JP2001191452A - Laminate, method for manufacturing the same and container using laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in the adhesive strength between a resin layer and the metal surface of a metal foil or a metal vapor deposition film even if no anchor coat agent is used and reduced in offensive smell and container using this laminate. SOLUTION: A laminate has a resin layer (I) comprising a resin material based on an ethylene (co)polymer (A), wherein (a) density is 0.86-0.97 g/cm3, (b) a melt flow rate is 0.01-50 g/10 min, (c) molecular weight distribution (Mw/Mn) is 1.5-4.5 and (d) the difference T75-T25 between temperature T25 wherein 25% of the whole is eluted calculated from the integrated elusion curve of an elution temperature-elution quantity curve by a continuous temperature rise elution and fractionation method (TREF) and temperature T75 wherein 75% of the whole is eluted and density (d) satisfy a specific relation, and a metal layer (II) comprising a metal foil or a metal vapor deposition film provided on the single surface of the resin layer (I). A container using this laminate is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a gas barrier,
Excellent in tear strength, impact resistance, moldability, adhesive strength between layers, low-temperature heat sealing, etc., less transition of taste, odor, etc., suitable for packaging foods, especially liquids, a method for producing the same, and this laminate For containers using the body, in particular, moisture, oxygen, barrier packaging material for the purpose of blocking light,
Clean packaging materials used for retort foods, medical supplies, electronic materials, etc., laminates used for containers, etc.
The present invention relates to a laminate suitable for a food container conforming to a ministerial ordinance such as milk, a method for producing the same, and a container using the laminate, particularly in the fields of food and medical care.

[0002]

2. Description of the Related Art Hitherto, as a gas barrier packaging material, a retort container, a milk container, and the like, a laminate using a metal foil such as an aluminum foil or a metal-deposited film has been used. These laminates usually consist of a laminate containing a gas barrier resin, low density polyethylene and metal foil. These laminates are provided with a gas barrier resin and a low density polyethylene (LD) in order to maintain the adhesive strength between the layers.
PE), or aluminum foil (Al foil) and LDP
An anchor coat agent or the like is used as an adhesive between E and E.

[0003] However, when an anchor coat agent or the like is used, the adhesive strength between the layers is maintained, but the use of a solvent causes problems such as safety, contamination of the working environment, and equipment costs. On the other hand, when the anchor coating agent is not used, the adhesive strength is weakened, so that the bag is broken or A
(1) There is a problem that pinholes are easily generated in the foil, and the quality as containers and packaging materials is not stable.

[0004] Even if an anchor coating agent is not used, A
(1) As a resin having excellent adhesiveness to a metal such as a foil, a copolymer of ethylene and methyl acrylate (EMMA), a copolymer of ethylene and acrylic acid (EAA), an ionomer, a polymethyl methacrylate (PMMA), etc. Is used in some cases. However, containers using these resins not only have the disadvantage that the odor and the eluted components (off-flavors) due to the decomposition of the resin are transferred to the contents, leading to deterioration of the quality of the contents, and are expensive. He also had points.

Recently, a laminate in which a composition of a specific ethylene / α-olefin copolymer and LDPE is extrusion-laminated on a metal surface of a metal foil or a metallized film is disclosed in Japanese Patent Application Laid-Open No. 9-234837. It has been disclosed.
However, the specific ethylene / α-olefin copolymer is usually produced with a metallocene catalyst using zirconium halide, and halogen remains in the copolymer. In such a copolymer, hydrogen halide is generated at the time of molding, so that it has been necessary to add an acid absorbent or the like.

[0006] Additives such as acid absorbers elute from the laminate,
And in the container using such a laminated body, there existed a problem that the quality of the content deteriorated by the eluted additive. In particular, when the laminate is used for food containers and packaging materials such as milk conforming to the Ministerial Ordinance for Milk, etc., the addition of these additives is not desirable in terms of hygiene.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to achieve excellent adhesive strength between a resin layer and a metal surface of a metal foil or a metal-deposited film without using an anchor coat agent, and to reduce odor. An object of the present invention is to provide a laminate having a small number, a method for producing the laminate, and a container using the laminate. Further, another object of the present invention is to provide a laminate suitable for packaging foods, especially liquids, which has no dissolution of additives and the like, has little shift in taste, has low odor and the like, a method for producing the laminate, and a container using the laminate. Is to provide. Furthermore, an object of the present invention is to provide a laminate excellent in gas barrier properties, tear strength, impact resistance, moldability, low-temperature heat sealing, etc., a method for producing the same, and a container using the laminate. .

[0008]

Means for Solving the Problems The laminate of the present invention comprises a resin layer comprising a resin material mainly composed of an ethylene (co) polymer (A) satisfying the following requirements (a) to (d). I)
And a metal layer (II) made of a metal foil or a metal-deposited film in contact with one surface of the resin layer (I). (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 whole elutes
−T ₂₅ and density d satisfy the following relationship (Equation 1) and the following relationship (Equation 2) (Equation 1) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation 2) T ₇₅ −T ₂₅ ≦ −670 × d + 644

Further, the laminate of the present invention comprises a base material layer (III)
And the ethylene (co) in contact with one surface of the base material layer (III).
A resin layer (I) made of a resin material containing a polymer (A) as a main component, and a metal foil or a metal vapor-deposited film in contact with the surface of the resin layer (I) that is not in contact with the base material layer (III). And a metal layer (II). Also,
The laminate of the present invention comprises the ethylene (co) polymer (A) on the surface of the metal layer (II) and / or the base material layer (III) on the side not in contact with the resin layer (I). It is characterized in that a second resin layer (IV) and / or a third resin layer (V) made of a resin material as a main component are laminated.

The resin material containing the ethylene (co) polymer (A) as a main component is an ethylene (co) polymer (A).
20 to 100% by weight and density 0.88 to 0.97 g / c
It is desirable to contain 80 to 0% by weight of m ³ of another ethylene-based polymer (B). Further, the other ethylene-based polymer (B) is desirably a low-density polyethylene obtained by a high-pressure radical polymerization method. Further, no additive is blended in the resin material containing the ethylene (co) polymer (A) as a main component, or it is blended in a resin material containing the ethylene (co) polymer (A) as a main component. The additive is preferably an additive that does not elute to the outside or an additive that does not affect the contents.

The ethylene (co) polymer (A)
Is preferably (A1) an ethylene (co) polymer that further satisfies the following requirements (e) and (f). (E) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by weight), the density d, and the melt flow rate (MFR) satisfy the following relations (Equation 3) When d−0.008 log MFR ≧ 0.93, X <2.0 (Equation 3) 4) When d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR)
² + 2.0 (f) Multiple peaks in the elution temperature-elution volume curve by continuous temperature elution fractionation (TREF)

The ethylene (co) polymer (A)
Is preferably (A2) an ethylene (co) polymer satisfying the following requirements (g) and (h). (G) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF). (H) One or two melting point peaks, and the highest melting point T _m1 and density d among them Satisfies the following equation (Equation 5). (Equation 5) T _m1 ≧ 150 × d−17

It is desirable that the ethylene (co) polymer (A2) further satisfies the following requirement (i). (I) The melt tension (MT) and the melt flow rate (MFR) satisfy the relationship of the following (Equation 6). (Equation 6) logMT ≦ −0.572 × logMFR + 0.3 The union (A) is desirably 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. The halogen concentration in the resin material containing the ethylene (co) polymer (A) as a main component is 10%.
It is desirably at most ppm.

Further, the method for producing a laminate according to the present invention is characterized in that a resin layer (I) made of a resin material containing the ethylene (co) polymer (A) as a main component, and one surface of the resin layer (I) A method for producing a laminate having a metal layer (II) made of a metal foil or a metal vapor-deposited film in contact with the resin, wherein the resin material containing the ethylene (co) polymer (A) as a main component is a metal foil or a metal vapor-deposited film It is characterized by direct extrusion lamination on top. In the method for producing a laminate according to the present invention, the resin material containing the ethylene (co) polymer (A) as a main component contains no additive or the ethylene (co) polymer (A) It is desirable that the additive compounded in the resin material containing (1) as a main component is an additive that does not elute to the outside or an additive that does not affect the contents.

When a resin material mainly composed of the ethylene (co) polymer (A) is directly extruded and laminated on a metal foil or a metallized film, the ethylene (co) polymer (A) is used as a main component. It is desirable to perform extrusion lamination at a molding temperature not lower than the melting point of the resin material containing the ethylene (co) polymer (A) as a main component and not higher than 300 ° C. while the molten resin of the resin material to be subjected to the ozone treatment. And the container of the present invention is characterized by comprising the laminate of the present invention.

[0016]

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 is one having 3 to 20, preferably 3 to 12 carbon atoms, and specifically, propylene, 1-pentene, 4-methyl-1-
Pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene and the like. Further, the content of these α-olefins is desirably selected in a range of usually 30 mol% or less, preferably 3 to 20 mol% or less.

In the present invention, the ethylene (co) polymer (A) 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 (lumbar strength) and the heat resistance are inferior. 0.97g
/ Cm ³ is difficult to produce industrially.

The ethylene (co) polymer (A) used in the present invention has a melt flow rate (MFR) (b) of 0.01 to 50 g / 10 minutes, preferably 0.05 g / 10 min.
The range is 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).

The ethylene (co) polymer (A) in the present invention can be obtained, for example, from the integrated elution curve of elution temperature-elution amount curve (TREF) as shown in FIG. The temperature T at which 25% of the obtained total elutes
The difference between the temperature T _{75 to 25} and the total 75% eluting T ₇₅ -T ₂₅
And the density d satisfy the relationship of the following (formula 1) and the relationship of the following (formula 2). (Formula 1) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Formula 2) T ₇₅ −T ₂₅ ≦ −670 × d + 644

If T ₇₅ -T ₂₅ and the density d do not satisfy the relationship of the above (formula 1), the heat seal strength and heat resistance will be inferior. If the relationship of the above (formula 2) is not satisfied, Is inferior in low-temperature heat sealability. The ethylene (co) polymer (A) in the present invention has one or more TREF peaks, and differs from the conventional ethylene (co) polymer obtained by the general metallocene catalyst shown in FIG. It is clearly distinguished by the relational expression of 1) or (Equation 2).

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

The (A1) ethylene (co) polymer of the present invention (e) at 25 ° C., the amount X (% by weight) of the ODCB-soluble component at 25 ° C., the density d and the MFR 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, and when 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 08 log MFR ≧ 0.93, X <0.5, and when d−0.008 log MFR <0.93, X <5.6 × 10 ³ × (0.9300−d + 0.008 log M
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 filtrate is collected by filtering through a Teflon filter. This filtrate, which is a sample solution, was subjected to infrared spectroscopy to measure the asymmetric stretching vibration wave number of methylene 2925c.
The absorption peak intensity around m ^-1 is measured, and the sample concentration is calculated from a calibration curve created in advance. From this value, the ODCB-soluble content at 25 ° C. is determined.

The ODCB-soluble component at 25 ° C. is a component having a high branching degree and a low molecular weight contained in the ethylene (co) polymer, which causes a decrease in heat resistance and stickiness of the surface of the 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 article and the like. In addition, low molecular weight components cause smoke during molding. OD
The amount of the CB soluble component is affected by the content and molecular weight of the α-olefin in the whole 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.

In the present invention, the (A1) ethylene (co) polymer is prepared by (f) a continuous heating elution fractionation method (TRE).
In the elution temperature-elution amount curve obtained by F), a plurality of peaks are present. 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 is 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 at a constant flow rate through this column, the column temperature was raised to 50 ° C.
The sample is sequentially eluted while heating 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 homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms. α-
The olefin preferably has 5 to 10 carbon atoms, and specifically includes 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and the like. Can be Further, the content of these α-olefins is desirably selected in a range of usually 30 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 (h) 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

Among the ethylene (co) polymers (A2), ethylene (co) polymers that further satisfy the following requirement (i) are preferred. (I) The melt tension (MT) and the melt flow rate (MFR) satisfy the relationship of the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR + 0.3 By satisfying the relationship of (1), molding processability such as film molding is improved.

Here, the ethylene (co) polymer (A1)
As shown in FIG. 2, the continuous heating elution fractionation method (TR
In the elution temperature-elution amount curve obtained by EF), a specific ethylene / α-olefin copolymer has a plurality of peaks substantially. 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 is a typical metallocene-based copolymer. Also,
Although the ethylene (co) polymer (A2) of the present invention has one TREF peak, the copolymer using a conventional typical metallocene-based catalyst has the formulas (1) and (2) as described above.
Are not clearly satisfied.

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 it satisfies the above parameters, but is preferably an organic cyclic compound having at least a conjugated double bond. It is a linear ethylene (co) polymer obtained by polymerizing ethylene or copolymerizing ethylene with 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, excellent 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 benzoylacetonato 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 general formula Me ² R ⁴ _m (OR ⁵ ) _n X ² _zmn ( In the formula, Me ² is an element of 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 above-mentioned 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. Above all, 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 an indenyl group and a naphthyl group; and aralkyl groups such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group and a 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 and 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 monochlorodiconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrabutoxy titanium , Tetrabutoxy hafnium and the like, and especially 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)
And di-n-butoxide zirconium.

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 around
Elements of the Periodic Table Group I-III, 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, benzyl
Hydryl group, phenylbutyl group, neofuyl group, etc.
And an aralkyl group. 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 Is Me when hydrogen is a hydrogen atom^Two Is boron, aluminum
Only in the case of Group III elements in the periodic table
Things. Z is Me^Two And m and m
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; wherein the cyclic hydrocarbon compound partially has 1 to 6 hydrocarbon residues (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 an alkali metal salt (sodium or lithium salt) 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 above-mentioned 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. And 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- C5-C24 cyclopolyene or substituted cyclopolyene such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadiene Examples include enylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

The modified organoaluminum oxy compound containing an Al—O—Al bond of the catalyst component a4 is a modified organoaluminum oxy compound usually obtained by reacting an alkylaluminum compound with water and usually called aluminoxane. Usually contains 1 to 100, preferably 1 to 50 Al-O-Al bonds in the molecule.
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 (triethylammoniumtetra (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 or 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 these, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable. Further, 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
To 200 ° C, more preferably 50 to 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 about 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a single-stage polymerization method, as well as a multi-stage polymerization method of two or more stages in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and 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 or a container suitably used in the field of food packaging materials and the like.

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 and
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 with a density of 0.91 to 0.94 g / 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
Ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber of 6 to 0.91 g / cm ³ is included.

The LLDPE using the Ziegler-type catalyst refers to ethylene • α- 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, and 4-methyl-
1-pentene, 1-hexene, 1-octene and the like can be mentioned.

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-based (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 α, β-unsaturated carboxylic acids or derivatives 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.
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 , and more preferably 0.91 to 0.935 g / cm ³ . The melt tension is 1.5 to 25 g, preferably 3 to 20 g, 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 above-mentioned 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 them, 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. Further, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight.

Further, as a typical copolymer of the above-mentioned copolymer of ethylene and α, β-unsaturated carboxylic acid or a derivative thereof, ethylene / (meth) acrylic acid or its alkyl ester copolymer may be mentioned. 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, alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate are particularly preferable. In particular, the (meth) acrylate content is 3 to 20% by weight,
Preferably it is in the range of 5 to 15% by weight. Among these other ethylene-based polymers (B), the high-pressure radical method low-density polyethylene is most preferable because of its excellent moldability.

When the resin material containing the ethylene (co) polymer (A) as the main component in the present invention is a composition containing the other ethylene polymer (B), the ethylene (co) polymer (A) Resin material whose main component is ethylene (co)
It is a resin composition containing 20 to 100% by weight of the polymer (A) and 80 to 0% by weight of another ethylene-based polymer (B), and preferably 50 to 9 of an ethylene (co) polymer (A).
A resin composition containing 8% by weight and 50 to 2% by weight of another ethylene-based polymer (B), more preferably 60 to 95% by weight of an ethylene (co) polymer (A) and a high-pressure radical polymerization method. Is a resin composition containing 40 to 5% by weight of the low-density polyethylene (hereinafter, referred to as LDPE) obtained by the above method. If the content of the ethylene (co) polymer (A) is less than 20% by weight, the low-temperature heat sealability of the laminate becomes poor, which is not preferable.

The resin material containing the ethylene (co) polymer (A) as the main component 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. By performing the low-temperature molding, there is an advantage that deterioration of the resin due to heat hardly occurs, and it is not necessary to add an antioxidant. Also, by being molded at low temperature,
Since blocking of the resin is reduced, 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) as a main component may contain a known additive such as an acid absorbent, an antioxidant and an antiblocking agent, as well as a lubricant and an antistatic agent, depending on the use. It is desirable to be formed of a material that does not contain any known additives such as an antifogging agent, an ultraviolet absorber, an organic or inorganic pigment, a nucleating agent, and a crosslinking agent.
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 out or does not affect the contents. In the present invention, an additive that elutes to the outside, for example, when the content is a liquid, an additive that is eluted in the liquid, an additive in which odor is transferred, or with time Since an additive that is unevenly distributed on the film surface is not included in the resin material containing the ethylene (co) polymer (A) as a main component, a clean laminate and a container can be provided.

An additive that does not substantially elute to the outside is a filler such as an organic or inorganic filler, which does not alter the contents of the container and essentially gives the characteristics of the laminate or container of the present invention. It is an additive that can be added in a range that does not inhibit the addition. As the inorganic filler, 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, zinc oxide, 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. In addition, it is desirable that the resin material containing the ethylene (co) polymer (A) as a main component should not contain an additive that may reduce the adhesiveness to the metal layer (II).

The metal foil or metal-deposited film in the present invention is a metal foil such as aluminum, gold, silver, iron, steel, copper, nickel or an alloy containing these as a main component; ,aluminum,
It refers to a deposited film on which a metal such as silicon or a metal oxide thereof is deposited.

Examples of the base material in the present invention include paper, polyester, polyamide, saponified ethylene / vinyl acetate copolymer, polypropylene, polyvinylidene chloride resin and other films, nonwoven fabric, woven fabric, cellophane, or a stretched product thereof. And printed matter.

The first aspect of the laminate of the present invention is that a resin layer (I) composed of a resin material containing the ethylene polymer (A) as a main component and a metal layer (II) composed of a metal foil or a metal-deposited film. It is a laminate including a directly joined (I / II) structure. Here, when the metal layer (II) is a layer made of a metal vapor-deposited film, what is in contact with the resin layer (I) is a metal surface of the metal vapor-deposited film. As a specific example, SL
L / Al foil, (SLL + LD) / Al foil, SLL / Al
Evaporated PET film, (SLL + LD) / Al evaporated PE
T film, SLL / Al foil / SLL, (SLL + L
D) / Al evaporated PET film / (SLL + LD),
(SLL + LL + LD) / Al foil / (SLL + LL + L)
D), (SLL + HD + LD) / Al foil / (SLL + H)
D + LD), SLL / Al foil / LD, SLL / Al evaporated PET film / LD, and the like. (Where SL
L: (A) ethylene (co) polymer, LD: high pressure radical low density polyethylene, LL: linear low density polyethylene,
HD: high density polyethylene; PET: polyester resin. )

The second laminate of the present invention comprises ethylene (co)
A resin layer (I) composed of a resin material containing a polymer (A) as a main component and a metal layer (II) composed of a metal foil or a metal vapor-deposited film are directly bonded to each other and in contact with the resin layer (I). This is a laminate including a (II / I / III) structure in which a material layer (III) is laminated. As a specific example, Al foil / SLL /
Plastic film, Al foil / SLL / paper, paper / (S
LL + LD) / Al foil, Al foil / (SLL + LD) / Plastic film, Al evaporated PET film / SLL
/ Paper, Al-deposited PET film / (SLL + LD) / paper.

The third laminate of the present invention has the above (II / I /
III) Metal layer (II) and / or substrate layer of laminated structure
On (III), a second resin layer (IV) and / or a third resin layer (V) made of a resin material containing an ethylene (co) polymer as a main component was laminated (IV / II). / I / III /
V), or (IV / II / I / III), (II / I / III / V)
It is a laminate having a structure. As a specific example, LD
/ Al foil / SLL / Plastic film / SLL, S
LL / Al foil / SLL / paper / LD, SLL / paper / (SL
L + LD) / Al foil / SLL, (SLL + LD) / Al
Foil / (SLL + LD) / plastic film / LD,
SLL / Al evaporated PET film / SLL / paper / SL
L, LD / Al evaporated PET film / (SLL + LD)
/ Paper / (SLL + LL + LD).

The method for producing a laminate of the present invention is not particularly limited. For example, (A) an ethylene (co) polymer as a main component is formed on a metal surface of a metal foil or a metal-deposited film. Examples of the method include laminating a resin material by an extrusion lamination method, a dry lamination method, a tandem lamination method, or the like. Among them, the extrusion lamination method is particularly preferable.

In the method for producing a laminate of the present invention, (A) a resin material containing, as a main component, an ethylene (co) polymer containing no additive, or substantially no outside as an additive. It is preferable to use a resin material containing (A) an ethylene (co) polymer as a main component and containing only additives. By using such a resin material containing (A) an ethylene (co) polymer as a main component, a clean laminate and a container are produced, in which no odor is transferred or eluted due to additives and taste and deterioration are hardly generated. It becomes possible.

When extruding and laminating (A) a resin material containing an ethylene (co) polymer as a main component, the molten resin is subjected to an ozone treatment while the melting temperature is not lower than the melting point to 300 ° C., preferably 200 to 300 ° C. It is desirable to carry out extrusion lamination at a molding temperature of. By applying ozone treatment,
Even in the case of extrusion lamination at a low temperature, the adhesive strength between the resin layer (I) and the metal layer (II) 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 substrate, the substrate layer (II
The adhesive strength between I) and the resin layer (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 the shape of a container. Examples of uses 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. Can be

[0071]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

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.

[TREF] With the column kept 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 the glass beads. The temperature was raised and the polymer concentration eluted at each temperature was detected by 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 cm)
φ × 12 cmL (filled with glass beads), sample concentration:
0.05% by weight) [Adhesive strength] Using a tensile tester, a tensile speed of 300 mm
Peeling between the metal layer (II) and the resin layer (I) and between the metal layer (II) and the second resin layer (IV) of the test piece (15 mm width) of the laminate under the condition of / min And then 18
The 0 degree peel strength was determined.

Various components used in Examples and Comparative Examples are as follows. 1) (A) Ethylene (co) polymers A1-1 and A1-
2 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 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 is fed continuously, ethylene, 1-hexene and water
The polymerization is carried out by supplying the element so that the molar ratio is maintained at a predetermined value.
Obtaining a Tylene (co) polymer (A1-1 and A1-2)
Was. The physical properties are shown in Table 1.

2) (A) Ethylene (co) polymer A2 was polymerized by the following method. Ethylene and 1-hexene were copolymerized at a polymerization temperature of 75 ° C. and a total pressure of 20 kgf / cm ² G using the continuous fluidized-bed gas-phase polymerization apparatus described above. The solid catalyst was continuously supplied, and ethylene, 1-hexene and hydrogen were supplied so as to maintain a predetermined molar ratio to carry out polymerization to obtain an ethylene (co) polymer (A2). The physical properties are shown in Table 1.

3) Ethylene-catalyzed by general metallocene catalyst
Hexene-1 copolymer (A3) 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). Table 1 shows the physical properties of the copolymer (A3).
It was shown to. 4) The physical properties of linear low density polyethylene (LLDPE: B-1) using a commercially available Ziegler type catalyst are shown in Table 1.

[0078]

[Table 1]

5) Commercially available high-pressure low-density polyethylene (L
DPE: C-1) Density: 0.918 g / cm ³ , MFR: 7 g / 10 min Commercially available high-pressure low-density polyethylene (LDPE: C-2) Density: 0.919 g / cm ³ , MFR: 7 g / 10 min 6) Ethylene methacrylic acid copolymer (EMAA: D-
1) MAA concentration: 11% by weight, MFR: 8 g / 10 min

Example 1 150 g of paperboard having a width of 960 mm
LDPE (C-1) on one surface of (base material layer (III)),
Corona treatment (6 kW) and ozone treatment (50 g / m
^At the molding temperature of 285 to 295 ° C,
Coating was performed with a thickness of 5 μm (third resin layer (V)). next,
The other side of the paperboard and the metal foil AL # 7 (7
0 μm thick aluminum foil, metal layer (II))
70% by weight of ethylene (co) polymer (A1-1) and LDP
A resin material composed of 30% by weight of E (C-1) was extrusion-laminated to a thickness of 20 μm at a molding temperature of 315 to 320 ° C. while performing corona treatment (6 kW) (resin layer (I)).

Further ethylene was added to the AL surface of the laminate.
70% by weight of (co) polymer (A1-1) and LDPE (C-
1) A resin material consisting of 30% by weight is treated with ozone (5
0 g / m ^Three ), The molding temperature of 280 to 290 ° C.
The second resin layer (IV) was coated with a thickness of 30 μm.
The line speed was 150 m / min. metal
Bonding strength between layer (II) and resin layer (I), and metal
Measures adhesive strength between layer (II) and second resin layer (IV)
did. Table 2 shows the results.

Example 2 As a resin for the third resin layer (V), 70% by weight of ethylene (co) polymer (A1-1) and LDPE (C-1) were used instead of LDPE (C-1). 30
The procedure was performed in the same manner as in Example 1 except that a resin material consisting of% by weight was used. Table 2 shows the results.

Example 3 55 g of high quality paper (substrate layer (II
I)) and a metal foil AL # 7 (a metal layer (I
I)), an ethylene (co) polymer (A1-2) 7
Tree consisting of 0% by weight and 30% by weight of LDPE (C-1)
While applying the corona treatment (6 kW) to the fat material,
Extrusion lamination with a thickness of 20 μm at a molding temperature of
Layer (I)). Further ethylene is added to the AL surface of this laminate.
70% by weight of (co) polymer (A1-2) and LDPE (C-
1) A resin material consisting of 30% by weight is treated with ozone (5
0 g / m ^Three ) And isocyanate anchor
280 while applying a coating agent (hereinafter referred to as AC agent).
30 μm thick at a molding temperature of ２290 ° C. (second
Resin layer (IV)). All line speeds are 150m / m
was in. Contact between metal layer (II) and resin layer (I)
Strength of the metal layer (II) and the second resin layer (IV)
The adhesive strength between them was measured. Table 2 shows the results.

Example 4 AL # 30 (3
0 μm-thick aluminum foil, metal layer (II)), and 70% by weight of ethylene (co) polymer (A1-2) and L
The resin material composed of 30% by weight of DPE (C-1) was subjected to ozone treatment (50 g / m ³ ) while performing 280-29.
It was coated at a molding temperature of 0 ° C. with a thickness of 30 μm (resin layer (I)). The line speed was 100 m / min. The adhesive strength between the metal layer (II) and the resin layer (I) was measured. Table 2 shows the results.

Example 5 AL # 30 (3
0 μm-thick aluminum foil, metal layer (II)), 70% by weight of ethylene (co) polymer (A2) and LDP
E (C-1) A resin material consisting of 30% by weight is subjected to ozone treatment (50 g / m ³ ) while being subjected to 280 to 290 ° C.
At a molding temperature of 30 μm (resin layer (I)). The line speed was 100 m / min. The adhesive strength between the metal layer (II) and the resin layer (I) was measured. Table 2 shows the results.

[0086]

[Table 2]

Comparative Example 1 150 g of paperboard having a width of 960 mm
LDPE (C-1) on one surface of (base material layer (III)),
Corona treatment (6 kW) and ozone treatment (50 g / m
^At the molding temperature of 285 to 295 ° C,
Coating was performed with a thickness of 5 μm (third resin layer (V)). next,
While the LDPE (C-1) is subjected to corona treatment (6 kW) between the other surface of the paperboard and the metal foil AL # 7 (metal layer (II)) of the sand substrate, a molding temperature of 320 to 330 ° C. And extrusion sand lamination at a thickness of 20 μm (resin layer (I)).

An LDPE (C
-1) was applied to a thickness of 30 μm at a molding temperature of 320 to 330 ° C. while applying an AC agent (the second resin layer (I
V)). The line speed was 150 m / min. The adhesive strength between the metal layer (II) and the resin layer (I) and the adhesive strength between the metal layer (II) and the second resin layer (IV) were measured. Table 3 shows the results. Due to the high content of low molecular weight components in the resin, there was much smoke during lamination. Also,
The adhesive strength between the metal layer (II) and the resin layer (I) was poor.

[Comparative Example 2]
LDPE (C-1) and EMAA (D-
1) is co-extruded onto the metal layer (II) at a resin temperature of 280 ° C. immediately below the T-die, and an EMAA (D) layer ( 15 μm), and the same procedure as in Comparative Example 1 was performed. The adhesive strength between the metal layer (II) and the resin layer (I) and the adhesive strength between the metal layer (II) and the second resin layer (IV) (D layer) were measured. Table 3 shows the results. Although the molding temperature was low, there were many smokes during lamination due to the large amount of low molecular weight components in the resin.
Further, the adhesive strength between the metal layer (II) and the resin layer (I) was poor.

[Comparative Example 3] As a resin for the resin layer (I),
70% by weight of ethylene (co) polymer (A1-2) and LDP
LDPE (C-1) was used in place of the resin material consisting of E (C-1) 30% by weight, and LDPE (C-
1) was performed in the same manner as in Example 3 except that the second resin layer (IV) was provided by applying a 30 μm thickness at a molding temperature of 320 to 330 ° C. while applying an AC agent. Table 3 shows the results. Due to the high content of low molecular weight components in the resin, relatively large amounts of smoke were generated during lamination. Further, the adhesive strength between the metal layer (II) and the resin layer (I) was poor. Also, the odor was inferior.

Comparative Example 4 As a resin for the resin layer (I) and the second resin layer (IV), an ethylene (co) polymer (A1
-2) Instead of a resin material consisting of 70% by weight and 30% by weight of LDPE (C-1), Ziegler-based LLDPE (B
-1) The same operation as in Example 3 was performed except that a resin material composed of 70% by weight and 30% by weight of LDPE (C-1) was used. Table 3 shows the results. Due to the high content of low molecular weight components in the resin, there was much smoke during lamination. The adhesive strength between the metal layer (II) and the resin layer (I) was poor.

[Comparative Example 5] As a resin for the resin layer (I),
70% by weight of ethylene (co) polymer (A1-2) and LDP
Instead of the resin material consisting of 30% by weight of E (C-1), 70% by weight of Ziegler-based LLDPE (B-1) and LDP
Example 4 was carried out in the same manner as in Example 4 except that a resin material composed of 30% by weight of E (C-1) was used. Table 3 shows the results. The adhesive strength between the metal layer (II) and the resin layer (I) was poor. Also, the odor was inferior.

[Comparative Example 6] As a resin for the resin layer (I),
70% by weight of ethylene (co) polymer (A3) and LDPE
(C-1) The same procedure as in Example 5 was carried out except that a resin material consisting of 30% by weight was used. Table 3 shows the results.

[0094]

[Table 3]

[Relative odor] A regular tetrahedron-shaped container having a side of about 20 cm was prepared from the laminates of the examples and comparative examples by impulse sealing. Relative odor test was performed in tests # 1 to #
In the combination shown in No. 3, 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. . Evaluation of the relative odor test is performed by giving a score of 1 point for the strong odor, 0 point for the weak odor, and 0.5 point for both if the odor is indistinguishable, and sums the scores of all subjects. Was. If there were any notable types of odors, they were recorded separately. Tables 4 to 9 show the combinations and results of the relative odor test. In the table, the polyodor is
It is a paraffin odor, and the sour odor is an irritating odor that smells like a nose. The burning odor is the odor that is emitted when things burn or burn.

[0096]

[Table 4]

[Table 5]

[0097]

[Table 6]

[Table 7]

[0098]

[Table 8]

[Table 9]

[0099]

As described above, the laminate of the present invention comprises a metal layer (I) made of a metal foil or a metallized film.
Since a resin layer (I) made of a resin material mainly composed of an ethylene (co) polymer (A) satisfying the above-mentioned requirements (a) to (d) is provided on the surface of I), Even without using an anchor coat agent, the adhesive strength between the resin layer (I) and the metal layer (II) is excellent and the odor is small. In addition, since the low molecular weight component is small in the ethylene (co) polymer (A),
Less smoke and associated odor during extrusion. Furthermore, the laminate of the present invention is also excellent in gas barrier properties, tear strength, impact resistance, moldability, low-temperature heat sealing, and the like.

Further, the resin material containing the ethylene (co) polymer (A) as a main component is an ethylene (co) polymer (A).
50 to 98% by weight and other ethylene-based polymer (B)
If the content is 50% by weight, the molding stability during 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. In addition, no additive is blended in the resin material containing the ethylene (co) polymer (A) as a main component, or it is blended in a resin material containing the ethylene (co) polymer (A) as a main component. If the additive does not elute to the outside, the laminate will be free from odor migration and taste change.

The temperature at which 25% of the ethylene (co) polymer eluted from the integral elution curve obtained from the elution temperature-elution amount curve (TREF) of the ethylene (co) polymer (A) by the continuous heating elution fractionation method (TREF). the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to T ₂₅ and the entire 75% elutes, the following relationship (equation 1),
If the relationship of the following (formula 2) is satisfied, the moldability can be further improved. (Formula 1) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Formula 2) T ₇₅ −T ₂₅ ≦ −670 × d + 644 If the ethylene (co) polymer (A) is (A1) an ethylene (co) polymer that further satisfies the requirements of the above (e) and (f), hygiene and Heat resistance and rigidity can be further improved. If the ethylene (co) polymer (A) is (A2) an ethylene (co) polymer that further satisfies the above requirements (g) and (h), heat resistance, heat seal strength, and low temperature Heat sealability can be further improved. In addition, when the ethylene (co) polymer (A2) further satisfies the above requirement (i), the moldability can be further improved.

The ethylene (co) polymer (A)
However, 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) as a main component is 10 ppm or less,
There is no need to add an acid absorbent, and the hygiene of the laminate can be further improved. The resin material containing the ethylene (co) polymer (A) as a main component can be molded at a low temperature and its surface treatment such as ozone treatment is effective, although the reason is not clear. By performing the low-temperature molding, there is an advantage that deterioration of the resin due to heat hardly occurs, and it is not necessary to add an antioxidant. Also, by being molded at low temperature,
Since blocking of the resin is reduced, 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.

According to the method for producing a laminate of the present invention, the resin material containing the ethylene (co) polymer (A) as a main component is directly extrusion-laminated on a metal foil or a metallized film. A laminate having excellent adhesive strength between the resin layer (I) and the metal layer (II) and low odor can be obtained without using an anchor coating agent or the like. In addition, since the ethylene (co) polymer (A) has a small amount of low molecular weight components, there is little smoke during extrusion molding and odor associated therewith. Furthermore, a laminate having excellent gas barrier properties, tear strength, impact resistance, moldability, low-temperature heat sealing, and the like can be obtained. In addition, no additive is blended in the resin material containing the ethylene (co) polymer (A) as a main component, or it is blended in a resin material containing the ethylene (co) polymer (A) as a main component. If the additive does not substantially elute to the outside or does not affect the contents, a laminate can be produced that does not cause odor migration or change in taste.

When a resin material mainly composed of the ethylene (co) polymer (A) is directly extruded and laminated on a metal foil or a metallized film, the ethylene (co) polymer (A) is used as a main component. Extrusion lamination at a molding temperature of not less than the melting point of the resin material containing the ethylene (co) polymer (A) as a main component and not more than 300 ° C. while performing the ozone treatment on the molten resin of the resin material to form the resin layer (I) A laminate having more excellent adhesive strength between the metal layer and the metal layer (II) can be manufactured.

Since the container of the present invention is made of the laminate of the present invention, the container has low odor. In addition, since it is made of a laminate having a high adhesive strength between the resin layer (I) and the metal layer (II),
Does not break the bag or generate pinholes in the metal layer (II). Furthermore, gas barrier properties, tear strength, impact resistance,
Excellent moldability, low temperature heat sealing, etc. And
A container made of a laminate containing no additive does not cause odor transfer or deterioration of taste. Such a container can be suitably used for a food container such as milk conforming to a ministerial ordinance such as milk and a packaging material.

[Brief description of the drawings]

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

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

FIG. 3 is a graph showing an example of an elution temperature-elution amount curve of an ethylene (co) polymer with a general metallocene catalyst.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ippei Kagaya 2-3-2, Yakko, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Inside the Research and Development Center, Japan Polyolefin Co., Ltd. (72) Inventor Hiroshi Kasahara Kawasaki City, Kawasaki City, Kanagawa Prefecture 2-3-2, Kamiyo-ku, Tokyo F-term (Reference) in Research and Development Center, Technology Headquarters, Japan Polyolefin Co., Ltd. AK04A AK04D AK04E AK04J AK06A AK06D AK06E AK28A AK28D AK28E AK28J AK62 AL01A AL01D AL01E AL05A AL05D AL05E AT00C BA02 BA03 BA04 BA05 BA07 BA10B BA10C BA10D BA10E BA13 DG10 EH231 EH232 EH66B EJ131 EJ132 GB16 GB23 GB41 GB66 JA04A JA04D JA04E JA06A JA06D JA06E JA07A JA07D JA07E JA13A JA13D JA13E JB08A JB08D JB08 E JD02 JJ03 JK02A JK02D JK02E JK03 JK06 JK10 JL00 JL01 JL12 YY00A YY00D YY00E

Claims (15)

[Claims] 1. A resin layer (I) composed of a resin material mainly composed of an ethylene (co) polymer (A) satisfying the following requirements (a) to (d): A laminate having a metal layer (II) made of a metal foil or a metal-deposited film in contact with one surface. (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 whole elutes
−T ₂₅ and density d satisfy the following relationship (Equation 1) and the following relationship (Equation 2) (Equation 1) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation 2) T ₇₅ −T ₂₅ ≦ −670 × d + 644 2. A base material layer (III) and an ethylene (co) polymer (A) which is in contact with one surface of the base material layer (III) and satisfies the following requirements (a) to (d): And a metal layer (II) made of a metal foil or a metal-deposited film in contact with the surface of the resin layer (I) that is not in contact with the base material layer (III). A laminate comprising: (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 whole elutes
−T ₂₅ and density d satisfy the following relationship (Equation 1) and the following relationship (Equation 2) (Equation 1) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation 2) T ₇₅ −T ₂₅ ≦ −670 × d + 644 3. The ethylene copolymer (A) as a main component on the surface of the metal layer (II) and / or the base material layer (III) on the side not in contact with the resin layer (I). The laminate according to claim 2, wherein the second resin layer (IV) and / or the third resin layer (V) made of a resin material are laminated. 4. The resin material containing the ethylene (co) polymer (A) as a main component is an ethylene (co) polymer (A) 20.
And a density of 0.88 to 0.97 g / cm ^3.
The laminate according to any one of claims 1 to 3, further comprising 80 to 0% by weight of another ethylene-based polymer (B). 5. The laminate according to claim 4, wherein the other ethylene polymer (B) is a low-density polyethylene obtained by a high-pressure radical polymerization method. 6. The resin material containing the ethylene (co) polymer (A) as a main component, in which no additives are blended, or the resin material containing the ethylene (co) polymer (A) as a main component, The laminate according to any one of claims 1 to 5, wherein the compounded additive is an additive that does not elute to the outside or an additive that does not affect the content. 7. The ethylene (co) polymer (A) further satisfies the following requirements (e) and (f) (A1):
2. An ethylene (co) polymer.
7. The laminate according to any one of claims 6 to 6. (E) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by weight), the density d, and the melt flow rate (MFR) satisfy the following relations (Equation 3) When d−0.008 log MFR ≧ 0.93, X <2.0 (Equation 3) 4) When d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR)
² + 2.0 (f) Multiple peaks in the elution temperature-elution volume curve by continuous temperature elution fractionation (TREF) 8. The ethylene (co) polymer (A) further satisfies the following requirements (g) and (h) (A2):
2. An ethylene (co) polymer.
7. The laminate according to any one of claims 6 to 6. (G) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF). (H) One or two melting point peaks, and the highest melting point T _m1 and density d among them Satisfies the following equation (Equation 5). (Equation 5) T _m1 ≧ 150 × d−17 9. The (A2) ethylene (co) polymer,
The laminate according to claim 8, further satisfying the following requirement (i). (I) 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 by 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) as a main component is 10 ppm or less. . 12. A resin layer (I) made of a resin material mainly containing an ethylene (co) polymer (A) satisfying the following requirements (a) to (d): A method for producing a laminate having a metal layer (II) made of a metal foil or a metal-deposited film in contact with one side, wherein the resin material containing the ethylene (co) polymer (A) as a main component is made of a metal foil or a metal. A method for producing a laminate, wherein extrusion lamination is performed directly on a vapor-deposited film. (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 whole elutes
−T ₂₅ and density d satisfy the following relationship (Equation 1) and the following relationship (Equation 2) (Equation 1) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (Equation 2) T ₇₅ −T ₂₅ ≦ −670 × d + 644 13. An additive is not added to the resin material containing the ethylene (co) polymer (A) as a main component or the resin material containing the ethylene (co) polymer (A) as a main component. The method for producing a laminate according to claim 12, wherein the compounded additive is an additive that does not elute to the outside or an additive that does not affect the contents. 14. When extruding and laminating a resin material containing an ethylene (co) polymer (A) as a main component directly onto a metal foil or a metallized film, the ethylene (co) polymer (A) is used as a main component. The extrusion lamination is performed at a molding temperature of not less than the melting point of the resin material containing the ethylene (co) polymer (A) as a main component and not more than 300 ° C. while subjecting the molten resin of the resin material to be subjected to ozone treatment. The method for producing a laminate according to claim 12 or 13. A container comprising the laminate according to any one of claims 1 to 11.