JP2002019060A - Laminate, its manufacturing method and container using the laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate not deteriorating quality of a content even by using as a container or a packaging material having an excellent adhesive strength between a base and a resin layer even without using an anchor coating agent and small odor, a method for manufacturing the same and a container using the laminate. SOLUTION: The laminate comprises a base layer (I) made of at least one type of a material selected from the group consisting of a thermoplastic resin, paper, nonwoven fabric and a woven fabric, a resin layer (II) made of a resin material containing a specific ethylene (co)polymer (A) and directly adhered to at least one surface of the layer (I) in such a manner that an additive is not compounded with the resin material, or the additive compounded with the material is not externally eluted or the additive does not affect the content. The method for manufacturing the laminate and the container using the laminate are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a laminate which is excellent in adhesive strength between layers, has little shift in taste and odor, and is suitable for packaging foods, especially liquids, without using an anchor coating agent. A laminate having excellent tear strength, impact resistance, molding processability, heat seal strength, heat resistance, etc., and capable of imparting gas barrier properties, and a production method of a laminate which is economical with a small number of production steps, And a container using the laminate. More specifically, barrier packaging materials for the purpose of blocking moisture, oxygen, light, etc., clean packaging materials used for retort foods, medical supplies, electronic materials, etc., laminates used for containers, etc. TECHNICAL FIELD The present invention relates to a laminate suitable for food containers conforming to ministerial ordinances such as milk, food, and medical fields, particularly to a container for food, a method for producing the same, and a container using the laminate.

[0002]

2. Description of the Related Art Gas barrier packaging materials, retort containers, liquor containers, beverage containers, and the like generally include paper, plastic (polyester, polyamide, etc.) base materials, anchor coating agents, and the like. A laminate obtained by extrusion-laminating low-density polyethylene (LDPE) or the like via an adhesive described above and further providing a heat seal layer thereon is used.

When an adhesive such as an anchor coating agent is used, the adhesive strength between layers of the laminate is maintained. However, since the adhesive such as the anchor coating agent contains a solvent, it has problems such as safety, contamination of the working environment, and increase in equipment cost. Further, in a container made of a laminate using an adhesive such as an anchor coat agent, the odor and elution components (off-flavors) migrate from the laminate to the contents, thereby deteriorating the quality of the contents. There was a problem. In recent years, there has been a growing interest in the consumer's environment (environmental hormones, dioxins, recyclability of packaging containers, etc.).

On the other hand, when the anchor coating agent is not used, the adhesive strength between the layers of the laminate becomes weak, so that the container made of this laminate is easily broken, and the quality of the container and the packaging material is not stable. However, there is a problem that it cannot be used as a packaging material. Further, since the LDPE layer is provided between the base material and the heat seal layer, the number of steps for manufacturing the laminate increases.

As a laminate which solves these problems, a laminate obtained by extrusion-laminating a composition of a specific ethylene / α-olefin copolymer and LDPE on a metal surface of a metal foil or a metallized film is disclosed in No. 9-234837. However, the above specific ethylene / α-olefin copolymer is usually produced by a metallocene catalyst using zirconium halide, and halogen remains in the copolymer. Since such a copolymer generates hydrogen halide during molding,
It has been necessary to add an acid absorbent and the like.

[0006] Additives such as acid absorbents elute from the laminate,
And in the container using such a laminated body, there was a problem that the quality of the contents was deteriorated by the eluted additive. In particular, when the laminate is used for food containers and packaging materials such as milk conforming to ministerial ordinances for milk and the like, the addition of these additives is extremely restricted in terms of sanitation, and in particular, antioxidants are prohibited.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a container or packaging material which has excellent adhesive strength between a substrate and a resin layer, has low odor, and does not require an anchor coat agent. An object of the present invention is to provide a laminate suitable for packaging foods, particularly liquids, a method for producing the laminate, and a container using the laminate without deteriorating the quality of contents even when used. Further, an object of the present invention is to provide a laminate having excellent tear strength, impact resistance, moldability, heat seal strength, heat resistance, etc., and capable of imparting gas barrier properties, a method for producing the same, and a laminate thereof. An object of the present invention is to provide a container using a body.

[0008]

The laminate of the present invention comprises at least one surface of a base material layer (I) comprising at least one material selected from the group consisting of a thermoplastic resin, paper, nonwoven fabric and woven fabric. A resin layer (II) made of a resin material containing an ethylene (co) polymer (A) satisfying the following requirements (a) to (d) is directly bonded, and no additives are blended in the resin material: Alternatively, an additive compounded in the resin material is an additive which does not elute to the outside or does not affect the contents. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 50 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.5 to 4.5 (d ) elution temperature by continuous Atsushi Nobori elution fractionation (TREF) - the difference T ₇₅ between the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes −T ₂₅ and density d satisfy the relationship of the following (Equation 1) (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644

The ethylene (co) polymer (A)
Desirably satisfies the following requirement (e). (E) Difference between the temperature T _{25 at} which 25% of the whole is eluted and the temperature T _{75 at} which 75% of the whole is eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF) T ₇₅ −T ₂₅ and density d satisfy the relationship of the following (Formula 2) (Formula 2) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 d ≧ 0.950 g / Cm ³ T ₇₅ −T ₂₅ ≧ 0 In addition, the laminate of the present invention provides the second base material layer (III) in contact with the surface of the resin layer (II) on the side not in contact with the base material layer (I). ) Is desirable. In addition, the laminate of the present invention is characterized in that the surface of the second base material layer (III) and / or the base material layer (I) on the side not in contact with the resin layer (II) has the ethylene (co)
Second resin layer (I) made of a resin material containing polymer (A)
V) and / or the third resin layer (V) is desirably laminated.

[0010] The resin material containing the ethylene (co) polymer (A) may be an ethylene (co) polymer (A) 100 to 100%.
It is desirable to contain 10% by weight and less than 90% by weight of another ethylene polymer (B) having a density of 0.88 to 0.97 g / cm ³ . Further, the other ethylene-based polymer (B) is desirably a low-density polyethylene obtained by a high-pressure radical polymerization method. The ethylene (co) polymer (A) further comprises the following (f) and (g)
It is desirable that the (A1) ethylene (co) polymer satisfy the requirement of (1). (F) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by weight), the density d, and the melt flow rate (MFR) satisfy the following relationship. 4) When d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR)
² + 2.0 (g) Presence of multiple peaks in elution temperature-elution amount curve by continuous heating elution fractionation method (TREF)

The ethylene (co) polymer (A)
Is preferably an (A2) ethylene (co) polymer satisfying the following requirements (h) and (i). (H) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF). (I) One or two melting point peaks, and the highest melting point T _m1 and density d among them Satisfies the following relationship (Equation 5). (Equation 5) T _m1 ≧ 150 × d−17 Further, the (A2) ethylene (co) polymer further satisfies the following requirement (j). Is desirable. (J) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR +
0.3 The ethylene (co) polymer (A) may be one produced by a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. desirable. Further, the halogen concentration in the resin material containing the ethylene (co) polymer (A) is 10 ppm.
It is desirable that:

[0012] Further, the method for producing a laminate of the present invention is characterized in that at least one surface of a base material layer (I) made of at least one material selected from the group consisting of thermoplastic resin, paper, non-woven fabric and woven fabric, It contains an ethylene (co) polymer (A) that satisfies the requirements of (a) to (d) and contains no additives, or the added additives do not elute to the outside or affect the contents. The resin layer (II) is formed by directly extruding and laminating a resin material which is an additive which is not provided. (A) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 50 g / 10 min, (c)
Molecular weight distribution (Mw / Mn) of 1.5 to 4.5, (d) Temperature at which 25% of the whole is eluted from the integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) Difference T ₇₅ between T ₂₅ and temperature T _{75 at} which 75% of the total elutes
−T ₂₅ and density d satisfy the relationship of the following (Equation 1) (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644

In the method for producing a laminate according to the present invention, when the resin material containing the ethylene (co) polymer is directly extrusion-laminated on the base material layer (I), the ethylene (co) polymer It is desirable to perform extrusion lamination at a molding temperature of not less than the melting point of the resin material containing the ethylene (co) polymer (A) and not more than 330 ° C. while performing ozone treatment on the molten resin of the resin material containing (A). Further, the container of the present invention is characterized by comprising the laminate of the present invention.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The ethylene (co) polymer (A) in the present invention is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin. Here, the α-olefin has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and specifically includes propylene, 1-pentene, 4-methyl-1-pentene, 1-hexene, -Octene, 1-decene, 1
-Dodecene and the like. Further, the content of these α-olefins is desirably generally selected in a range of 30 mol% or less, preferably 3 to 20 mol% or less.

The ethylene (co) polymer (A) of the present invention has a (a) density of 0.86 to 0.97 g / cm.
³ , preferably 0.89 to 0.94 g / cm ³ , more preferably 0.90 to 0.93 g / cm ³ . If the density is less than 0.86 g / cm ³ , the rigidity (strength) and heat resistance are inferior. 0.97g
/ Cm ³ is difficult to produce industrially.

The (b) melt flow rate (hereinafter referred to as MFR) of the ethylene (co) polymer (A) in the present invention is from 0.01 to 50 g / 10 min, preferably from 0.0 to 50 g / 10 min.
It is in the range of 3 to 30 g / 10 minutes. MFR 0.01g
If it is less than / 10 minutes, the moldability will be poor, and if it exceeds 50 g / 10 minutes, the tear strength, impact resistance, etc. will be poor.

The (c) molecular weight distribution (Mw / Mn) of the ethylene (co) polymer (A) in the present invention is 1.5 to 1.5.
The range is 4.5, preferably 2.0 to 4.0, and more preferably 2.5 to 3.0. Mw / Mn is 1.
If it is less than 5, the moldability is poor, and if it exceeds 4.5, the tear strength, impact resistance and the like are poor. Here, the molecular weight distribution (Mw / Mn) of the ethylene (co) polymer is obtained by determining the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculating the ratio (Mw). / Mn).

Ethylene (co) polymer of the present invention
(A) shows, for example, as shown in FIG.
Product of elution temperature-elution amount curve by the fractionation method (TREF)
Temperature at which 25% of the total eluted from the elution curve_{twenty five}
And the temperature T at which 75% of the whole elutes ₇₅Difference T from₇₅−T_{twenty five}You
And the density d satisfies the relationship of the following (formula 1).
You. (Equation 1) T₇₅−T_{twenty five}≦ −670 × d + 644 T₇₅−T_{twenty five}And the density d do not satisfy the relationship of the above (Equation 1)
In this case, heat seal strength and heat resistance will be inferior.
You.

The ethylene (co) polymer (A) in the present invention preferably further satisfies the following requirement (e). (E) Difference between the temperature T _{25 at} which 25% of the whole is eluted and the temperature T _{75 at} which 75% of the whole is eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve obtained by continuous temperature elution fractionation (TREF) T ₇₅ −T ₂₅ and density d satisfy the relationship of the following (Formula 2) (Formula 2) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 d ≧ 0.950 g / Cm ³ T ₇₅ −T ₂₅ ≧ 0 When the relationship of the above (Equation 2) is not satisfied, the low-temperature heat sealability is poor.

The ethylene (co) polymer (A) in the present invention is different from the conventional ethylene (co) polymer obtained by the general metallocene catalyst shown in FIG.
Or it is clearly distinguished by the relational expression of (Equation 2).

The ethylene (co) polymer (A) in the present invention is (A1) an ethylene (co) polymer that further satisfies the requirements of (f) and (g) described below, or (h) that is further described below. And (A2) an ethylene (co) polymer satisfying the requirements of (i).

In the present invention, (A1) the amount X (% by weight) of the ODCB-soluble component at 25 ° C., the density d and the MFR of the ethylene (co) polymer at 25 ° C. are represented by the following (formula 3) and (formula 4). (Equation 3) When d−0.008 log MFR ≧ 0.93, X <2.0 (Equation 4) When d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300-d + 0.008logMFR)
² + 2.0 Preferably, when d−0.008 log MFR ≧ 0.93, X <1.0 d−0.008 log MFR <0.93, X <7.4 × 10 ³ × (0.9300− d + 0.008logMF
R) ² +1.0, and more preferably d−0.0.
When 08logMFR ≧ 0.93, X <0.5 d−0.008logMFR <0.93, X <5.6 × 10 ³ × (0.9300−d + 0.008logMF
R) ² +0.5 is satisfied.

Here, the amount X of the ODCB-soluble component at 25 ° C. is measured by the following method. Sample 0.5
g in 20 ml ODCB at 135 ° C. for 2 hours,
After completely dissolving the sample, cool it to 25 ° C. After leaving this solution at 25 ° C. overnight, the solution is filtered through a Teflon (registered trademark) filter to collect a filtrate. The filtrate, which is a sample solution, is measured for the absorption peak intensity near the wave number of 2925 cm ^-1 of asymmetric stretching vibration of methylene using an infrared spectrometer, and the sample concentration is calculated based on a previously prepared calibration curve. From this value, the ODCB-soluble content at 25 ° C. is determined.

The ODCB-soluble matter at 25 ° C. is a high branching degree component and a low molecular weight component contained in the ethylene (co) polymer, which causes a decrease in heat resistance and a sticky surface of a molded product, and a problem of hygiene. It is desirable that this content be low because it causes blocking of the inside of the molded body. In addition, low molecular weight components cause smoke during molding. OD
The amount of the CB-soluble component is affected by the α-olefin content and the molecular weight of the entire copolymer, that is, the density and the MFR.
Therefore, these indices density, MFR and ODCB
When the amount of the soluble component satisfies the above relationship, it indicates that the α-olefin contained in the whole copolymer is less unevenly distributed.

As shown in FIG. 2, the (A1) ethylene (co) polymer according to the present invention has a peak in the elution temperature-elution amount curve obtained by (g) continuous heating elution fractionation (TREF). Are plural. It is particularly preferred that the plurality of peak temperatures be between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.

The method of measuring TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) has been added so that the sample concentration becomes 0.05% by weight, and heated and dissolved at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, while flowing ODCB through this column at a constant flow rate, the column temperature was raised to 50 ° C.
The sample is sequentially eluted while increasing the temperature at a constant rate of ° C./hr. At this time, the concentration of the sample eluted in the solvent is continuously detected by measuring the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm ^-1 with an infrared detector. From this value, the concentration of the ethylene (co) polymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. T
According to the REF analysis, the change in the elution rate with respect to the temperature change can be continuously analyzed with a very small amount of sample, so that relatively fine peaks that cannot be detected by the fractionation method can be detected.

The (A2) ethylene (co) polymer in the present invention is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms. The α-olefin has preferably 5 to 10 carbon atoms, specifically 1-pentene,
4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. The content of these α-olefins is usually 3
It is desirably selected in a range of 0 mol% or less, preferably 3 to 20 mol% or less.

In the present invention, (A2) ethylene (co) heavy
As shown in FIG. 1, the coalescence was carried out by the
The peak of the elution temperature-elution amount curve by (TREF) is one
And (i) having one or two melting point peaks,
And the highest melting point T _m1And the density d are given by
This satisfies the relationship of 5). (Equation 5) T_m1≧ 150 × d-17 Melting point T_m1And the density d do not satisfy the relationship of the above (Equation 5)
, Heat resistance is inferior.

Further, among the ethylene (co) polymers (A2), ethylene (co) polymers which further satisfy the following requirement (j) are preferred. (J) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR +
When 0.3 MT and MFR satisfy the relationship of the above (Equation 6), molding processability such as film molding is improved.

Here, the ethylene (co) polymer (A1)
As shown in FIG. 2, a continuous heating elution fractionation method (TR
The peak is substantially a plurality of special ethylene / α-olefin copolymers in the elution temperature-elution amount curve obtained by EF). On the other hand, FIG. 3 shows an ethylene / α-olefin copolymer having substantially one peak in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method (TREF). This corresponds to a typical metallocene-based catalyst-based copolymer. Also,
Although the ethylene (co) polymer (A2) of the present invention has one TREF peak, a copolymer using a conventional typical metallocene catalyst does not satisfy (Equation 2) as described above. They are clearly distinguished.

The ethylene (co) polymer (A) in the present invention is not particularly limited to a catalyst, a production method and the like as long as the above parameters are satisfied. A linear ethylene (co) polymer obtained by homopolymerizing ethylene or copolymerizing ethylene and an α-olefin in the presence of a compound and a catalyst containing a transition metal compound of Group IV of the periodic table. It is desirable. Such a linear ethylene (co) polymer has a narrow molecular weight distribution and a narrow composition distribution, and thus has excellent mechanical properties, excellent heat sealing properties, heat blocking properties, and the like, and has good heat resistance. .

In the production of the ethylene (co) polymer (A) in the present invention, it is particularly desirable to polymerize with a catalyst obtained by mixing the following compounds a1 to a4. a1: Compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr (in the formula, Me ¹ represents zirconium, titanium and hafnium, and R ¹ and R ³ each have 1 carbon atom) ~ 24
R ² is a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof, X ¹ is a halogen atom, and p is q and r are each 0 ≦ p ≦
4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4) a2: Compound represented by the general formula Me ² R ⁴ _m (OR ⁵ ) _n X ² _zmn ( In the formula, Me ² is an element in Groups I to III of the periodic table, R ⁴
And R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, X ²
Represents a halogen atom or a hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table), z represents a valence of Me ² , and m and n each represent An integer satisfying the range of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z) a3: Organic cyclic compound having a conjugated double bond a4: Including Al—O—Al bond Modified organic aluminum oxy compound and / or boron compound

The details will be described below. The catalyst component a1
In the formula of the compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr , Me ¹ represents zirconium, titanium or hafnium. The types of these transition metals are not limited, and plural types can be used. Among them, it is particularly preferable to include zirconium from which a copolymer having excellent weather resistance can be obtained. R ¹ and R ³ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms;
More preferably, it is 1 to 8. Specifically, a methyl group,
Alkyl groups such as ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group,
Aryl groups such as indenyl group and naphthyl group; and aralkyl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofuyl group. These may have branches. R ² represents a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof. X ¹ is fluorine,
Shows halogen atoms such as iodine, chlorine and bromine. p
And q are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r
≦ 4, 0 ≦ p + q + r ≦ 4 are integers.

Examples of the compounds represented by the general formula of the catalyst component a1 include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodichloroconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrabutoxy titanium , Tetrabutoxy hafnium and the like, and particularly, Z such as tetrapropoxy zirconium and tetrabutoxy zirconium.
r (OR) ₄ compounds are preferred, and two or more of these may be used in combination. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonato ligand or derivative thereof include tetra (2,4-pentanedionato) zirconium. , Tri (2,4-pentanedionato)
Zirconium chloride, di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride zirconium, di (2,4-pentanedionato) diethoxide zirconium, di (2,4- Pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n
-Butoxide zirconium, di (2,4-pentanedionato) dibenzyl zirconium, di (2,4-pentanedionato) dineofylzirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) die Zirconium toxide, zirconium di (dibenzoylmethanato) di-n-propoxide, zirconium di (dibenzoylmethanato), zirconium di-n-butoxide, zirconium diethoxide zirconium, di (benzoylacetonate) ) Di-n-propoxide zirconium, di (benzoylacetonate)
Di-n-butoxide zirconium and the like.

The general formula Me of the catalyst component a2^TwoR^Four _m(O
R^Five)_nX^Two _zmn In the formula of the compound represented by^Two Is lap
Group I to III elements in the Periodic Table, lithium, sodium
, Potassium, magnesium, calcium, zinc, bor
Element, aluminum and the like. R ^Four And R^Five Is it
A hydrocarbon group having 1 to 24 carbon atoms, preferably 1 carbon atom
To 12, more preferably 1 to 8, and specifically,
Chill, ethyl, propyl, isopropyl, buty
Alkyl groups such as vinyl group; alkyl groups such as vinyl group and allyl group
Kenyl group; phenyl group, tolyl group, xylyl group, mesity
Aryl groups such as phenyl, indenyl and naphthyl;
Benzyl, trityl, phenethyl, styryl,
Hydrhydryl group, phenylbutyl group, neofuyl group, etc.
Aralkyl groups and the like. These have branches
You may. X^Two Is fluorine, iodine, chlorine and bromine, etc.
Represents a halogen atom or a hydrogen atom. However
Then X ^Two When Me is a hydrogen atom,^Two Is boron, aluminum
Only in the case of Group III elements in the periodic table, such as
Things. Z is Me^Two , And m and
And n satisfy the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively.
Is an integer, and 0 ≦ m + n ≦ z.

Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyllithium and ethyllithium; organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; Organic zinc compounds such as zinc and diethyl zinc; organic boron compounds such as trimethyl boron and triethyl boron; trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride , Ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum Derivatives of organoaluminum compounds such as Idoraido the like.

The organic cyclic compound having a conjugated double bond of the catalyst component a3 has one or more rings having two or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. A cyclic hydrocarbon compound having two or more carbon atoms and having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially a hydrocarbon residue of 1 to 6 (typically, carbon A cyclic hydrocarbon compound substituted with an alkyl group or an aralkyl group of the formulas 1 to 12; two or more, preferably 2 to 4, more preferably 2 to 2, conjugated double bonds.
One or more rings having three rings and a total carbon number of 4
An organosilicon compound having a cyclic hydrocarbon group of from 24 to 24, preferably 4 to 12; said cyclic hydrocarbon group being partially substituted by 1 to 6 hydrocarbon residues or alkali metal salts (sodium or lithium salts) Organosilicon compounds. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

The preferred compounds include cyclopentadiene, indene, azulene and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Further, a compound obtained by bonding (crosslinking) these compounds via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) is also preferably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A _L SiR _4-L wherein A represents the aforementioned cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group. Alkyl groups such as methoxy, ethoxy, propoxy and butoxy groups; aryl groups such as phenyl groups; aryloxy groups such as phenoxy groups; aralkyl groups such as benzyl groups. Represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, or hydrogen, and L represents 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-
Indene, 4,7-dimethylindene, butylcycloheptadiene, 1-methyl-3-propylcyclopentadiene and indene, 1-methyl-3-butylcyclopentadiene and indene, propylcyclopentadiene, 1-
Methyl-3-ethylcyclopentadiene, 1,2,4-
Trimethylcyclopentadiene cycloheptatriene,
C5-C24 cyclopolyene or substituted cyclopolyene such as methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadiene Examples include enylsilane, monoindenylsilane, bisindenylsilane, trisindenylsilane, and methylcyclopentadientinemethylsilane.

In the present invention, a4: Al—O—Al
A modified organoaluminum compound containing a bond and / or a boron compound is used. Specific examples of the modified organic aluminum oxy compound containing an Al-O-Al bond include:
Modified organic aluminum oxy compounds usually called aluminoxanes, which are obtained by reacting an alkyl aluminum compound with water, may be mentioned. The modified organoaluminum oxy compound usually has 1 to
Those containing 100, preferably 1 to 50 Al-O-Al bonds are mentioned. The modified organic aluminum oxy compound may be linear or cyclic.

The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred. The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2.
/ 1, preferably 0.5 / 1 to 1/1.

Examples of the boron compound include triethylaluminum tetra (pentafluorophenyl) borate and triethylammonium tetra (pentafluorophenyl)
Borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, butylammonium tetra (pentafluorophenyl) borate, N, N-
Dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (3,5 difluorophenyl) borate and the like can be mentioned.

The above catalyst may be used by mixing and contacting a1 to a4, but it is preferable to use the catalyst by supporting it on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or the particulate polymer carrier (a5) include a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate, a mixture thereof, a thermoplastic resin, and a thermosetting resin. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Specifically, Si
O ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ ,
CaO, ZnO, BaO, ThO ₂ and the like or mixtures _{thereof, SiO 2 -Al 2 O 3,} SiO 2 -V
₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂
—MgO, SiO ₂ —Cr ₂ O _{3 and the} like. Among them, those mainly containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ are preferable. In addition, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are converted to an organic aluminum compound or a modified organic aluminum compound containing an Al—O—Al bond. After the contact treatment, it can be used as the component a5.

The process for producing the ethylene (co) polymer (A) in the present invention is carried out by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like in the presence of the above-mentioned catalyst, in which substantially no solvent is present. In a state where oxygen, water, etc. are substantially turned off, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane It is produced in the presence or absence of an inert hydrocarbon solvent exemplified as above. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to
~ 200 ° C, more preferably 50 ~ 110 ° C,
The polymerization pressure is usually from normal pressure to 70 kg / cm ^{2 in} the case of the low and medium pressure method.
G, preferably normal pressure to 20 kg / cm ² G, the case of high pressure process typically 1500 kg / cm ² G or less.
The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high-pressure method, it is usually 1 minute to 30 minutes, preferably 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a one-stage polymerization method and a multi-stage polymerization method of two or more stages in which polymerization conditions such as a hydrogen concentration, a monomer concentration, a polymerization pressure, a polymerization temperature, and a catalyst are different from each other.

The ethylene (co) polymer (A) in the present invention is produced by using a catalyst containing no halogen such as chlorine in the above-mentioned catalyst components, so that the halogen concentration is at most 10 ppm or less. Preferably 5 pp
m or less, more preferably substantially free of (ND: 2
ppm or less). By using a halogen-free ethylene (co) polymer such as chlorine, there is no need to use an acid neutralizer (acid absorber) as in the prior art, and chemical stability and hygiene are excellent.
In particular, it is possible to provide a laminate and a container suitably utilized in the field of food packaging materials and the like. Also, by using a halogen-free ethylene (co) polymer, it is not necessary to add calcium stearate. Therefore, it is possible to provide a laminate having good adhesion strength between layers without causing adhesion inhibition by calcium stearate.

As the other ethylene polymer (B) in the present invention, a high / medium /
Examples thereof include an ethylene homopolymer, a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms by a low pressure method and other known methods, and an ethylene (co) polymer by a high pressure radical polymerization method.

High / medium /
An ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms by a low pressure method or another known method has a density of 0.94 to 0.97 g / cm ^3.
High polyethylene, density 0.91-0.94g / cm
³ linear low-density polyethylene (hereinafter referred to as LLDPE), ultra-low-density polyethylene having a density of 0.86 to 0.91 g / cm ³ (hereinafter referred to as VLDPE), density of 0.8
6 to 0.91 g / cm ³ of ethylene / propylene copolymer rubber and ethylene / α-olefin copolymer rubber such as ethylene / propylene / diene copolymer rubber.

The LLDPE using the Ziegler type catalyst is defined as ethylene • α-density having a density of 0.91 to 0.94 g / cm ³ , preferably 0.91 to 0.93 g / cm ^3.
An olefin copolymer, wherein the α-olefin has 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and specifically includes propylene, 1-butene, 4-methyl-
1-pentene, 1-hexene, 1-octene and the like can be mentioned.

Further, the ultra low density polyethylene (VLDPE) using the Ziegler type catalyst has a density of 0.86 to 0.86.
0.91 g / cm ³ , preferably 0.88 to 0.905
g / cm ^{3 in} the range of ethylene / α-olefin copolymer, such as linear low density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EPD).
M) is a polyethylene exhibiting intermediate properties.

The above-mentioned ethylene / α-olefin copolymer rubber includes ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber having a density of 0.86 to less than 0.91 g / cm ^3. Examples of the ethylene-propylene rubber include those obtained by adding a random copolymer (EPM) containing ethylene and propylene as main components and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as a third component. A random copolymer (EPDM) as a main component is exemplified.

The ethylene (co) polymer obtained by the high-pressure radical polymerization method includes ethylene homopolymer (low-density polyethylene) obtained by the high-pressure radical polymerization method, ethylene
Examples include vinyl ester copolymers and copolymers of ethylene with an α, β-unsaturated carboxylic acid or a derivative thereof.

The low-density polyethylene is produced by a known high-pressure radical polymerization method. The high pressure radical polymerization method
Either the tubular method or the autoclave method may be used.
The low-density polyethylene (LDPE) obtained by the high-pressure radical polymerization method has an MFR of 0.05 to 100 g / 10
Min, more preferably in the range of 0.1 to 50 g / 10 min. The density is in the range of 0.91 to 0.94 g / cm ³ , more preferably 0.91 to 0.935 g / cm ³ . The melt tension is 1.5 to 25 g, preferably 3 to 20 g, and more preferably 3 to 15 g.
Further, the molecular weight distribution (Mw / Mn) is 3.0 to 12, preferably 4.0 to 8.0.

The ethylene / vinyl ester copolymer is produced by a high-pressure radical polymerization method. Ethylene and vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, It is a copolymer with vinyl ester monomers such as vinyl stearate and vinyl trifluoroacetate. Among these, particularly preferred is vinyl acetate. A copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferred. Furthermore, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight.

Further, typical copolymers of the above-mentioned copolymers of ethylene with an α, β-unsaturated carboxylic acid or a derivative thereof include ethylene / (meth) acrylic acid or an alkyl ester copolymer thereof. Can be These comonomers include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methacrylic acid
Examples thereof include n-butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and the like. Of these, particularly preferred are alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate. Particularly, the content of the (meth) acrylate is 3 to 20% by weight,
Preferably it is in the range of 5 to 15% by weight. Among these other ethylene polymers (B), the high-pressure radical method low-density polyethylene is most preferably used because of its excellent moldability.

When the resin material containing the ethylene (co) polymer (A) in the present invention is a composition containing the other ethylene polymer (B), the resin containing the ethylene (co) polymer (A) The material is ethylene (co) polymer (A)
100 to 10% by weight and other ethylene polymer (B)
A resin composition containing less than 90% by weight, preferably 95 to 50% by weight of an ethylene (co) polymer (A) and a low-density polyethylene (hereinafter referred to as LDPE) 5 to 5 obtained by a high-pressure radical polymerization method. 50% by weight, more preferably 90 to 60% by weight of the ethylene (co) polymer (A),
It is a resin composition containing 10 to 40% by weight of another ethylene-based polymer (B). 1 ethylene (co) polymer (A)
When the content is 0% by weight or less, the low-temperature heat sealability of the laminate is deteriorated, which is not preferable.

The resin material containing the ethylene (co) polymer (A) in the present invention can be molded at a low temperature and its surface treatment such as ozone treatment is effective, although the reason is not clear. Performing the low-temperature molding has the advantage that the resin hardly deteriorates due to heat and the need to add an antioxidant is eliminated. In addition, since molding at a low temperature reduces resin blocking, it is not necessary to add an anti-blocking agent or the like. In addition, if the ethylene (co) polymer (A) is produced using a halogen-free catalyst, it is not necessary to add an acid absorbent. Furthermore, even when molding is performed at the conventional molding temperature or at a higher temperature, the generation of smoke and odor can be suppressed because the molecular weight is essentially low.

The resin material containing the ethylene (co) polymer (A) may contain a known additive such as an acid absorbent, an antioxidant and an antiblocking agent, as well as a lubricant, an antistatic agent and an antifogging depending on the use. It is preferable that no known additives such as an agent, an ultraviolet absorber, an organic or inorganic pigment, a nucleating agent, and a crosslinking agent are included. Even when an additive is used, one of the features of the present invention is that the additive is an additive that does not substantially elute outside or does not affect the contents. Here, the additive which does not affect the contents is an ethylene (co) polymer (A)
It is an additive that does not transfer odors and elution components (off-flavors) to the contents of the container when a laminate containing a resin material containing is used as a container. In the present invention,
An additive that elutes to the outside, for example, when the content is a liquid, an additive that elutes into the liquid, an additive that transfers odor, or is unevenly distributed on the film surface with time. Since such an additive is not contained in the resin material containing the ethylene (co) polymer (A), a clean laminate and a container can be provided.

The additive that does not elute to the outside is a filler such as an organic or inorganic filler, which does not alter the contents of the container and does not essentially impair the properties of the laminate or container of the present invention. It is an additive that can be added in a range. As inorganic fillers, calcium carbonate, talc, silica,
Clay, carion, alumina, aluminum hydroxide, magnesia, magnesium hydroxide, calcium sulfate, calcium sulfite, barium sulfate, aluminum silicate, calcium silicate, sodium silicate, potassium silicate, magnesium carbonate, barium carbonate, calcium oxide, titanium oxide, oxidation Zinc, mica, glass flake, zeolite,
Diatomaceous earth, perlite, permiculite, shirasu balloon, glass microsphere, fly ash, glass beads and the like can be mentioned. Examples of the organic filler include a crosslinked product of polymethyl methacrylate, a crosslinked product of polyethylene terephthalate, phenol resin and other synthetic resin powders and fine beads, wood powder, pulp powder, and the like. The resin material containing the ethylene (co) polymer (A) includes:
It is desirable that additives that may decrease the adhesiveness to the base material layer (I) and the thermoplastic resin film layer (III), such as a lubricant such as calcium stearate, are not blended.

The material used for the substrate layer (I) in the present invention is a thermoplastic resin, paper, nonwoven fabric or woven fabric. Examples of the thermoplastic resin include polyester resin, polyamide resin, saponified ethylene / vinyl acetate copolymer, polypropylene, polyethylene resin, polyvinylidene chloride resin, and other films, and include stretched and printed products thereof. . Examples of the second base material layer (III) in the present invention include thermoplastic resin films, metal foils, metal-deposited films, papers, nonwoven fabrics, woven fabrics, cellophane, etc., which are the same or different from the base material layer (I). It is. As the metal foil or the metal deposited film, aluminum, gold, silver, iron,
Metal foils such as steel, copper, nickel and alloys containing these as a main component; on the surface of films such as polyester and polyamide,
Examples thereof include a vapor-deposited film obtained by vapor-depositing a metal such as aluminum or silicon or a metal oxide thereof.

In the laminate of the present invention, a resin layer (II) made of a resin material containing an ethylene (co) polymer (A) is provided on at least one surface of the base material layer (I) without interposing an anchor coat agent. It is directly bonded. The first of the laminate of the present invention is:
The base material layer (I) and the resin layer (II) made of a resin material containing the ethylene (co) polymer (A) were directly joined, (I / I
I) A laminate including a structure. As a specific example, P
A film / SLL, paper / SLL, nonwoven fabric / SLL, woven fabric / SLL, PA film / (SLL + LD), PET
Film / SLL, (SLL + LD) / PET film, SLL / PA film / SLL, (SLL + LD)
/ PET film / (SLL + LD), (SLL + LL
+ LD) / PET film / (SLL + LL + LD),
(SLL + HD + LD) / PET film / (SLL +
HD + LD), SLL / PET film / LD, SLL
/ PET film / LD, etc., but are not limited thereto. (Here, SLL: ethylene (co) polymer (A), LD: high pressure radical low density polyethylene, LL: linear low density polyethylene, HD: high density polyethylene, PA: polyamide resin, PET: polyester resin. )

In the second laminate of the present invention, the base layer (I) and the resin layer (II) made of a resin material containing the ethylene (co) polymer (A) are directly bonded to each other, and Second substrate layer (III) was laminated in contact with (II) (I / II / III)
It is a laminate including a structure. Specific examples include cellophane / SLL / PET film / SLL, PP / SLL
/ Paper / SLL, LD / paper / (SLL + LD) / PET film, LD / (SLL + LD) / PA film, LD
/ PET film / SLL / paper, HD film / (SL
L + LD) / paper / LD.

In addition, the laminate of the present invention is characterized in that the above-mentioned ethylene (co) is A second resin layer (IV) and / or a third resin layer (V) made of a resin material containing the polymer (A) are laminated (I / II /
III / IV) or (V / I / II / III) or (V / I /
It may be a laminate having a (II / III / IV) structure.

Since the resin material containing the ethylene (co) polymer (A) has excellent adhesiveness to the substrate, the laminate of the present invention can be used without using an anchor coat agent. Excellent adhesive strength between layers. Moreover, since the resin material containing the ethylene (co) polymer (A), which is the sealant layer, is directly laminated on the base material, the conventional LDPE layer can be dispensed with and can be replaced with the conventional LDPE layer. If a resin material containing the ethylene (co) polymer (A) is provided, a stronger laminate can be obtained, and the stability as a packaging material can be improved. In addition, since the additives blended in the resin material do not elute to the outside or do not affect the contents, they have low odor and deteriorate the quality of the contents even when used as containers and packaging materials. There is no.

As a method for producing a laminate of the present invention, (A) a resin material containing an ethylene (co) polymer as a main component is anchored on a substrate by extrusion lamination, dry lamination, tandem lamination, or the like. There is a method of laminating without using a coating agent. Among them, the extrusion lamination method is particularly preferable.

In the method for producing a laminate of the present invention, a resin material containing an ethylene (co) polymer (A) containing no additive, or an additive which does not substantially elute as an additive, A resin material containing an ethylene (co) polymer (A) containing only additives that do not affect the contents is used. Such an ethylene (co) polymer (A)
By using a resin material containing, it is possible to produce a clean laminate or container which does not cause odor migration or elution due to the additive and is less likely to cause taste and deterioration. Also,
Since a resin material containing an ethylene (co) polymer (A) having excellent adhesion to a substrate is used, it is not necessary to use an anchor coat agent. Moreover, since the LDPE layer provided between the base layer and the heat seal layer of the conventional laminate is not required, the laminate can be manufactured with a small number of steps.

When the ethylene (co) polymer (A) is extrusion-laminated with a resin material, the molten resin is subjected to an ozone treatment while the melting point is not lower than the melting point and not higher than 330 ° C., preferably 20 ° C.
It is desirable to perform extrusion lamination at a molding temperature of 0 to 300 ° C. By performing the ozone treatment, the base material layer (I) and the resin layer (II) can be formed even by extrusion lamination at a low temperature.
And the adhesive strength between them can be maintained. At the time of lamination, it is preferable to perform a surface treatment such as a corona discharge treatment on the substrate. In addition, by performing a surface treatment on both the molten film and the base material, the base material layer (I) and the resin layer (I
Adhesion strength with (I) can be further improved.

The container of the present invention is obtained by molding the above-mentioned laminate having excellent gas barrier properties into a container shape. Examples of the use of the container of the present invention include containers for liquids such as milk, alcohol, juice, coffee, drinking water, and oil; containers for packing frozen desserts such as yokan and jelly, dried foods, oils and fats, and confectioneries. It is.

[0070]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to restrict the scope of the present invention. The test method in this example is as follows. [Density] Based on JIS K6760. [MFR] Based on JIS K6760. [Mw / Mn] GPC (150C type manufactured by Waters)
And 135 ° C. ODCB was used as a solvent. The column used was Shodex HT806M. [Measurement of T _ml by DSC] A sheet having a thickness of 0.2 mm was formed by hot pressing, and a sample of about 5 mg was punched out of the sheet. This sample was kept at 230 ° C. for 10 minutes and then cooled to 0 ° C. at 2 ° C./min. Then again at 10 ° C / min.
C., and the temperature at the top of the highest temperature peak that appeared was defined as the highest peak temperature T _ml . [TREF] With the column maintained at 140 ° C., a sample was injected into the column, the temperature was lowered to 25 ° C. at 4 ° C./hr, and the polymer was deposited on glass beads. Then, the column was heated under the following conditions. The concentration of the polymer eluted at each temperature was detected with an infrared detector. (Solvent: ODCB, flow rate: 1 ml /
Min, heating rate: 50 ° C./hr, detector: infrared spectrometer (wavelength: 2925 cm ⁻¹ ), column: 0.8 cmφ × 12 cm
L (filled with glass beads), sample concentration: 0.05% by weight)

[Melt tension (MT)] The stress when the melted polymer was stretched at a constant speed was determined by measuring with a strain gauge. The measurement sample was granulated and pelletized, and was manufactured by Toyo Seiki Seisakusho M
It was measured using a T measuring device. The orifice used has a hole diameter of 2.09 mmφ and a length of 8 mm. The measurement conditions are a resin temperature of 190 ° C., a cylinder descending speed of 20 mm / min, and a winding speed of 15 m / min. [Chlorine concentration] It was measured by a fluorescent X-ray method, and when chlorine of 10 ppm or more was detected, this was taken as an analytical value.
When the concentration was lower than 10 ppm, it was measured with a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd. [Adhesive strength] Using a tensile tester, a tensile speed of 300 mm
Each layer of the test piece (15 mm width) of the laminate was peeled under the condition of / min, and the 180 degree peel strength at that time was obtained. [Smoke emission during lamination] The amount of smoke emitted from the resin material during extrusion lamination was visually observed and evaluated according to the following criteria. ：: Smoke is extremely low. Δ: Operation is possible although there is smoke. ×: Smoke is generated and operation is hindered (deterioration may adhere to rolls and the like in long-term operation).

Various components used in Examples and Comparative Examples are as follows. 1) Ethylene (co) polymer (A) (A11 and A1
2) was polymerized by the following method. (A11) The ethylene copolymer was polymerized by the following method. [Preparation of solid catalyst] To a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ), 75 g of indene and 88 g of methylbutylcyclopentadiene were added, and 90 ° C. 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the
The reaction was performed at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration 2.5 mmol /
ml) was added and stirred for 2 hours. Next, 2000 g of silica (manufactured by Grace, # 952, surface area: 300 m ² / g), which had been calcined at 450 ° C. for 5 hours, was added. After stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. A solid catalyst (a) having good properties was obtained.

[Gas phase polymerization] Continuous type fluidized bed gas phase polymerization apparatus
At a polymerization temperature of 65 ° C. and a total pressure of 20 kgf / cm ^Two In G
Copolymerization of ethylene and 1-hexene was performed. The solid touch
The medium (a) is continuously supplied, and ethylene, 1-hexene and
And hydrogen are supplied so as to maintain a predetermined molar ratio to carry out polymerization.
Thus, an ethylene copolymer (A11) was obtained.

(A12) The ethylene copolymer was polymerized by the following method. [Preparation of solid catalyst] To a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ) and 74 g of indene were added. 100 g of aluminum is dropped over 100 minutes,
Thereafter, the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration: 2.5 m
(mol / ml) and stirred for 2 hours.
Next, silica (manufactured by Grace, # 952, surface area: 300 m ² / g) 2 previously calcined at 450 ° C. for 5 hours 2
After stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (b) having good fluidity.

[Gas phase polymerization] Continuous type fluidized bed gas phase polymerization apparatus
At a polymerization temperature of 70 ° C. and a total pressure of 20 kgf / cm ^Two In G
Copolymerization of ethylene and 1-hexene was performed. The solid touch
The medium (b) is continuously supplied, and ethylene, 1-hexene and
And hydrogen are supplied so as to maintain a predetermined molar ratio to carry out polymerization.
Thus, an ethylene copolymer (A12) was obtained.

(A2) The ethylene copolymer was polymerized by the following method. [Preparation of solid catalyst] To a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetrabutoxyzirconium (Zr (OBu) ₄ ), 40 g of indene and 21 g of methylpropylcyclopentadiene were added, and 90 ° C. , 100 g of tripropylaluminum was added dropwise over 100 minutes, and then reacted at the same temperature for 2 hours. After cooling to 40 ° C,
Methylalumoxane toluene solution (concentration 2.5mmo
1 / ml) and stirred for 2 hours. Next, silica (manufactured by Grace, # 952, surface area: 300 m ² / g) 2,000 calcined in advance at 450 ° C. for 5 hours
After stirring for 1 hour at room temperature, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (c) having good fluidity.

[Gas phase polymerization] Continuous type fluidized bed gas phase polymerization apparatus
At a polymerization temperature of 80 ° C. and a total pressure of 20 kgf / cm ^Two In G
Copolymerization of ethylene and 1-hexene was performed. The solid touch
The medium (c) is continuously supplied, and ethylene, 1-hexene and
And hydrogen are supplied so as to maintain a predetermined molar ratio to carry out polymerization.
Thus, an ethylene copolymer (A2) was obtained.

(MLL) Ethylene / hexene-1 copolymer using a general metallocene catalyst Purified toluene was placed in a pressure reactor equipped with a stirrer and purged with nitrogen, then 1-hexene was added, and bis (n-
A mixture of (butylcyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) was mixed with (Al /
(Zr molar ratio = 500), and the temperature was raised to 80 ° C. to prepare a metallocene catalyst. Then, add ethylene,
While continuously polymerizing ethylene, polymerization was carried out while maintaining the total pressure at 6 kg / cm ³ to produce an ethylene / hexene-1 copolymer (A3). The physical properties are shown in Table 1.

[0079]

[Table 1]

Table 1 shows the physical properties of a commercially available Ziegler-catalyzed linear low-density polyethylene (LLDPE: B1). Commercial high-pressure low-density polyethylene (LDPE: C1) Density: 0.918 g / cm ³ , MFR: 7 g / 10 min Commercial high-pressure low-density polyethylene (LDPE: C2) Density: 0.919 g / cm ³ , MFR: 7 g / 10 min Ethylene methacrylic acid copolymer (EMAA: D1) MAA concentration 11% by weight, MFR: 8 g / 10 min

Example 1 A 12 μm-thick polyethylene terephthalate (PET) substrate was coated with ethylene (co)
A resin material composed of 70% by weight of the polymer (A11) and 30% by weight of LDPE (C1) was subjected to corona treatment (6 kW) and ozone treatment (50 g / m ³ ) on the surface of the molten resin film on the side in contact with the base material. Extrusion lamination was performed at 290 ° C. with a thickness of 30 μm. The line speed was 150 m / min. The adhesive strength between the base material layer (I) and the resin layer (II) was measured. Table 2 shows the results.

[Example 2] 70% by weight of ethylene (co) polymer (A11) and L
A resin material composed of 30% by weight of DPE (C1) was extrusion-laminated at 316 ° C. with a thickness of 30 μm while a corona treatment (6 kW) was applied to the surface of the PET substrate on which the resin was laminated. The line speed was 150 m / min. The adhesive strength between the base material layer (I) and the resin layer (II) was measured.
Table 2 shows the results.

Example 3 An ethylene (co) polymer (A1) was coated on the surface of a 15 μm-thick stretched nylon (ONy)
2) While applying a corona treatment (6 kW) and an ozone treatment (50 g / m ³ ) to the surface of the molten resin film on the side in contact with the base material, a resin material composed of 70% by weight and 30% by weight of LDPE (C1) is Extrusion lamination was performed at 290 ° C. with a thickness of 30 μm. The line speed was 150 m / min. The adhesive strength between the base material layer (I) and the resin layer (II) was measured. Table 2 shows the results.

Example 4 PE having a thickness of 12 μm as a base material
T film, 7 μm thick aluminum foil (AL # 7) as sand side substrate, and ethylene (co)
A resin material composed of 70% by weight of the polymer (A12) and 30% by weight of LDPE (C1) was treated with ozone (50 g / m2).
³ ) at 310 ° C. while applying corona treatment (6 kW) to the PET and AL surfaces and applying corona treatment (6 kW) to the PET surface.
Extrusion sand lamination was performed at a thickness of 0 μm. Further, ethylene (co) is formed on the aluminum foil (second base material layer (III)).
A resin material composed of 70% by weight of the polymer (A12) and 30% by weight of LDPE (C1) was treated with ozone (50 g / m2).
Extrusion lamination was performed at 290 ° C. with a thickness of 30 μm while ³ ) was applied to the AL surface. All line speeds are 150m / m
was in. The adhesive strength between the layers was measured. Table 2 shows the results.

[Example 5] 52.5 g / m2 as base material^Three 
High quality paper, 12μm thick PET
And an ethylene (co) polymer (A)
2) 70% by weight and 30% by weight of LDPE (C2)
Ozone treatment (50 g / m^Three )
And corona treatment (6 kW) while applying to PET and PET surfaces
Extrusion sand at 310 ° C with a thickness of 30 μm while applying on paper
Laminated. Further, a PET film (second base material)
Ethylene (co) polymer (A12) 70 on layer (III))
Resin consisting of 30% by weight and 30% by weight of LDPE (C1)
Ozone treatment (50 g / m ^Three ) On the PET surface
It was extrusion-laminated at 290 ° C. with a thickness of 30 μm. La
The in-speed was 150 m / min in all cases. Each layer
Was measured for adhesive strength. Table 2 shows the results.

[0086]

[Table 2]

[Comparative Example 1] LDPE (C
A laminate was produced in the same manner as in Example 1 except that only 1) was used. The adhesive strength between the base material layer (I) and the resin layer (II) was measured. Table 3 shows the results. The adhesive strength between the base material layer (I) and the resin layer (II) was poor. Also, the results of the relative odor test described below were inferior to those of Example 1.

[Comparative Example 2] LDPE (C
A laminate was produced in the same manner as in Example 2 except that only 1) was used. The adhesive strength between the base material layer (I) and the resin layer (II) was measured. Table 3 shows the results. The adhesive strength between the base material layer (I) and the resin layer (II) was poor. The results of the relative odor test described later were also inferior to those of Example 2.

Comparative Example 3 EMAA (D
A laminate was produced in the same manner as in Example 1 except that only 1) was used. The adhesive strength between the base material layer (I) and the resin layer (II) was measured. Table 3 shows the results. Although the resin layer (II) was cut (poly cut), the adhesive strength between the base material layer (I) and the resin layer (II) was better as compared with Comparative Examples 1 and 2. However, the results of the relative odor test described below indicate that:
It was inferior to Example 1.

[Comparative Example 4] LDPE (C
A laminate was produced in the same manner as in Example 3 except that only 2) was used. The adhesive strength between the base material layer (I) and the resin layer (II) was measured. Table 3 shows the results. The adhesive strength between the base material layer (I) and the resin layer (II) was poor. The results of the relative odor test described later were also inferior to those of Example 3.

[Comparative Example 5] LLDPE was applied to the resin layer (II).
A laminate was produced in the same manner as in Example 1, except that a resin material consisting of (B1) 70% by weight and LDPE (C1) 30% by weight was used. The adhesive strength between the base material layer (I) and the resin layer (II) was measured. Table 3 shows the results. The adhesive strength between the base material layer (I) and the resin layer (II) was poor.
Also, the results of the relative odor test described below were inferior to those of Example 1.

[0092]

[Table 3]

[Comparative Example 6] LLDPE was applied to the resin layer (II).
A laminate was produced in the same manner as in Example 3, except that a resin material composed of (B1) 70% by weight and LDPE (C1) 30% by weight was used. The adhesive strength between the base material layer (I) and the resin layer (II) was measured. Table 4 shows the results. The adhesive strength between the base material layer (I) and the resin layer (II) was poor.
The results of the relative odor test described later were also inferior to those of Example 3.

[Comparative Example 7] EMAA (D
A laminate was produced in the same manner as in Example 4 except that only 1) was used, the molding temperature was 290 ° C., and only LDPE (C2) was used for the second resin layer (IV). The adhesive strength between the layers was measured. Table 4 shows the results. The result of the relative odor test described later was inferior to that of Example 4.

Comparative Example 8 A laminate was produced in the same manner as in Example 5, except that only EMAA (D1) was used for the resin layer (II) and the second resin layer (IV), and the molding temperature was 290 ° C. Was prepared. The adhesive strength between the layers was measured. Table 4 shows the results. The result of the relative odor test described later was inferior to that of Example 5.

[Comparative Example 9] LLDPE was applied to the resin layer (II).
(B1) A resin material composed of 70% by weight of LDPE (C1) and 30% by weight of LDPE (C1) was used. A laminate was produced in the same manner as in Example 5, except that a resin material consisting of The adhesive strength between the layers was measured. Table 4 shows the results. The adhesive strength of the resin layer (II) and the second resin layer (IV) to the second base material layer (III) was poor.

[0097]

[Table 4]

[Relative odor] A regular tetrahedral container having a side of about 20 cm was prepared by heat sealing using the laminates of the examples and comparative examples. Relative odor test was performed in tests # 1 to #
In the combination shown in FIG. 5, the odor was compared by comparing two types of containers. Specifically, after storing the two types of containers in air at 70 ° C. for 3 hours, the condition was adjusted at room temperature for 24 hours, and opened with scissors to have a plurality of subjects compare their odors. . The evaluation of the relative odor test is performed by giving a score of 1 for the strong odor, 0 for the weak odor, and 0.5 for both if the odor is indistinguishable, and summing the scores of all the subjects. Was. If there was a noteworthy type of odor, it was recorded separately. The results are shown in Tables 5 to 14.
Shown in In the table, the poly odor is a paraffin odor, and the sour odor is a pungent odor that smells like an acid. The burning odor is an odor that is emitted when things burn or burn.

[0099]

[Table 5]

[0100]

[Table 6]

[0101]

[Table 7]

[0102]

[Table 8]

[0103]

[Table 9]

[0104]

[Table 10]

[0105]

[Table 11]

[0106]

[Table 12]

[0107]

[Table 13]

[0108]

[Table 14]

[0109]

As described above, the laminate of the present invention comprises a base material layer (I) comprising at least one material selected from the group consisting of thermoplastic resin, paper, nonwoven fabric and woven fabric.
A resin layer (II) made of a resin material containing an ethylene (co) polymer (A) satisfying the requirements (a) to (d) described above is directly adhered to at least one surface of the resin material, and an additive is added to the resin material. Is not blended, or the additive blended in the resin material is an additive that does not elute or affect the outside, so even if an anchor coat agent is not used, the The adhesive strength between them is excellent, the odor is small, and the quality of the contents does not deteriorate even when used as a container or packaging material. Further, such a laminate is excellent in tear strength, impact resistance, moldability, heat seal strength, heat resistance, and the like, and can also impart gas barrier properties. Further, the LDPE layer, which has been conventionally required, becomes unnecessary, and the number of layers can be reduced by one. In addition, when the ethylene (co) polymer (A) further satisfies the above requirement (e), a laminate having excellent low-temperature heat sealability is obtained.

If the second base material layer (III) is in contact with the surface of the resin layer (II) on the side not in contact with the base material layer (I), a barrier property against water vapor is imparted. Is possible. Also, the second side on the side not in contact with the resin layer (II)
A second resin layer (IV) and / or a third resin layer made of a resin material containing the ethylene (co) polymer (A) on the surface of the base material layer (III) and / or the base material layer (I). When the resin layer (V) is laminated, water resistance is imparted, and a strong seal can be provided between the front and back surfaces of the base material (so-called “back waist”).

The resin material containing the ethylene (co) polymer (A) may be an ethylene (co) polymer (A) 50 to 9
If it contains 8% by weight and 2 to 50% by weight of another ethylene polymer (B) having a density of 0.88 to 0.97 g / cm ³ , the molding stability at the time of extrusion coating can be further improved. . Further, when the other ethylene polymer (B) is a low-density polyethylene obtained by a high-pressure radical polymerization method, the moldability can be further improved.

The ethylene (co) polymer (A)
However, if the (A1) ethylene (co) polymer further satisfies the above requirements (f) and (g), the sanitary properties, heat resistance, and rigidity can be further improved, and down gauges are also possible. Further, the ethylene (co) polymer (A) further satisfies the above requirements (h) and (i) (A2)
If it is an ethylene (co) polymer, heat resistance, heat seal strength and low temperature heat sealability can be further improved. Further, when the (A2) ethylene (co) polymer further satisfies the above requirement (j), the moldability can be further improved.

The ethylene (co) polymer (A)
Is, if produced by a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table, mechanical properties, heat sealing properties, heat blocking properties, heat resistance, etc. Can be further improved. Further, when the halogen concentration in the resin material containing the ethylene (co) polymer (A) is 10 ppm or less, it is not necessary to add an acid absorbent, and the hygiene of the laminate can be further improved.

Further, the method for producing a laminate according to the present invention is characterized in that at least one surface of the base material layer (I) comprising at least one material selected from the group consisting of thermoplastic resin, paper, nonwoven fabric and woven fabric, Direct extrusion lamination of a resin material containing ethylene (co) polymer (A) as a main component and containing no additives, or additives that do not elute or have no influence on the outside Then, if the method of forming the resin layer (II) is used, even if an anchor coating agent is not used, the adhesive strength between the base material and the resin layer is excellent, the odor is small, and it is used as a container or a packaging material. Even if it does not deteriorate the quality of the contents, it is possible to obtain a laminate having excellent tear strength, impact resistance, moldability, heat seal strength, heat resistance, etc., and also provided with gas barrier properties. it can. Further, since the LDPE layer provided between the base layer and the heat seal layer of the conventional laminate becomes unnecessary, the laminate can be manufactured in a small number of steps.

In the method for producing a laminate of the present invention, when the resin material containing the ethylene (co) polymer (A) is directly extruded and laminated on the base material layer (I), the ethylene (co) polymer By extruding and laminating the molten resin of the resin material containing (A) at a molding temperature of not less than the melting point of the resin material containing ethylene (co) polymer (A) and 300 ° C. or less while performing ozone treatment, the base material layer (I ) And the resin layer (II) can be manufactured as a laminate having further excellent adhesive strength.

Since the container of the present invention is made of the laminate of the present invention, the container has low odor. Moreover, since it is made of a laminate having a high adhesive strength between the base material layer (I) and the resin layer (II),
No bag breaks or pinholes. further,
Tear strength, impact resistance, moldability, heat seal strength,
Excellent heat resistance. And the container which consists of a laminated body which does not contain an additive does not give the transfer of the odor to the contents, nor the deterioration of the taste of the contents. Such a container can be suitably used as a food container or packaging material for milk or the like that complies with the ministerial ordinance for milk.

[Brief description of the drawings]

FIG. 1 is a graph showing an elution temperature-elution amount curve of an ethylene (co) polymer (A) or (A2) in the present invention.

FIG. 2 is a graph showing an elution temperature-elution amount curve of the (A1) ethylene (co) polymer in the present invention.

FIG. 3 is a graph showing an elution temperature-elution amount curve of an ethylene copolymer by a general metallocene catalyst.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 4/642 C08F 10/02 4J002 10/02 C08J 5/00 CES 4J028 C08J 5/00 CES C08L 23/04 4J100 C08L 23/04 B29K 23:00 // B29K 23:00 105: 08 105: 08 B29L 9:00 B29L 9:00 B65D 1/00 B (72) Inventor Ippei Kagaya 2-chome Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture No. 3-2 Japan Polyolefin Co., Ltd. Research and Development Center (72) Inventor Hiroshi Kasahara 2-3-2 Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term in Technical Research and Development Center of Japan Polyolefin Co., Ltd. 3E033 AA20 BA10 BA13 BA14 BA15 BA30 BB08 CA03 CA07 CA16 GA02 GA03 3E086 AB01 AD03 AD06 BA0 4 BA14 BA15 BA18 BA19 BB02 BB05 BB22 CA01 CA11 CA27 CA31 4F071 AA12X AA15 AA15X AA19 AA20X AA21X AA28X AA32X AA33X AA76 AA80 AA81 AA82 AA84 AA88 BA05 AT04 BA01 BC04 BC01 BC04 BC01 BC04 BC01 BC04 BC01 BC04 BC01 BC04 BA10D BA13 CA30B DG10A DG12A DG15A EC18 EH112 EH232 EJ132 EJ422 EK172 GB15 GB16 GB23 JA04D JA06B JA06D JA07B JA13B JA13D JB08B JB08D JB16A JD02 JJ03 JK03 JK10 JL01 JL08 AAD04 A12A04 A12A04 A12A04 KB26 KF01 KF02 KJ09 KK82 KK85 4J002 BB03W BB03X BB05W BB05X BB06X BB07X BB08X BB15W BB15X ED010 GF00 GG01 4J028 AA01A AB00A AB01A AC01A AC20A AC28A BA00A BA02B BA03B BB00A BB00B BB01B BB02B BC01B BC05B BC06B BC09B BC12B BC13B BC15B BC16B BC17B BC25B CB03C CB91C EA01 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EC01 EC02 FA02 FA04 FA06 FA07 GA01 GA06 GA07 GA08 GA19 GA21 4J100 AA02P AA03Q AA07Q AA16Q AA17Q AA19Q CA01 CA04 DA01 DA04 DA13 DA14 DA40 DA43 FA10

Claims (14)

[Claims] 1. The following requirements (a) to (d) are provided on at least one surface of a base material layer (I) made of at least one material selected from the group consisting of thermoplastic resin, paper, nonwoven fabric and woven fabric. A resin layer (II) made of a resin material containing a satisfactory ethylene (co) polymer (A) is directly adhered, and no additive is added to the resin material, or an additive added to the resin material is A laminate characterized in that it is an additive that does not elute into the product or does not affect the contents. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 50 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.5 to 4.5 (d ) elution temperature by continuous Atsushi Nobori elution fractionation (TREF) - the difference T ₇₅ between the temperature T ₇₅ to 75% of the total temperature T ₂₅ to 25% of the total determined from the integral elution curve of elution amount curve is eluted elutes −T ₂₅ and density d satisfy the relationship of the following (Equation 1) (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644 2. The laminate according to claim 1, wherein the ethylene (co) polymer (A) further satisfies the following requirement (e). (E) Difference between the temperature T _{25 at} which 25% of the whole is eluted and the temperature T _{75 at} which 75% of the whole is eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF) T ₇₅ −T ₂₅ and density d satisfy the relationship of the following (Formula 2) (Formula 2) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 d ≧ 0.950 g / Cm ³ T ₇₅ −T ₂₅ ≧ 0 3. The laminate according to claim 1, further comprising a second base layer (III) in contact with the surface of the resin layer (II) on the side not in contact with the base layer (I). body. 4. The surface of the second base material layer (III) and / or the base material layer (I) on the side not in contact with the resin layer (II),
The resin composition according to claim 3, wherein a second resin layer (IV) and / or a third resin layer (V) made of a resin material containing the ethylene (co) polymer (A) are laminated. Laminate. 5. It contains the ethylene (co) polymer (A).
The resin material is an ethylene (co) polymer (A) 100 to 10
Weight% and density 0.88 to 0.97 g / cm ^Three Other d
Contains less than 90% by weight of a tylene polymer (B)
The method according to any one of claims 1 to 4, wherein
On the laminate. 6. The laminate according to claim 5, wherein the other ethylene polymer (B) is a low-density polyethylene obtained by a high-pressure radical polymerization method. 7. The ethylene (co) polymer (A) further satisfies the following requirements (f) and (g) (A1):
2. An ethylene (co) polymer.
7. The laminate according to any one of claims 6 to 6. (F) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by weight), the density d, and the melt flow rate (MFR) satisfy the following relationship. 4) When d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR)
² + 2.0 (g) Presence of multiple peaks in elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) 8. The ethylene (co) polymer (A) further satisfies the following requirements (h) and (i) (A2):
2. An ethylene (co) polymer.
7. The laminate according to any one of claims 6 to 6. (H) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF). (I) One or two melting point peaks, and the highest melting point T _m1 and density d among them Satisfies the relationship of (Equation 5) below (Equation 5) T _m1 ≧ 150 × d−17 9. The (A2) ethylene (co) polymer,
The laminate according to claim 8, further satisfying the following requirement (j). (J) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR +
0.3 10. The ethylene (co) polymer (A),
The laminate according to any one of claims 1 to 9, wherein the laminate is produced using a catalyst containing an organic cyclic compound having at least a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. . 11. The laminate according to claim 1, wherein a halogen concentration in the resin material containing the ethylene (co) polymer (A) is 10 ppm or less. 12. A substrate layer (I) composed of at least one material selected from the group consisting of thermoplastic resin, paper, nonwoven fabric and woven fabric, on at least one surface of the substrate layer (I):
Including an ethylene (co) polymer (A) satisfying the requirements of
And forming a resin layer (II) by directly extruding and laminating a resin material which is an additive in which no additive is blended or in which the blended additive does not elute to the outside or does not affect the contents. A method for producing a laminate, characterized in that: (A) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 50 g / 10 min, (c)
Molecular weight distribution (Mw / Mn) of 1.5 to 4.5, (d) Temperature at which 25% of the whole is eluted from the integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) Difference T ₇₅ between T ₂₅ and temperature T _{75 at} which 75% of the total elutes
−T ₂₅ and density d satisfy the relationship of the following (Equation 1) (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644 13. When extruding and laminating a resin material containing an ethylene (co) polymer (A) directly on a substrate layer (I),
Extrusion lamination at a molding temperature not lower than the melting point of the resin material containing the ethylene (co) polymer (A) and not more than 330 ° C. while applying ozone treatment to the molten resin of the resin material containing the ethylene (co) polymer (A). The method for producing a laminate according to claim 12, wherein: 14. A container comprising the laminate according to any one of claims 1 to 11.