resins such as ethylene resins and propylene resins have been variously used by taking advantage of their excellent moldability, mechanical properties, water vapor barrier properties, chemical resistance, heat sealing properties, etc. It is often used as a packaging / container material, but it is inferior in gas barrier properties such as oxygen gas and carbon dioxide gas, and content resistance properties such as flavor and aroma retention.
Further, there is a drawback that the design properties such as surface gloss and transparency are poor depending on the molding method and the type of resin.

As a method for improving these drawbacks of polyolefin resins, polyamide resins,
Ethylene-saponified vinyl acetate copolymer, polyester-based resin, polycarbonate-based resin, the form of a laminate is formed by laminating various resins such as polystyrene-based resin, in which the polyolefin-based resin and these various resins Due to the poor adhesion between the two, it has been practiced to form a laminated body with an adhesive layer interposed therebetween.

As the adhesive layer, conventionally,
Various adhesive compositions comprising a mixture of a modified ethylene-based resin and an unmodified ethylene-based resin with an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof are known, and further, among them, a uniform composition distribution is obtained. With the expectation that the adhesiveness will be improved by the property, a linear ethylene-α-olefin copolymer with a metallocene catalyst is used in place of the conventional Ziegler catalyst, etc., and its modified product and other unmodified ethylene resin are used. Many adhesive compositions comprising a mixture, a mixture of an unmodified product thereof and another modified ethylene resin, or a mixture of a modified product thereof and an unmodified product have been proposed (for example, JP-A-6-206946). Issue 6-206947
No. 6, No. 207058, No. 6-207062, No. 7-102133, No. 8-41261, No. 8-20.
No. 8915, No. 8-283868, No. 9-3137.
No., No. 9-3138, No. 9-87603, etc. ). However, any of the conventionally known adhesive compositions, particularly in the adhesion with a gas barrier resin such as a polyamide-based resin, an ethylene-vinyl acetate copolymer saponified product, and a polyester-based resin, has a sufficient market demand. The current situation is that we are not satisfied with the above.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art. Therefore, the present invention provides a polyamide resin, an ethylene-vinyl acetate copolymer saponified product,
And various laminates containing a layer of a gas barrier resin such as a polyester resin, particularly an adhesive polymer composition suitable as an adhesive in the production of a laminate of a polyolefin resin and these gas barrier resins, and It is an object of the present invention to provide a laminate of a polyolefin resin using the adhesive polymer composition and these gas barrier resins.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polymer composition using a specific modified ethylene polymer can achieve the above object. In other words, in the present invention, the following components (A) and (B) are used [however, the weight% of the two components is based on 100% by weight of the total of the two components. ] The adhesive polymer composition containing these, and
Any one selected from the group consisting of a polyolefin resin layer, a polyamide resin, a saponified product of an ethylene-vinyl acetate copolymer, and a gas barrier resin consisting of a polyester resin, with a layer of the adhesive polymer composition interposed therebetween. A gist of the present invention is a laminated body formed by laminating the resin layer.

(A) Density is 0.850 to 0.960 g /
cm ³ and the melt flow rate at 190 ° C. are 0.01 to
An ethylene polymer having a weight of 50 g / 10 minutes is modified by subjecting it to a graft reaction condition in the presence of an unsaturated carboxylic acid or a derivative thereof.
The content of the unsaturated carboxylic acid or its derivative unit was determined from the peak area of the 791cm ^-1 and [M] (wt%), the peak area of the wave number 1785 cm ^-1 that the peak of wavenumber 1791cm ^-1 was separated by curve fitting method Wave number 1
The ratio [X] to the peak area of 791 cm ⁻¹ satisfies the relationship of the following formula (I) and the following formula (II): 5 to 95% by weight 0.50 ≦ 1-X (I ) 0.25% by weight ≦ (1-X) M ≦ 10% by weight (II) (B) Density is 0.850 to 0.960 g / cm ³ , 19
Melt flow rate at 0 ° C is 0.01 to 50 g / 10
An ethylene-based polymer other than the component (A);
5-5% by weight

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The modified ethylene polymer as the component (A) which constitutes the adhesive polymer composition of the present invention is prepared by using an ethylene polymer as a modifier in the presence of an unsaturated carboxylic acid or a derivative thereof. It is obtained by subjecting the composition to a grafting condition and modifying the same.

The ethylene polymer subjected to the reaction conditions has a density of 0.850 to 0. 0 in terms of moldability, material strength, adhesiveness, etc. as an adhesive polymer composition.
960 g / cm ³ is essential, 0.850
~ 0.915 g / cm ³ , preferably JI
Melt flow rate measured according to SK7210 at 190 ° C. under a load of 21.18 N is 0.01 to 50 g / 1.
It is essential that the time is 0 minutes, and preferably 0.1 to 30 g / 10 minutes.

Specific examples of the ethylene-based polymer include ethylene, a homopolymer of ethylene such as branched low-density polyethylene and linear high-density polyethylene, and ethylene.
Copolymers with vinyl compounds such as vinyl acetate, acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and ethylene with propylene, 1-butene,
3-methyl-1-butene, 1-pentene, 4-methyl-
1-pentene, 4,4-dimethyl-1-pentene, 1-
Hexene, 4-methyl-1-hexene, 1-heptene,
Examples include linear ethylene-α-olefin copolymers with α-olefins having 3 to 18 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-octadecene. A linear ethylene-α-olefin copolymer is preferable.

Further, as the linear ethylene-α-olefin copolymer, ethylene and 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1
-Hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene or the like with an α-olefin having 6 to 12 carbon atoms, or further, for example, 1,4-hexadiene , 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,5-heptadiene, 1,4-octadiene,
7-methyl-1,6-octadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, 5-
Methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 5-
A copolymer of a non-conjugated diene such as isopropenyl-2-norbornene, which is a binary or ternary or higher copolymer, is preferable, and as the linear ethylene-α-olefin copolymer, it has been conventionally used widely. A copolymer using a metallocene catalyst is preferable to a known copolymer using a Ziegler catalyst.

Linear ethylene with metallocene catalyst
The α-olefin copolymer is described, for example, in JP-A-58-19.
309, 59-95292, 60-35005.
No. 60, No. 60-35006, No. 60-35007, No. 60-35008, No. 60-35009, No. 61-
130314, Japanese Patent Laid-Open No. 163088/1993,
European Patent Publication No. 420436, US Pat. No. 505
No. 5438 and International Publication WO91 / 04257
Described in the publication, using a metallocene-based catalyst, particularly a metallocene-alumoxane-based catalyst, or, for example,
A catalyst composed of a metallocene compound and a compound which reacts with the compound to form a stable anion, as described in International Publication WO92 / 01723, is used, for example, a gas phase method, a slurry method, a solution method, a high-pressure ion weight method. It can be produced by a polymerization method such as a legal method, and preferably by a high pressure ionic polymerization method.

Further, as the linear ethylene-α-olefin copolymer with the metallocene catalyst, those having a single peak in the elution curve of the temperature rising elution fractionation are preferable, and the temperature of the single peak is It is preferably 90 ° C. or lower.

Here, the temperature rising elution fractionation (Temperat
What is ure Rising Elution Fractionation (TREF)?
In known analytical methods, the polymer is, in principle, completely dissolved in the solvent at elevated temperature and then cooled to form a thin polymer layer on the surface of the inert carrier which has been in solution. At this time, the polymer layer is formed in the order of the highly crystalline component which is easily crystallized and the low crystalline or amorphous component which is hard to be crystallized. Then, when the temperature is raised continuously or stepwise,
Contrary to the above, elution from low crystalline or amorphous components,
Finally, the highly crystalline component elutes. The composition distribution of the polymer is analyzed from the elution curve drawn by the elution amount at each temperature and the elution temperature.For details of the measurement method, see, for example, the Journal of Applied Polymer Science, V
ol. 26, 4217-4231 (1981).

Specific examples of the unsaturated carboxylic acid or its derivative as a modifier include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, Tetrahydrophthalic acid, endocis-bicyclo [2.2.1]
Unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid and derivatives thereof such as anhydrides, acid halides, amides, imides and esters thereof are mentioned. And particularly maleic acid or its anhydride is preferred.

The graft reaction conditions are, for example, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxy) Dialkyl peroxides such as (oxyisopropyl) benzene, t-butylperoxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxybenzoate, t-butylperoxide Peroxyesters such as oxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane and 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3, 3, Diacyl peroxide such as 5,5-trimethylhexanoyl peroxide, octanoyl peroxide and benzoyl peroxide Kishido acids, t- butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,
Hydroperoxides such as 5-di (hydroperoxy) hexane, organic peroxides such as ketone peroxides such as methylethylketone peroxide and cyclohexanone peroxide, or 2,2′-azobisisobutyronitrile , 2,2'-azobis (isobutylamide) dihalide, 2,2'-azobis [2-methyl-N- (2-
Hydroxyethyl) propionamide], azodi-t-
An azo compound such as butane is used as the ethylene polymer 1
About 0.001 to 10 parts by weight is used with respect to 00 parts by weight, and the reaction is carried out in a molten state or a solution state, preferably in a molten state.

In the present invention, the graft reaction conditions satisfy the conditions in the infrared absorption spectrum described below as the component (A), so that the ethylene polymer and the unsaturated carboxylic acid or its modifier as a modifier are used. It is preferable to subject the derivative to a graft reaction condition in a state of being uniformly mixed. For example, in the reaction method in a molten state, a powdery one is used as the ethylene polymer, and the unsaturated carboxylic acid or its When the derivative is a solid such as maleic anhydride, which is preferable, it is preferably used in the form of fine powder, and after uniformly mixing them with a mixer such as a Henschel mixer, 160 ° C or higher, preferably 180 ° C or higher. More preferably, the reaction is carried out at a temperature of 200 ° C. or higher.

The modified ethylene polymer as the component (A) in the present invention has a content [M] of the unsaturated carboxylic acid or its derivative unit obtained from the peak area at a wave number of 1791 cm ^-1 in the infrared absorption spectrum. (Wt%),
The ratio [X] of the peak area of the wave number 1785 cm ^-1 obtained by separating the peak of the wave number 1791 cm ^-1 by the curve fitting method to the peak area of the wave number 1791 cm ^-1 is
It is essential to satisfy the relationship of the following formula (I) and the following formula (II), and when either of the following formula (I) and the following formula (II) is not satisfied, as an adhesive polymer composition This means that a sufficient adhesive force cannot be expressed.

[0019] 0.50 ≦ 1-X (I) 0.25 wt% ≤ (1-X) M ≤ 10 wt% (II)

The content [M] (% by weight) of the unsaturated carboxylic acid or derivative unit thereof and the ratio [X] of the peak area at the wave number of 1785 cm ^{-1 to} the peak area at the wave number of 1791 cm ^-1 are as follows. It is preferable to satisfy the relationship of the formula (III) and the following formula (IV). 0.60 ≦ 1-X (III) 0.30% by weight ≦ (1-X) M ≦ 10% by weight (IV)

Here, the value of [1-X] is less than the above range,
And the value of [(1-X) M] is less than the above range, sufficient adhesive strength as an adhesive polymer composition cannot be obtained, while
When the value of [(1-X) M] exceeds the above range, a gel or the like is generated in the modified ethylene polymer, which becomes fish eyes or lumps in the adhesive polymer composition to lower the adhesive strength. In addition to the above, the surface appearance of the laminated body is deteriorated.

The unsaturated carboxylic acid or its derivative
The content [M] (% by weight) of the unit is an unsaturated carboxylic acid or
Is the content of its derivative and the wave in the infrared absorption spectrum.
Number 1791 cm^-1Is it a calibration curve created from the peak area of
The wave number is 1785 cm.^-1The peak of
Area wave number 1791 cm^-1Of the peak area
[X] is basically the Journal of Applied Polymer S
Cars listed in cience, vol.62, 1205-1210 (1996)
The infrared absorption spectrum is
Wave number 1791 cm^-1The peak of the wave number is 1792 cm
^-1, 1785cm ^-1, And 1776 cm^-1The three pea
1785 cm^-1About the peak of
1850 cm to 1750 cm^-1Calculate the area as
Then, the wave number calculated in the same manner is 1791 cm.^-1To the peak area of
It is obtained as a ratio to the ratio.

Further, the ethylene polymer as the component (B) constituting the adhesive polymer composition of the present invention is an ethylene polymer other than the component (A), and in the component (A), For the same reason, the density is 0.850-0.960g
/ Cm ³ is essential, and 0.850 to 0.9
20 g / cm ³ is preferred, and JIS K7
It is essential that the melt flow rate measured at 190 ° C. under a load of 21.18 N in accordance with 210 is 0.01 to 50 g / 10 minutes, and preferably 0.1 to 30 g / 10 minutes.

Specific examples of the ethylene polymer as the component (B) include those similar to the ethylene polymer before modification mentioned in the modified ethylene polymer as the component (A). , A linear ethylene-α-olefin copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms is preferable, and further, the linear ethylene-α-olefin copolymer includes ethylene and 6 carbon atoms. The linear ethylene-α-olefin copolymer with α-olefin of 12 to 12 is preferable, and the linear ethylene-α-olefin copolymer is a copolymer with a metallocene catalyst. Preferably, further, as the linear ethylene-α-olefin copolymer with the metallocene catalyst,
It is preferable that the elution curve of the temperature rising elution fractionation has a single peak. The ethylene polymer as the component (B) in the present invention may be modified in the same manner as the component (A).

The adhesive polymer composition of the present invention comprises the modified ethylene polymer as the component (A) and the ethylene polymer as the component (B), and the total amount of the two components is 100% by weight. %, It is essential that the composition ratio of the component (A) is 5 to 95% by weight and that of the component (B) is 95 to 5% by weight, and the composition ratio of the component (A) is 10 to 60% by weight. )
It is preferred that the components are 90-40% by weight. If the proportion of the modified ethylene polymer of the component (A) is less than the above range and the proportion of the ethylene polymer of the component (B) exceeds the above range, the adhesive polymer composition will have insufficient adhesive force,
When the ratio of the modified ethylene polymer as the component (A) exceeds the above range and the ratio of the ethylene polymer as the component (B) is less than the above range, the adhesive strength of the adhesive polymer composition is insufficient and the laminate is If so, the surface appearance will be deteriorated.

The adhesive polymer composition of the present invention contains, in addition to the above-mentioned components (A) and (B), other polyolefin-based resins, rubbers, etc. within a range that does not impair the effects of the present invention. Further, if necessary, tackifier, and various additives usually used, for example, antioxidants, light stabilizers, ultraviolet absorbers, nucleating agents, neutralizing agents,
A lubricant, an antiblocking agent, a dispersant, a fluidity improver, a release agent, a flame retardant, a coloring agent, a filler and the like may be added.

The adhesive polymer composition of the present invention comprises the modified ethylene polymer as the component (A), the ethylene polymer as the component (B), and other resins and rubbers used as necessary. , Additives, tumbler blender,
It is prepared by uniformly mixing with a ribbon blender, a V-type blender, a Henschel mixer, etc., and then melt-kneading with a single-screw or twin-screw extruder, roll, Banbury mixer, kneader, Brabender, etc.

The adhesive polymer composition of the present invention may be subjected to sequential extrusion laminating, sandwich extrusion laminating, coextrusion laminating on an adherend with or without an anchor coating agent by a conventionally known method. , And, the adherend and the adhesive polymer composition, and further formed into a laminate by a method such as a method of coextruding a different resin or the same resin, or formed into a film or sheet, or further stretched. It is formed into a stretched product, subjected to thermoforming such as vacuum forming or pressure forming, or coextrusion blow-molded to be shaped into a container. It is suitable.

Here, as the adherend, specifically, for example, one side of the layer made of the adhesive polymer composition of the present invention is a polyolefin resin such as polyethylene or polypropylene, and the other side. Nylon 6, nylon 12, nylon 66, nylon MXD
Polyamide resins such as 6, nylon 6/66, saponified ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polybutylene terephthalate, polyethylene naphthalate, polycyclohexylene terephthalate, etc. Gas barrier resin such as polyester resin, polycarbonate resin, polystyrene (GPPS
Resin), high impact polystyrene (HIPS resin), styrene-acrylonitrile graft polymer (A
Examples thereof include polystyrene resins such as BS resin), and of the latter, the gas barrier resin is preferable.

As the adherend in the present invention, in addition to unstretched or stretched films or sheets of the various resins described above, printed films or sheets having their surfaces printed, aluminum, copper, iron, etc. Examples include metal foil, metal such as plate, and paper such as paper and paperboard.

[0031]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following Examples and Comparative Examples, the following were used as the modified ethylene polymer as the component (A) and the ethylene polymer as the component (B) of the adhesive polymer composition.

(A) Modified ethylene polymer A-1: a copolymer of ethylene and 1-hexene with a metallocene catalyst, wherein the elution curve for temperature rising elution fractionation has a single peak and the density is 0.880 g / cm ³ , 1
100 parts by weight of a linear ethylene-1-hexene copolymer having a melt flow rate at 90 ° C. of 30 g / 10 min, 0.8 part by weight of maleic anhydride, and 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane 0.04
After uniformly mixing the parts by weight with a Henschel mixer,
200 ° C with a twin-screw extruder, screw rotation speed 600r
The content of maleic anhydride unit [M] was 0.6% by weight, and the wave number of the peak area at a wave number of 1785 cm ⁻¹ in the infrared absorption spectrum was 1791.
A modified linear ethylene-1-hexene copolymer modified so that the ratio [X] to the peak area of cm ⁻¹ is 0.44.

A-2: The screw rotation speed is 100 rpm
Except that the above was modified in the same manner as in the above-mentioned A-1, the content of maleic anhydride unit [M] was 0.6% by weight, and the wave number of the peak area at the wave number of 1785 cm ⁻¹ in the infrared absorption spectrum was 17
A modified linear ethylene-1-hexene copolymer modified to have a ratio [X] of 0.60 with respect to a peak area of 91 cm ⁻¹ .

A-3: Meta of ethylene and 1-hexene
Copolymer with a rosene-based catalyst
Another elution curve has a single peak with a density of 0.913 g
/ Cm³, Melt flow rate at 190 ° C is 2g / 1
0 minute linear ethylene-1-hexene copolymer was used
Other than the above, the maleic anhydride unit is modified in the same manner as A-1.
Content [M] of 0.6% by weight in the infrared absorption spectrum
Wave number 1785 cm ^-1Wavenumber of peak area of 1791c
m^-1The ratio [X] to the peak area is 0.40.
Modified linear ethylene-1-hexene copolymer
body.

A-4: Screw rotation speed is 100 rpm
Except that the above was modified in the same manner as in the above A-3, the content of maleic anhydride unit [M] was 0.6% by weight, and the wave number of the peak area at the wave number of 1785 cm ^-1 in the infrared absorption spectrum was 17
A modified linear ethylene-1-hexene copolymer modified so that the ratio [X] to the peak area of 91 cm ⁻¹ is 0.75.

A-5: A copolymer of ethylene and 1-hexene with a metallocene catalyst, which has a single peak in the elution curve for temperature rising elution fractionation and has a density of 0.880 g.
/ Cm ³ , melt flow rate at 190 ° C is 4g / 1
100 parts by weight of a linear ethylene-1-hexene copolymer at 0 minutes, 1.0 part by weight of maleic anhydride, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. 0.05 parts by weight were uniformly mixed with a Henschel mixer, and then subjected to a melt grafting reaction condition at 200 ° C. and a screw rotation speed of 600 rpm by a twin-screw extruder to obtain a maleic anhydride unit content [M] 0.8 part by weight. %, the ratio of the peak area of the wavenumber 1791cm ^-1 of the peak area of wave number 1785 cm ^-1 in an infrared absorption spectrum (X) 0.2
A modified linear ethylene-1-hexene copolymer modified so as to be 5.

A-6: Screw rotation speed is 100 rpm
Except that the content of the maleic anhydride unit [M] was 0.8% by weight and the peak number was 1785 cm ^-1 in the infrared absorption spectrum.
A modified linear ethylene-1-hexene copolymer modified to have a ratio [X] of 0.74 with respect to a peak area of 91 cm ⁻¹ .

A-7: A copolymer of ethylene and 1-hexene using a metallocene catalyst, which has a single peak in the elution curve for temperature rising elution fractionation and has a density of 0.900 g.
/ Cm ³ , melt flow rate at 190 ° C is 4g / 1
Using a 0-minute linear ethylene-1-hexene copolymer,
In addition to the screw rotation speed of 300 rpm, the above-mentioned A-
Modified in the same manner as in 5, and the content of maleic anhydride unit [M]
0.6% by weight, wave number 178 in infrared absorption spectrum
Denatured modified linear ethylene-1-hexene copolymer such that the ratio (X) 0.26 to the peak area of the wavenumber 1791cm ^-1 of the peak area of 5 cm ^-1.

A-8: Metallo of ethylene and 1-butene
Copolymer with sen-based catalyst, temperature rising elution fractionation
Has a single peak and a density of 0.880 g /
cm ³, Melt flow rate at 190 ° C is 4g / 10
Minute linear ethylene-1-butene copolymer,
Except for setting the Liu rotation speed to 300 rpm,
Similarly modified, the content of maleic anhydride unit [M] 0.
6% by weight, wave number 1785c in infrared absorption spectrum
m^-1Wave area of the peak area of 1791cm^-1To the peak area of
To the ratio [X] of 0.51
Chain ethylene-1-butene copolymer.

A-9: A copolymer of ethylene and 1-butene using a Ziegler catalyst, having a density of 0.920.
g / cm ³ , melt flow rate at 190 ° C. is 2 g /
Using a 10-minute linear ethylene-1-butene copolymer,
In addition to the screw rotation speed of 300 rpm, the above-mentioned A-
Modified in the same manner as in 5, and the content of maleic anhydride unit [M]
0.6% by weight, wave number 178 in infrared absorption spectrum
Denatured modified linear ethylene-1-butene copolymer so that the ratio (X) 0.55 to the peak area of the wavenumber 1791cm ^-1 of the peak area of 5 cm ^-1.

A-10: Density 0.955 g / cm ³ ,
The melt flow rate at 190 ° C. was 3 g / 10 minutes, a homopolymer of ethylene with a Ziegler-based catalyst was used, and the screw rotation speed was 300 rpm.
Modified in the same manner as described above, and the content of maleic anhydride unit [M]
0.6% by weight, wave number 178 in infrared absorption spectrum
Modified ethylene homopolymer modified such that the ratio (X) 0.20 to the peak area of the wavenumber 1791cm ^-1 of the peak area of 5 cm ^-1.

(B) Ethylene polymer B-1: a copolymer of ethylene and 1-hexene using a Ziegler catalyst, having a density of 0.920 g / c.
m ³ , melt flow rate at 190 ° C is 3.5 g / 1
0 minute linear ethylene-1-hexene copolymer. B-2: a copolymer of ethylene and 1-hexene by a metallocene catalyst, which has a single peak in the elution curve of temperature rising elution fractionation, and has a density of 0.900 g / cm ³ , 1
A linear ethylene-1-hexene copolymer having a melt flow rate at 90 ° C. of 3.5 g / 10 min.

The elution curve for the temperature rising elution fractionation was prepared by the following method. <Elution curve of temperature rising elution fractionation> As a measuring device, a temperature rising elution fractionation (TREF) mechanism that separates samples using the difference in melting temperature, and a size exclusion chromatograph that further separates the separated fractions by molecular size (Size Exclusion
Chromatography (SEC) connected online with a cross fractionation device (“CFC T150A” manufactured by Mitsubishi Chemical Corporation). Using o-dichlorobenzene as the solvent, the polymer is dissolved at 140 ° C. so that the concentration becomes 4 mg / ml, and this is injected into the sample loop of the measuring device.
The sample solution in the sample loop was filled with glass beads as an inert carrier and had an inner diameter of 4 mm and a length of 150 mm.
After injecting into the stainless steel column attached to the REF device, 1
Cool from 140 ° C to 0 ° C at a rate of ° C / min to coat the surface of the inert carrier. After holding the column at 0 ° C. for 30 minutes, 1 ml of 2 ml of the components dissolved at a temperature of 0 ° C.
It is injected from the TREF column to the SEC column (“AD80M / S” manufactured by Showa Denko KK, three) at a flow rate of ml / min. S
While the molecular size was sorted by EC, TREF
The column is heated to the next elution temperature (5 ° C) at which temperature 3
After holding for 0 minutes, the operation of injecting into the SEC column is repeated. The measurement of each elution section by SEC was performed at intervals of 39 minutes. The elution temperature is 0, 5, 10, 15, 20, 2
5, 30, 35, 40, 45, 49, 52, 55, 5
8, 61, 64, 67, 70, 73, 76, 79, 8
2, 85, 88, 91, 94, 97, 100, 102,
The temperature was set to 120 and 140 ° C., and the temperature was raised stepwise. S
The solution sorted into the molecular size by the EC column was measured for the absorbance proportional to the polymer concentration with an infrared spectrophotometer attached to the device (detected by stretching vibration of methylene having a wavelength of 3.42μ),
Obtain a chromatogram for each elution temperature category. Using the built-in data processing software, draw the baseline of the obtained chromatogram of each elution temperature segment and perform the arithmetic processing. The area of each chromatogram is integrated and the integrated elution curve is calculated.
Also, this integrated elution curve is differentiated with temperature to calculate the differential elution curve. The plot of the calculation result is output to the printer, and the plot of the differential elution curve output is the elution temperature of 100 ° C on the horizontal axis.
Per 89.3 mm, the vertical axis represents the differential amount (total integrated elution amount was standardized to 1.0, and the change amount at 1 ° C. was defined as the differential amount).
76.5 mm per one.

The content [M] of the maleic anhydride unit was measured by the following method. <Content [M] of maleic anhydride unit> Content of unsaturated carboxylic acid or its derivative, and in infrared absorption spectrum obtained by Fourier transform infrared spectrophotometer "FT-IR-610" manufactured by JASCO Corporation It was determined from a calibration curve prepared from the peak area at a wave number of 1791 cm ^-1 .

[0045] The proportion (X) to the peak area of the wavenumber 1791cm ^-1 of the peak area of wave number 1785 cm ^-1 in the infrared absorption spectrum was measured by the following methods. <Wavenumber 1785 cm ^-1 peak area wavenumber 1791 cm
^-1 ratio to the peak area [X]> The peak of wave number 1791 cm ^-1 in the infrared absorption spectrum obtained by the Fourier transform infrared spectrophotometer "FT-IR-610" manufactured by JASCO Corporation Wavenumbers of 1792 cm ^-1 , 1785 cm ^-1 , and 1776
It separated into three peaks in cm ^-1, 1850~1750cm baseline for the peak of 1785 cm ^-1
The area was calculated as ^-1 , and the wave number was calculated in the same manner as 1791c.
It was calculated as the ratio of m ^{-1 to} the peak area.

Examples 1 to 3 and Comparative Examples 1 to 3 The modified ethylene polymer of the component (A) and the ethylene polymer of the component (B) shown in Tables were uniformly mixed with a Henschel mixer, and then a 65 mm diameter Supply to a single-screw extruder, 180 ℃
By melt-kneading with, extruding into a strand shape, and cutting, a pellet-shaped adhesive polymer composition was produced.

Each of the obtained adhesive polymer compositions was melt-kneaded with a uniaxial extruder having a diameter of 45 mm as an intermediate layer, and
Linear low-density polyethylene resin as the resin for the inner layer (“Novatech LLDPE SF840 manufactured by Nippon Polychem Co., Ltd.
2 ”) is melted and kneaded with a 40 mm diameter uniaxial extruder, and a polyamide resin (“ Novamid 1020CA2 ”manufactured by Mitsubishi Engineering Plastics Co., Ltd.) as a resin for the outer layer is melt-kneaded with a 65 mm diameter uniaxial extruder and set to 220 ° C. Co-extrusion from a die and inflation molding at a molding rate of 70 mm / min to give a linear low-density polyethylene resin inner layer 40 μm / adhesive polymer composition layer 10
A laminate having a layer structure of 3 layers of 3 types of 3 μm / outer layer of polyamide resin 20 μm was manufactured.

The adhesive strength of each of the obtained laminates was measured by the following method, and the results are shown in Table 1. <Adhesive Strength> Using a strip-shaped sample cut into a width of 10 mm from the obtained laminate, the outer layer of the polyamide resin at one end thereof and the adhesive polymer composition layer were preliminarily peeled and peeled in accordance with JIS K6854. 23 at a speed of 50 mm / min
A T-type peel test was conducted at ° C. Incidentally, the linear low-density polyethylene resin inner layer and the adhesive polymer composition layer could not be peeled off.

[0049]

[Table 1]

Examples 4 to 8 and Comparative Examples 4 to 8 Saponified ethylene-vinyl acetate copolymer (“Eval F101A” manufactured by Kuraray Co., Ltd.) was used as the resin for the outer layer, and the temperature of the annular die was 210 ° C. A laminated body was manufactured in the same manner as in the above-mentioned Examples and Comparative Examples, and the adhesive strength of each obtained laminated body was measured, and the results are shown in Table 2.

[0051]

[Table 2]

[0052]

INDUSTRIAL APPLICABILITY According to the present invention, various laminated bodies including layers of gas barrier resin such as polyamide resin, ethylene-vinyl acetate copolymer saponification product, and polyester resin, particularly polyolefin resin and gas barriers thereof are provided. PROBLEM TO BE SOLVED: To provide an adhesive polymer composition suitable as an adhesive in the production of a laminate with a hydrophobic resin, and a laminate of a polyolefin resin using the adhesive polymer composition and these gas barrier resins. can do.

Continued front page    F term (reference) 4F100 AK01C AK03B AK04A AK41C                       AK46C AK63A AK63B AK69C                       AL04A AL05A AL06A BA03                       BA07 BA10B BA10C EH20                       EJ37 GB15 JA06A JA13A                       JD02C JL11A YY00A                 4J040 DA041 DA161 GA05 HB41                       LA01 MA02 MA09 MA10 MB03                       NA06 NA08

Claims (9)

[Claims] 1. A component (A) and a component (B) described below, wherein the weight% of the two components is based on 100% by weight of the total of the two components. ] The adhesive polymer composition characterized by including these. (A) Density is 0.850 to 0.960 g / cm ³ , 19
Melt flow rate at 0 ° C is 0.01 to 50 g / 10
Which is a partial ethylene polymer, denatured made by subjected to graft reaction conditions in the presence of an unsaturated carboxylic acid or its derivative, wavenumber in the infrared absorption spectrum 1791cm ^-1
Content [M] (% by weight) of the unsaturated carboxylic acid or its derivative unit determined from the peak area of
The wave number of the peak area of 1785 cm ^{-1 where} the peak of m ^-1 was separated by the curve fitting method was 1791 cm ^-1.
The ratio [X] to the peak area of the modified ethylene polymer satisfying the relationships of the following formulas (I) and (II);
~ 95 wt% 0.50 ≤ 1-X (I) 0.25 wt% ≤ (1-X) M ≤ 10 wt% (II) (B) Density is 0.850 to 0.960 g / cm ³ , 19
Melt flow rate at 0 ° C is 0.01 to 50 g / 10
An ethylene-based polymer other than the component (A);
5-5% by weight 2. The ethylene-based polymer as the component (A) is a linear ethylene-α-olefin copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms.
The adhesive polymer composition according to item 1. 3. Linear ethylene-α in the component (A)
The adhesive polymer composition according to claim 2, wherein the olefin copolymer is a copolymer of ethylene and an α-olefin having 6 to 12 carbon atoms with a metallocene catalyst. 4. The adhesive according to claim 3, wherein the linear ethylene-α-olefin copolymer with the metallocene-based catalyst in the component (A) has a single peak in the elution curve for temperature rising elution fractionation. Polymer composition. 5. The ethylene-based polymer as the component (B) is a linear ethylene-α-olefin copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms. The adhesive polymer composition according to item 1. 6. The metallocene catalyst-based copolymer of ethylene and an α-olefin having 6 to 12 carbon atoms as the component (B), which is a linear ethylene-α-olefin copolymer. The adhesive polymer composition of. 7. The adhesion according to claim 6, wherein the metallocene-based linear ethylene-α-olefin copolymer as the component (B) has a single peak in the elution curve for temperature rising elution fractionation. Polymer composition. 8. A laminate comprising a polyolefin resin layer and a layer of another resin, which are laminated with a layer comprising the adhesive polymer composition according to any one of claims 1 to 7 interposed therebetween. body. 9. The resin according to claim 8, wherein the other resin is any resin selected from the group of gas barrier resins consisting of a polyamide resin, an ethylene-vinyl acetate copolymer saponification product, and a polyester resin. Laminate.