JP2003175576A - Packaging material and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body which is excellent in a bonding strength between a resin layer (I) and a CPP layer (II) without using an anchor-coating agent, causes less smoking at the time of the molding and has less odor as a product, and does not deteriorate the quality of a content even when being used as a container or a packaging material; its manufacturing method; and a container using the laminated body. <P>SOLUTION: The resin layer (I) comprising a resin material containing a specified ethylene (co)polymer (A) is directly bonded onto at least one surface of a base material layer (III) comprising at least one kind of a material which is selected from a group comprising a thermoplastic resin, a paper, a non-woven fabric and a woven fabric for the laminated material. Also, in the resin material, an additive is not blended. Alternatively, the additive which is blended in the resin material is an additive which does not elute to the outside, or does not affect the content. Such a laminated material and its manufacturing method are provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent adhesive strength between layers without using an anchor coating agent, tear strength, impact resistance, moldability, heat seal strength, heat resistance, oil resistance, and cleanness. The present invention relates to a manufacturing method of a packaging material which is excellent in, for example, can be directly bonded by extrusion lamination and has a small number of production steps and is economical. More specifically, the packaging material relates to a packaging material for snacks, a packaging material suitable for use in food fields such as microwave ovens, medical fields, electronic materials, etc., and a manufacturing method thereof.

[0002]

2. Description of the Related Art Conventionally, potato chips, shrimp rice crackers, snacks such as peanuts, and packaging materials for microwave ovens are required to have low-temperature heat-sealing properties, heat resistance and oil resistance in addition to adhesive strength. Generally, a base material such as paper, aluminum, biaxially oriented polypropylene, biaxially oriented polyester, biaxially oriented polyamide, saponified ethylene-vinyl acetate copolymer, etc., is subjected to an anchor coating agent and unstretched polypropylene. A sealant layer made of a system resin (hereinafter referred to as CPP) is laminated.

[0003]

However, when an adhesive such as an anchor coating agent is used, the adhesive strength between the layers of the laminate is maintained, but the adhesive such as the anchor coating agent contains a solvent. Therefore, there are problems such as safety, contamination of working environment, complicated work, and increase in equipment cost. Further, in recent years, solvent-free use has begun to be considered due to growing consumer interest in the 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 laminated body is weakened, so that the packaging material / container made of this laminated body is easily damaged and the quality of the packaging material / container is stable. There was a problem that it was not realized as a packaging material. Further, in order to increase the adhesive strength, a layer made of low-density polyethylene may be interposed between the base material layer and the sealant layer, but the adhesive strength is not always sufficiently increased, and the number of steps is Will increase. Furthermore, since the resin temperature becomes high during lamination molding, the linear low-density polyethylene obtained by the conventional Ziegler-based catalyst, which has a relatively low molecular weight component, may emit smoke and transfer odor to the laminate. Especially, in packaging materials such as foods, the transfer of such an odor becomes a serious problem. Therefore, the object of the present invention, even without using an anchor coating agent, excellent adhesive strength between the sealant layer and the resin layer composed of a non-stretched polypropylene film, low temperature heat sealability, excellent high-speed moldability, Another object of the present invention is to provide a clean packaging material in which residual solvent in the product is reduced, smoke is less likely to be generated during laminate molding, and odor is not transferred.

[0005]

The packaging material of the present invention comprises 100 to 20% by weight of an ethylene (co) polymer (A) satisfying the following requirements (a) to (d) and another polyolefin resin ( B) A resin layer (I) made of a resin material containing 0 to 80% by weight and a sealant layer (II) made of a non-stretched polypropylene film are directly bonded to each other to provide a laminate. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10
25% of the total (c) molecular weight distribution (Mw / Mn) obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) is 1.5-4.5. The difference T ₇₅ -T ₂₅ between the elution temperature T ₂₅ and the temperature T _{75 at} which 75% of the total elutes, and the density d satisfy the following expression (equation 1) (equation 1) T ₇₅ -T ₂₅ ≤ −670 × d + 644 Here, it is desirable that the ethylene (co) polymer (A) further satisfies the following requirement (e). (E) The 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 obtained, which is obtained from the integral elution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) T ₇₅ -T ₂₅ and density d satisfy the following to satisfy the relation of (formula 2) (formula 2) d <when _{^{0.950g / cm 3 T 75 -T 25}} ≧ -300 × d + 285 d ≧ 0.950g / Cm ³ T ₇₅ −T ₂₅ ≧ 0

As a layer structure, a laminate having at least a first base material layer (III) and laminating a first base material layer (III) / resin layer (I) / sealant layer (II) in this order is provided. It is preferable that Further, it has a first base material layer (III) and a second base material layer (IV), and has a first base material layer (III) / resin layer (I) /
Second base material layer (IV) / resin layer (I) / sealant layer (II)
It is also possible to have a laminated body in which the layers are laminated in this order. The first base material layer (III) is preferably at least one selected from the group consisting of paper, thermoplastic resin film, stretched film and printing film. Second base material layer (I
V) is preferably at least one selected from the group consisting of metal foils, vapor deposited films of metals and inorganic compounds, thermoplastic resins, and stretched films.

The other polyolefin resin (B) is preferably low density polyethylene obtained by a high pressure radical polymerization method. The ethylene (co) polymer (A) is preferably an ethylene (co) polymer (A1) which further satisfies the requirements (f) and (g) below. (F) Ortho-dichlorobenzene (ODC at 25 ° C)
B) Soluble content X (% by weight), density d and melt flow rate (MFR) satisfy the following relationship (Equation 3): d-0.008 log MFR ≧ 0.93 X <2.0 (Equation 3) 4) When d−0.008logMFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008logMFR)
² + 2.0 (g) Multiple peaks of elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF)

The ethylene (co) polymer (A) further satisfies the following requirements (h) and (i):
It is also desirable that it is a polymer (A2). (H) The number of peaks of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) is one. (I) One or two melting point peaks, and the highest melting point T _m1 and density d Satisfies the following relationship (Equation 5) (Equation 5) T _m1 ≧ 150 × d-17 It is desirable that the ethylene (co) polymer (A2) further satisfies the following requirement (j). . (J) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (Equation 6) (Equation 6) log MT ≦ −0.572 × log MFR + 0.
Three

The ethylene (co) polymer (A) is preferably 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) is preferably 10 ppm or less. Further, it is desirable that the resin material containing the ethylene (co) polymer (A) contains substantially no additive.

The method for producing a packaging material of the present invention is characterized in that the resin layer (I) and the sealant layer (II) made of an unstretched polypropylene resin are laminated by a laminating method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The packaging material of the present invention is used in various forms such as containers and bags, and has a laminated structure having a specific laminated body. The ethylene (co) polymer (A) in the present invention is a homopolymer of ethylene or a copolymer of ethylene and α-olefin. Here, the α-olefin has a carbon number of 3 to 20, preferably 3 to 12, and specifically, propylene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1 -Octene, 1-
Examples include decene and 1-dodecene. Further, it is desirable that the total content of these α-olefins is selected in the range of usually 30 mol% or less, preferably 3 to 20 mol% or less.

The (a) density of the ethylene (co) polymer (A) in the present invention is 0.86 to 0.97 g / cm ³ ,
The range is preferably 0.89 to 0.94 g / cm ³ , and more preferably 0.90 to 0.93 g / cm ³ . When the density is less than 0.86 g / cm ³ , the rigidity (strength of the waist) and the heat resistance are poor. Also, 0.97 g / c
It is difficult to industrially produce a product having a size of more than m ³ .

The melt flow rate (hereinafter referred to as MFR) (b) of the ethylene (co) polymer (A) in the present invention is 0.01 to 100 g / 10 minutes. Preferably 0.5-90 g / 10 minutes, more preferably 1-80 g
The range is / 10 minutes. If the MFR is less than 0.01 g / 10 minutes, the moldability will be poor, and if it exceeds 100 g / 10 minutes, the tear strength and impact resistance will be poor.

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

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

Further, the ethylene (co) polymer (A) in the present invention preferably further satisfies the following requirement (e). (E) The 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 obtained, which is obtained from the integral elution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) T ₇₅ -T ₂₅ and density d satisfy the following to satisfy the relation of (formula 2) (formula 2) d <when ^{_{0.950g / cm 3 T 75 -T 25}} ≧ -300 × d + 285 d ≧ 0.950g When T / cm ³ , T ₇₅ −T ₂₅ ≧ 0 By satisfying the relationship of the above (formula 2), a packaging material having a better balance of low temperature heat sealability, heat resistance and the like can be obtained.

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

In the present invention, the ethylene (co) polymer (A
The amount X (wt%) of the ODCB-soluble component at 25 ° C. (f) in 1), the density d, and the MFR satisfy the relationships of the following (formula 3) and (formula 4). (Equation 3) When d−0.008logMFR ≧ 0.93, X <2.0 (Equation 4) When d−0.008logMFR <0.93, X <9.8 × 10 ³ × (0.9300 -D + 0.008log MFR)
² + 2.0 Preferably, when d−0.008logMFR ≧ 0.93, X <1.0 When d−0.008logMFR <0.93, X <7.4 × 10 ³ × (0.9300− d + 0.008log MFR)
Satisfies the relationship of ² +1.0. More preferably, if d−0.008logMFR ≧ 0.93, X <0.5 If d−0.008logMFR <0.93, X <5.6 × 10 ³ × (0.9300−d + 0.008logMFR) )
^It satisfies the relationship of ² +0.5.

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 the sample is completely dissolved, it is cooled to 25 ° C. After leaving this solution at 25 ° C. overnight, it is filtered with a polytetrafluoroethylene filter to collect a filtrate. The absorption peak intensity of this filtrate, which is a sample solution, near the wave number 2925 cm ⁻¹ of the asymmetric stretching vibration of methylene is measured by an infrared spectroscope, and the sample concentration is calculated from a calibration curve prepared in advance. From this value, the ODCB soluble content at 25 ° C. can be obtained.

The ODCB-soluble component at 25 ° C. is a highly branched component and a low molecular weight component contained in the ethylene (co) polymer, which causes a decrease in heat resistance and causes stickiness on the surface of the molded product, resulting in a problem of hygiene. And blocking inside the molded body,
It is desirable that the content is low, as it causes stains on the cooling roll. Further, the low molecular weight component is likely to cause smoke during molding, which causes odor adhesion. The amount of ODCB-soluble matter is influenced by the content and molecular weight of α-olefin in the whole copolymer, that is, the density and MFR. Therefore, the fact that the density, the MFR, and the amount of the ODCB-soluble component, which are these indices, satisfy the above relationship indicates that the uneven distribution of the α-olefin contained in the entire copolymer is small.

The ethylene (co) polymer (A1) of the present invention has a peak in the elution temperature-elution amount curve (g) determined by the continuous temperature rising elution fractionation method (TREF) as shown in FIG. Is a plurality. The multiple peak temperatures range from 85 ° C to 100 ° C.
It is particularly preferred that it is present between ° C. The presence of this peak raises the melting point, raises the crystallinity, and improves the heat resistance and rigidity of the molded body.

The TREF measuring method is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) is added so that the sample concentration becomes 0.05% by weight, and heated and melted at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads and cooled to 25 ° C. at a cooling rate of 0.1 ° C./min to deposit the sample on the surface of the glass beads. Next, while the ODCB was flowed through this column at a constant flow rate, the column temperature was adjusted to 50
The sample is sequentially eluted while the temperature is raised 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 an extremely small amount of sample, so that a relatively fine peak that cannot be detected by the fractionation method can be detected. The ethylene (co) polymer (A1) in the present invention is
The conventional ethylene (co) polymer obtained by the general metallocene catalyst shown in FIG. 2 and shown in FIG. 3 is clearly distinguished by the relational expression (Equation 2).

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

The ethylene (co) polymer (A
In 2), as shown in FIG. 1, (h) the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) has one peak. Moreover, (i) it has 1 or 2 melting point peaks, and the highest melting point T _m1 and the density d among them satisfy the relationship of the following (formula 5). (Equation 5) T _m1 ≧ 150 × d−17 If the melting point T _m1 and the density d do not satisfy the relationship of the above (Equation 5), the heat resistance becomes poor.

Further, among the ethylene (co) polymers (A2), ethylene (co) polymers which further satisfy the following requirement (j) are preferable. (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 MT and MFR are the above (Equation 6). By satisfying the relationship of (1), the molding processability such as film molding becomes good.

Here, the ethylene (co) polymer (A1)
As shown in FIG. 2, the continuous temperature rising elution fractionation method (TR
It is a special ethylene / α-olefin copolymer having a plurality of peaks substantially 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 the elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF). This is a typical metallocene-based catalyst copolymer. Also,
The ethylene (co) polymer (A2) of the present invention has one TREF peak, but the copolymer using a conventional typical metallocene catalyst does not satisfy (Formula 2) as described above. It is 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, but preferably an organic cyclic compound having at least a conjugated double bond. A linear ethylene (co) polymer obtained by homopolymerizing ethylene or copolymerizing ethylene and α-olefin in the presence of a compound and a catalyst containing a transition metal compound of Group IV of the periodic table. Is desirable. Since such a linear ethylene (co) polymer has a narrow molecular weight distribution and compositional distribution, it is a polymer having excellent mechanical properties, heat sealing properties, heat blocking properties, and the like, and also having good heat resistance. .

Ethylene (co) polymer in the present invention
The production of (A) is carried out by mixing the following compounds a1 to a4 in particular.
It is desirable to polymerize with the catalyst obtained in this way. a1: general formula Me¹R¹ _pR² _q(OR³)_rX¹ _4-pqr Table
Compound (in the formula, Me¹ Is zirconium, titanium,
Indicates hafnium. R¹And R³Each has 1 to 1 carbon atoms
24 hydrocarbon groups, R² Is 2,4-pentanedionato
A ligand or a derivative thereof, a benzoylmethanato ligand,
Benzoylacetonato ligand or its derivative, X¹ Is
Indicates a halogen atom. p, q and r are each 0 ≦ p
≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4
Is an integer that satisfies the range) a2: general formula Me²R^Four _m(OR^Five)_nX² _zmn Represented by
Compound (in the formula, Me²Is an element of Group I to III of the periodic table, R^Four
And R^FiveAre each a hydrocarbon group having 1 to 24 carbon atoms, X²
Is a halogen atom or a hydrogen atom (provided that X²Is hydrogen
Me for children ² Is limited to Group III elements of the periodic table
Indicates). z is Me² Indicates the valence of. m and n are
Each is an integer satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z.
And 0 ≦ m + n ≦ z) a3: Organic cyclic compound having conjugated double bond a4: Modified organoaluminum containing Al-O-Al bond
Oxy compound and / or boron compound

Further 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 ¹ _4-pqr , Me ¹ represents zirconium, titanium or hafnium. The type of these transition metals is not limited, and a plurality of types can be used. Above all, it is particularly preferable that zirconium is contained, which can provide a copolymer having excellent weather resistance. 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 1-8. Specifically, a methyl group,
Alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group; alkenyl groups such as vinyl group, allyl group; phenyl group, tolyl group, xylyl group, mesityl group,
Examples thereof include 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 neophyl 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,
Indicates a halogen atom such as iodine, chlorine and bromine. p
And q are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ r, respectively.
An integer that satisfies the ranges of ≦ 4 and 0 ≦ p + q + r ≦ 4.

Examples of the compound represented by the general formula of the catalyst component a1 are tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetraethoxyzirconium, tetrabutoxyzirconium and tetrabutoxytitanium. , Tetrabutoxyhafnium and the like, and particularly Z such as tetrapropoxyzirconium and tetrabutoxyzirconium.
The r (OR) ₄ compound is preferable, and two or more kinds thereof may be mixed and used. Further, specific examples of the 2,4-pentanedionato ligand or its derivative, benzoylmethanato ligand, benzoylacetonato ligand or its derivative include tetra (2,4-pentanedionato) zirconium. , Bird (2,4-pentanedionato)
Chloride zirconium, di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride zirconium, di (2,4-pentanedionato) dietoxide zirconium, di (2,4-) Pentandionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n
-Butoxide zirconium, di (2,4-pentanedionato) dibenzylzirconium, di (2,4-pentanedionato) dineofoilzirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) die Toxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (dibenzoylmethanato) di-n-butoxide zirconium, di (benzoylacetonato) dietoxide zirconium, di (benzoylacetonato) ) Di-n-propoxide zirconium, di (benzoylacetonato)
Examples thereof include di-n-butoxide zirconium.

The above-mentioned catalyst component a2 has the general formula Me.²R^Four _m(O
R^Five)_nX² _zmn In the formula of the compound represented by: Me² Is Zhou
Periodic table Group I-III elements, lithium, sodium
Mu, potassium, magnesium, calcium, zinc, bor
It is a raw material or aluminum. 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
Cyl group, ethyl group, propyl group, isopropyl group, buty
Alkyl group such as vinyl group; alkyl group such as vinyl group and allyl group
Kenyl group; phenyl group, tolyl group, xylyl group, mesity
Aryl groups such as phenyl, indenyl and naphthyl groups;
Group, trityl group, phenethyl group, styryl group,
Inshydryl group, phenylbutyl group, neofoyl group, etc.
And the aralkyl group of. These have branches
May be. X² Is fluorine, iodine, chlorine and bromine, etc.
It represents a halogen atom or a hydrogen atom. However
Then X ² When is a hydrogen atom, Me² Is boron, aluminum
Only in the case of group III elements of the periodic table exemplified by um, etc.
It is something. Also, z is Me² Shows the valence of
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; dimethyl. Organozinc compounds such as zinc and diethylzinc; Organoboron compounds such as trimethylboron and triethylboron; Trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride , Ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum Derivatives of organoaluminum compounds such as Idoraido the like.

The above-mentioned organic cyclic compound having a conjugated double bond of the catalyst component a3 is a ring which has two or more conjugated double bonds, preferably 2 to 4 and more preferably 2 to 3 or A cyclic hydrocarbon compound having two or more and a total carbon number of 4 to 24, preferably 4 to 12; 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 formula 1 to 12; 2 or more, preferably 2 to 4, more preferably 2 to 2 conjugated double bonds.
Have 1 or 2 or more rings with 3 and have 4 total carbon atoms
An organosilicon compound having a cyclic hydrocarbon group of -24, preferably 4 to 12; the cyclic hydrocarbon group is partially substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt). Included organosilicon compounds. Particularly preferably, one having a cyclopentadiene structure in any of the molecules is desirable.

Examples of the above-mentioned suitable compounds include cyclopentadiene, indene, azulene or their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Moreover, the compound which these compounds couple | bonded (bridge | crosslink) through the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.

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

Specific examples of the organic cyclic hydrocarbon compound of the above component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene and 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, methylcycloheptatriene, cyclooctatetraene,
C5 to C24 cyclopolyene or substituted cyclopolyene such as azulene, fluorene and methylfluorene, monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindene Examples thereof include nylsilane, trisindenylsilane, methylcyclopentadi-entrymethylsilane and the like.

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

The reaction of organoaluminum with 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 preferable. The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2 /
It is desirable that it is 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-
Examples include dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (3,5-difluorophenyl) borate, trityl tetrakispentafluoroborate, ferrocenium tetrakispentafluoroborate, trispentafluoroborane. To be Among them, N, N'-dimethylanilinium tetra (pentafluorophenyl) borate,
Trityl tetrakispentafluoroborate, ferrocenium tetrakispentafluoroborate, and trispentafluoroborane are preferred.

The above catalysts may be used by mixing and contacting a1 to a4, but it is preferable to use them by supporting them on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or the particulate polymer carrier (a5) include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, or thermoplastic resins, thermosetting resins and the like. 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 ,
Examples thereof include CaO, ZnO, BaO, ThO _{2 and the} like, or a mixture 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, etc. SiO ₂ -Cr ₂ O ₃ and the like. Of these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ . Further, as the organic compound, either a thermoplastic resin or a thermosetting resin can be used, and specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.

The above inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are treated with an organoaluminum compound or a modified organoaluminum compound containing an Al--O--Al bond. It can also be used as the component a5 after the contact treatment.

The method for producing the ethylene (co) polymer (A) in the present invention is produced 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, which is substantially free of a solvent. Aliphatic hydrocarbons such as butane, pentane, hexane, heptane, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, etc., in a state where oxygen, water, etc. are substantially cut off. It is produced in the presence or absence of an inert hydrocarbon solvent as exemplified by. 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 to 110 ° C,
The polymerization pressure is usually normal pressure to 70 kg / cm ^{2 in} the case of low and medium pressure method.
G, preferably normal pressure to 20 kg / cm ² G, and usually 1500 kg / cm ² G or less in the high pressure method.
In the case of the low and medium pressure method, the polymerization time is usually 3 minutes to 10 hours, preferably about 5 minutes to 5 hours. In the case of the high pressure method, it is usually 1 minute to 30 minutes, preferably 2 minutes to 20 minutes. The polymerization is not limited to the one-step polymerization method, and is not particularly limited to a two-step or more multi-step polymerization method in which the 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 (ND: 2
ppm or less). By using a halogen-free ethylene (co) polymer such as chlorine, it is not necessary to use an acid neutralizer (acid absorber) as in the past, and chemical stability and hygiene are excellent.
In particular, it is suitably used as a clean packaging material / container in the food field, medical field, electronic material field, and the like. Further, by using a halogen-free ethylene (co) polymer, it is not necessary to add an additive such as calcium stearate. Further, by substantially not adding an additive such as an antioxidant and calcium stearate, it is possible to provide a laminate having good adhesion strength between layers without the inhibition of adhesion by the additive such as calcium stearate.

As the other polyolefin resin (B) in the present invention, a high / medium / high level catalyst using a Ziegler type catalyst or the like is used.
Ethylene homopolymers by low-pressure method and other known methods, copolymers of ethylene and α-olefins having 3 to 12 carbon atoms, ethylene-based (co) polymers by high-pressure radical polymerization method, polypropylene-based resin, etc. Can be mentioned.

High / medium / high using the above Ziegler type catalyst
An ethylene homopolymer or a copolymer of ethylene and an α-olefin having a carbon number of 3 to 12 obtained by the low pressure method and other known methods has a density of 0.94 to 0.97 g / cm ^3.
High density polyethylene, density 0.91-0.94g / c
m ³ linear low density polyethylene (hereinafter referred to as LLDPE), ultra-low density polyethylene (hereinafter referred to as VLDPE) having a density of 0.86 to 0.91 g / cm ³ , and density of 0.86
.About.0.91 g / cm ³ of ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber are included.

The above-mentioned ZLD-type catalyst-based LLDPE is an ethylene / α-olefin copolymer having a density in the range of 0.91 to 0.94 g / cm ³ , preferably 0.91 to 0.93 g / cm ³ . , MFR is 0.01-100g
/ 10 minutes, preferably 0.1 to 50 g / 10 minutes, more preferably 1 to 40 g / 10 minutes. The α-olefin has 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and specifically, propylene, 1-butene, and 4
-Methyl-1-pentene, 1-hexene, 1-octene and the like can be mentioned.

In addition, the above-mentioned Ziegler type catalyst has an extremely low density.
Degree polyethylene (VLDPE) has a density of 0.86 ~
0.91 g / cm³ , Preferably 0.88 to 0.905g
/ Cm ³ Ethylene / α-olefin copolymer in the range of
Yes, linear low density polyethylene (LLDPE) and ethyl
-Α-olefin copolymer rubber (EPR, EPDM)
It is a polyethylene showing intermediate properties. MFR is 0.
01 to 100 g / 10 minutes, preferably 0.1 to 50 g /
It is 10 minutes, more preferably 1 to 40 g / 10 minutes.

The ethylene / α-olefin copolymer rubber is an ethylene / propylene copolymer rubber or 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 a random copolymer (EPM) containing ethylene and propylene as main components, and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) added as a third component. Random copolymer (EPDM) which has as a main component is mentioned.

The ethylene-based (co) polymers produced by the high-pressure radical polymerization method are ethylene homopolymers (low-density polyethylene) produced by the high-pressure radical polymerization method, ethylene.
Examples thereof include a vinyl ester copolymer and a copolymer of ethylene and an α, β-unsaturated carboxylic acid or its derivative.

The low density polyethylene is produced by a known high pressure radical polymerization method. The high pressure radical polymerization method is
Either a tubular method or an autoclave method may be used.
Low density polyethylene (LDPE) obtained by the high pressure radical polymerization method has an MFR of 0.01 to 100 g / 10.
Min, more preferably 0.1 to 80 g / 10 min, and still more preferably 1 to 60 g / 10 min. The density is 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, it is 3 to 15 g. The molecular weight distribution (Mw / Mn) is 3.0 to 12, preferably 4.0.
It is 8.0.

The ethylene / vinyl ester copolymer is produced by a high-pressure radical polymerization method and comprises ethylene, 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. Of these, vinyl acetate is particularly preferable. A copolymer composed of 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 preferable. Further, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight. M
FR is 0.01 to 100 g / 10 minutes, more preferably 0.1 to 80 g / 10 minutes, and further preferably 1 to 60 g.
The range is / 10 minutes.

Further, a typical copolymer of ethylene and an α, β-unsaturated carboxylic acid or its derivative is ethylene / (meth) acrylic acid or its alkyl ester copolymer. To 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 and glycidyl methacrylate. Among these, alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate are particularly preferable. In particular, the (meth) acrylic acid ester content is 3 to 20% by weight,
It is preferably in the range of 5 to 15% by weight. MFR is 0.
01 to 100 g / 10 minutes, more preferably 0.1 to 8
It is in the range of 0 g / 10 minutes, more preferably 1 to 60 g / 10 minutes.

As the polypropylene resin, for example,
Propylene homopolymer obtained by low / medium / high pressure polymerization with Ziegler type catalyst, Phillips type catalyst, metallocene type catalyst or the like, random copolymer of propylene and other α-olefin having 2 to 20 carbon atoms, block copolymerization An example is coalescence.

Among these other polyolefin resins (B), the high-pressure radical method low-density polyethylene is most preferably used because it has excellent moldability and is halogen-free.

The resin material containing the ethylene (co) polymer (A) in the present invention is an ethylene (co) polymer (A).
It is also possible to use other polyolefin resin (B) 8
It is preferable that the resin composition contains less than 0% by weight. Particularly preferably, the ethylene (co) polymer (A) is 95 to 50% by weight, and the low density polyethylene (hereinafter referred to as LDPE) obtained by the high pressure radical polymerization method is 5 to 50% by weight, and more preferably ethylene (co) polymer. It is a resin composition containing 90 to 60% by weight of the coalescence (A) and 10 to 40% by weight of another polyolefin resin (B). When the ethylene (co) polymer (A) is 20% by weight or less, the low temperature heat-sealing property of the laminate becomes poor, which is not preferable.

Although the reason for the resin material containing the ethylene (co) polymer (A) in the present invention is not clear, low temperature molding is possible and surface treatment such as ozone treatment is effective. The above-mentioned low temperature molding has an advantage that the resin is less likely to be deteriorated by heat and that it is not necessary to add an antioxidant. Moreover, since the resin is less blocked by molding at a low temperature, it is not necessary to add an anti-blocking agent or the like. Further, when the ethylene (co) polymer (A) is produced using a catalyst containing no halogen, it is not necessary to add an acid absorbent. Further, even when molding is carried out at a conventional molding temperature or higher, the generation of smoke and odor can be suppressed because the low molecular weight is essentially small, and the contamination of the cooling roll can be suppressed.

For the resin material containing the ethylene (co) polymer (A), a known additive such as an acid absorbent, an antioxidant and an antiblocking agent, a lubricant, an antistatic agent, an antifogging agent may be added depending on the use. It is desirable that no agent, ultraviolet absorber, organic or inorganic pigment, nucleating agent, cross-linking agent, etc. be contained. One of the features of the present invention is that even when an additive is used, the additive is one that does not substantially elute outside or that does not affect the contents. Here, the additive that does not affect the contents means that when the laminate containing the resin material containing the ethylene (co) polymer (A) is used as a container, the contents of the container have an odor, an elution component ( It is an additive that does not transfer off-flavor. 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 with time Since the additive which is unevenly distributed on the film surface is not contained in the resin material containing the ethylene (co) polymer (A), it becomes possible to provide a clean laminate and container.

The additive which does not elute to the outside is a filler such as an organic or inorganic filler, which does not deteriorate the contents of the container and does not substantially impair the properties of the laminate or container of the present invention. It is an additive that can be added within the range. 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, oxidation Zinc, mica, glass flakes, zeolite,
Examples include diatomaceous earth, perlite, permiculite, shirasu balloon, glass micro fair, fly ash, and glass beads. Examples of the organic filler include polymethyl methacrylate crosslinked products, polyethylene terephthalate crosslinked products, powders of synthetic resins such as phenol resin and fine beads, wood powder, pulp powder and the like. The resin material containing the ethylene (co) polymer (A) includes
It is desirable that an additive that may reduce the adhesiveness with the base material layer or the sealant layer (II), for example, a lubricant such as calcium stearate is not mixed.

The sealant layer (II) in the present invention comprises a non-stretched polypropylene film (CPP), which is a polypropylene resin film that has not been stretched. Examples of the polypropylene resin used include propylene homopolymer and propylene-α-olefin copolymer. As the α-olefin, at least one selected from ethylene, butene-1, hexene-1, 4-methylpentene-1 and the like is selected. Also, MFR is 0.0
1 to 100 g / 10 minutes, preferably 0.1 to 80 g / 1
It is in the range of 0 minutes, more preferably 1 to 60 g / 10 minutes. These resins are produced with known catalysts such as Ziegler type catalysts and metallocene catalysts.

The packaging material of the present invention has a laminated structure, but it has the above-mentioned resin layer (I) and sealant layer (I).
I) and at least, in addition to this two-layer structure,
Multiple configurations of three or more with other layers apply. Examples of the other layer include the base material layer (III).

The material used for the first substrate layer (III) in the present invention is thermoplastic resin, paper, non-woven fabric, woven fabric or the like. As the thermoplastic resin, polyester resin,
Polyamide resin, polypropylene, polyethylene resin, polyvinylidene chloride resin, polycarbonate resin,
Films such as cellophane are mentioned, and these stretched products,
Includes printed material.

Further, in addition to the base material layer (III), a second base material layer (IV) can be provided. This second base material layer (I
Examples of V) include thermoplastic resins such as saponified ethylene / vinyl acetate copolymers, stretched films thereof, metal foils, metal vapor deposition films, inorganic vapor deposition films and the like. Examples of the metal foil or metal vapor deposition film or inorganic vapor deposition film include aluminum, gold, silver, iron, steel, copper, nickel, metal foils such as alloys containing these as main components; polyester, polyamide, etc. on the surface of the film; Examples include vapor-deposited films obtained by vapor-depositing metals such as aluminum and silicon or metal oxides thereof.

In the packaging material of the present invention, at least two layers, a resin layer (I) made of a resin material containing an ethylene (co) polymer (A) and a heat seal layer (II) made of unstretched polypropylene, are anchor coating agents. It includes a laminated structure in which it is directly adhered without interposing. As a concrete example, SLL
/ CPP, PA film / SLL / CPP, paper / SLL
/ CPP, non-woven fabric / SLL / CPP, woven fabric / SLL / C
PP, PA film / (SLL + LD) / CPP, PE
T film / SLL / CPP, PET film / (S
LL + LD) / CPP, SLL / PA film / SL
L / CPP, (SLL + LD) / PET film / (S
LL + LD) / CPP, (SLL + LL + LD) / CP
P, (SLL + LL + LD) / PET film / (SL
L + LL + LD) / CPP, PET film / (SLL
+ HD + LD) / CPP, LD / SLL / PET film / SLL / CPP, paper / SLL / aluminum deposited PET /
SLL / CPP, OPP / SLL / Aluminum deposited PET /
SLL / CPP, OPP / SLL / alumina vapor deposition PET
/ SLL / CPP and the like, but 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. )

As a specific combination of snacks and the like, OPP (OPET, ONY) / adhesive / S
LL / VM-PET / SLL / CPP, OPP (OP
ET, ONY) / SLL / VM-PET / SLL / CP
P, OPP (OPET, ONY) / SLL / AL / S
LL or Dry Lami / PET / SLL / CPP, O
NY / SLL / VM-PET / SLL / CPP, PE
Examples include T / SLL / VM-PET / SLL / CPP. (However, OPP: biaxially oriented polypropylene, OPET: biaxially oriented polyethylene terephthalate,
ONY: biaxially stretched nylon, SLL: ethylene (co) polymer of the present invention, VM-PET: metal evaporated polyethylene terephthalate, AL: aluminum foil, PET: polyethylene terephthalate, CPP: unstretched polypropylene)

In the packaging material of the present invention, since the resin material containing the ethylene (co) polymer (A) has excellent adhesiveness to CPP, the CPP and the resin material can be prepared without using an anchor coating agent. Excellent adhesion strength between Moreover, since the resin layer (I) made of the resin material containing the ethylene (co) polymer (A) is directly laminated on the sealant layer or the base material layer, the conventional LDPE layer can be dispensed with. When a resin material containing an ethylene (co) polymer (A) is provided as an alternative to the conventional LDPE layer, a stronger laminate can be obtained, and the stability as a packaging material can be improved. In addition, since the additive compounded in the resin material is an additive that does not elute to the outside or does not affect the contents, it has little odor, and it deteriorates the quality of the contents even when used as a container or packaging material. There is no.

As the method for producing the packaging material of the present invention, a resin material containing ethylene (co) polymer (A) as a main component and C
Examples thereof include an extrusion laminating method, a coextrusion method, a method of further laminating the extruded laminating material on another substrate by a dry laminating method, and a method of laminating PP without using an anchor coating agent by a tandem laminating method. Among them, the extrusion laminating method and the coextrusion method are particularly preferable.

In the method for producing the packaging material of the present invention,
Ethylene (co) polymer (A) containing no additive
Or a resin material containing an ethylene (co) polymer (A) in which only an additive that does not substantially elute outside or an additive that does not affect the contents is blended is used. . By using such a resin material containing the ethylene (co) polymer (A), it is possible to produce a clean laminate or container in which the odor is not transferred or eluted by the additive and the taste and the quality are not easily changed. Becomes
Further, since the resin material containing the ethylene (co) polymer (A) having excellent adhesiveness to the substrate is used, it is not necessary to use the anchor coating agent. Moreover, the LDPE provided between the base material layer and the heat seal layer of the conventional laminated body
Since the layer is unnecessary, the packaging material can be manufactured in a small number of steps.

When the resin material is extrusion-laminated with the ethylene (co) polymer (A), the molten resin is subjected to ozone treatment while having a melting point or higher to 330 ° C., preferably 20.
It is desirable to extrusion laminate at a molding temperature of 0 to 300 ° C. By performing the ozone treatment, the adhesive strength between the CPP layer (II) and the base material layer (III) and the resin material layer (I) can be maintained even by extrusion lamination at a low temperature. Moreover, it is preferable to perform a surface treatment such as a corona discharge treatment on the base material at the time of lamination.
Further, by performing the surface treatment on both the molten film and the substrate, the adhesive strength between the CPP layer (II) and the resin material layer (I) can be further improved.

[0069]

EXAMPLES The present invention will be described in more detail below 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) was used, and ODCB at 135 ° C. was used as a solvent. As the column, Showdex HT806M was used.

[Measurement of T _ml by DSC] Thickness 0.2 m
A sheet of m was formed by hot pressing, and a sample of about 5 mg was punched out from the sheet. This sample was kept at 230 ° C. for 10 minutes and then cooled to 0 ° C. at 2 ° C./minute. Then again 10
The temperature was raised to 170 ° C at a rate of ° C / min, and the temperature at the top of the highest temperature peak that appeared was taken as the highest peak temperature T _ml .

With the [TREF] column kept at 140 ° C., a sample was injected into the column and the temperature was lowered to 25 ° C. at 4 ° C./hr to deposit the polymer on the glass beads, and then the column was subjected to the following conditions. The temperature was raised and the polymer concentration eluted at each temperature was detected with an infrared detector. (Solvent: ODCB, flow rate: 1 ml / min, heating rate: 50 ° C./hr, detector: infrared spectroscope (wavelength 2925 cm ⁻¹ ), column: 0.8 cm
φ × 12 cmL (filled with glass beads), sample concentration:
0.05% by weight)

[Melt Tension (MT)] It was determined by measuring the stress when the molten polymer was stretched at a constant rate with a strain gauge. The measurement sample is granulated into pellets, and is manufactured by Toyo Seiki Seisakusho M
It measured using the T measuring device. The orifice used had a hole diameter of 2.09 mmφ and a length of 8 mm, and the measurement conditions were a resin temperature of 190 ° C., a cylinder descending speed of 20 mm / min, and a winding speed of 15 m / min.

[Chlorine concentration] 1 measured by fluorescent X-ray method
When chlorine of 0 ppm or more was detected, this was taken as the analytical value. When it is lower than 10 ppm, it is measured by a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd., and 2 ppm or less is not detected (N
D: non-detected), and not included substantially.

[Adhesive Strength] Using a tensile tester, a test piece of a laminate (15 mm
Width) was peeled between the layers, and the 180-degree peel strength at that time was determined.

[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 small. ○ to △: Some smoke is emitted, but long-term operation is within the allowable range. Δ: Operation is possible although smoke is generated. X: A lot of smoke is generated, which hinders driving. [Dirt on Cooling Roll] The resin layer was exposed from the substrate and brought into contact with the cooling roll to operate, and the stain on the cooling roll was visually observed. ○: No dirt △: Some dirt X: Some dirt

Various components used in Examples and Comparative Examples are as follows. Ethylene (co) polymer (A) (A11
And A12) were polymerized by the following method. The ethylene copolymer (A11) was polymerized by the following method. <1. Preparation of solid catalyst> 1000 ml of toluene purified under nitrogen and 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ) were added to a catalyst preparation device equipped with an electromagnetic induction stirrer.
And 75 g of indene and 88 g of methylbutylcyclopentadiene were added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and then reacted at the same temperature for 2 hours. After cooling to 40 ° C,
Toluene solution of methylalumoxane (concentration 2.5 mmo
1 / ml) was added and stirred for 2 hours. Next, silica (Grace Co., # 952, surface area 300 m ² / g) 2000, which was previously calcined at 450 ° C. for 5 hours.
g was added, and the mixture was stirred at room temperature for 1 hour, then blown with nitrogen and dried under reduced pressure at 40 ° C. to obtain a solid catalyst (a) having good fluidity.

<2. Gas phase polymerization> Continuous fluidized bed gas phase polymerization
Using a device, polymerization temperature 65 ℃, total pressure 20kgf / cm ² 
In G, ethylene and 1-hexene were copolymerized. The above
Continuous supply of body catalyst (a), ethylene, 1-hexene
Polymerization by supplying hydrogen and hydrogen at a specified molar ratio
Then, an ethylene copolymer (A11) was obtained. Its physical properties
Is shown in Table 1.

The ethylene copolymer (A12) was polymerized by the following method. <1. Preparation of solid catalyst> 1000 ml of toluene purified under nitrogen and 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ) were added to a catalyst preparation device equipped with an electromagnetic induction stirrer.
And 74 g of indene were added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and then the mixture was reacted at the same temperature for 2 hours. After cooling to 40 ° C, a solution of methylalumoxane in toluene (concentration 2.
(5 mmol / ml) was added and stirred for 2 hours. Next, silica pre-calcined at 450 ° C. for 5 hours (manufactured by Grace, # 952, surface area 300 m ² / g)
2000 g was added, and the mixture was stirred at room temperature for 1 hour, then blown with nitrogen and dried under reduced pressure at 40 ° C. to obtain a solid catalyst (b) having good fluidity.

<2. Gas phase polymerization> Continuous fluidized bed gas phase polymerization
Using a device, polymerization temperature 70 ℃, total pressure 20kgf / cm ² 
In G, ethylene and 1-hexene were copolymerized. The above
Continuous supply of body catalyst (b), ethylene, 1-hexene
Polymerization by supplying hydrogen and hydrogen at a specified molar ratio
Then, an ethylene copolymer (A12) was obtained. Its physical properties
Is shown in Table 1.

The ethylene copolymer (A2) was polymerized by the following method. <1. Preparation of solid catalyst> 1000 ml of toluene purified under nitrogen and 22 g of tetrabutoxyzirconium (Zr (OBu) ₄ ) were added to a catalyst preparation device equipped with an electromagnetic induction stirrer.
And 40 g of indene and 21 g of methylpropylcyclopentadiene were added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and then reacted at the same temperature for 2 hours. After cooling to 40 ° C, a toluene solution of methylalumoxane (concentration 2.5m
2000 ml of (mol / ml) was added and stirred for 2 hours.
Next, silica (Grace Co., # 952, surface area 300 m ² / g) 2 which had been preliminarily calcined at 450 ° C. for 5 hours 2
000 g was added, and the mixture was stirred at room temperature for 1 hour, then blown with nitrogen and dried under reduced pressure at 40 ° C. to obtain a solid catalyst (c) having good fluidity.

<2. Gas phase polymerization> Continuous fluidized bed gas phase polymerization
Using a device, polymerization temperature 80 ℃, total pressure 20kgf / cm ² 
In G, ethylene and 1-hexene were copolymerized. The above
Continuous supply of body catalyst (C), ethylene, 1-hexene
Polymerization by supplying hydrogen and hydrogen at a specified molar ratio
Then, an ethylene copolymer (A2) was obtained. Its physical properties
The results are shown in Table 1.

An ethylene / hexene-1 copolymer (mLL) with a general metallocene catalyst was produced as follows. Purified toluene was placed in a pressure reactor equipped with a stirrer, which was replaced with nitrogen, then 1-hexene was added, and a mixed solution of bis (n-butylcyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) was added. After adding (Al / Zr molar ratio = 500), the temperature was raised to 80 ° C. to prepare a metallocene catalyst. Then, add ethylene and polymerize ethylene continuously while the total pressure is 6 kg.
/ Cm ³ Polymerization was conducted by keeping the ethylene-hexene -
1 copolymer (mLL) was produced. The physical properties are shown in Table 1.

High pressure radical method low density polyethylene (LDPE) blended with A1, A2 and mLL: density = 0.
918 g / cm ³ , MFR = 5 g / 10 min, Resin B1: Commercial high pressure radical method low density polyethylene (L
DPE); Density = 0.918 g / cm ³ , MFR = 7 g / 10
min, Resin B2: Commercial Ziegler linear low density polyethylene (solution method: LLDPE); Density = 0.910 g / cm ³ ,
MFR = 8g / 10min, comonomer: 1-octene

[0085]

[Table 1]

Example 1 Using a composition of 75% by weight of the above-mentioned ethylene-hexene 1 copolymer (A11) and 25% by weight of high-pressure radical method low density polyethylene (LDPE), a resin temperature of 320 ° C. and a line speed were set. 150m / min,
A laminate having a laminating thickness of 10 μm and protruding from the substrate, a substrate layer (III) made of a 20 μm thick biaxially oriented polypropylene (OPP) film and a 30 μm thick unstretched polypropylene sealant layer (II) were sand laminated. . In addition, a corona treatment (6 kW) was applied to the adhesive surface of the OPP. Obtained laminate: OPP 20 μm / (A11 + LD) 1
The adhesive strength between the layers of 0 μm / CPP of 30 μm was measured. The results are shown in Table 2. Good adhesive strength was obtained for each layer. Further, there was little smoke generation, and there was no stain on the portion of the protruding portion that came into contact with the cooling roll.

[Examples 2 to 4] The ethylene-hexene-1 copolymer (A11) of Example 1 was replaced with the ethylene-hexene-1 copolymer (A12) and ethylene-hexene-1 copolymer (A2) of the present invention. A laminate was produced in the same manner as in Example 1 except that the metallocene-based ethylene-hexene-1 copolymer (mLL) was used and the composition was blended at the ratios shown in Table 2. It was measured. Good adhesive strength was obtained from each layer, and smoke generation was good as in Example 1.

[0088]

[Table 2]

Example 5 Using a composition of 70% by weight of the above ethylene-hexene 1 copolymer (A11) and 30% by weight of high-pressure radical method low density polyethylene (LDPE), a resin temperature of 320 ° C. and a line speed were set. 150m / min,
With a lamination thickness of 10 μm, an OPP (biaxially oriented polypropylene) film having a thickness of 20 μm and a vapor deposition surface of an aluminum vapor deposition PET film having a thickness of 12 μm were sand laminated (α). The surface of the OPP film was subjected to corona treatment (6 kW). Furthermore, with the PET surface of this laminate,
Similarly, a 30 μm thick CPP film was sand laminated to a thickness of 10 μm (β). At this time, the PET surface was not subjected to anchor coating or corona treatment, but the PET surface was subjected to corona treatment at the time of shipping the film, and the wetting index was 43 to 47 dyn. Obtained laminate: OPP 20 μm / (A11 + LD) 1
0 μm / Al evaporated PET / (A11 + LD) 10 μm /
The adhesive strength between each layer of CPP of 30 μm was measured. The results are shown in Table 3. Good adhesive strength was obtained for each layer. Further, both the sand laminate (α) and the sand laminate (β) generated little smoke, and could be operated for a long time.

Example 6 A laminate was prepared in the same manner as in Example 5 except that biaxially oriented nylon (ONY) was used instead of OPP in Example 5, and the adhesive strength thereof was measured. The results are shown in Table 3. Good adhesive strength was obtained for each layer.
Also, there was little smoke emission. Example 7 The ethylene-hexene 1 copolymer (A1
1) Using a composition of 80% by weight and 20% by weight of high-pressure radical method low density polyethylene (LDPE), a resin temperature of 320 ° C., a line speed of 150 m / min, and a laminating thickness of 13
A single-sided coated paper having a basis weight of 200 g and a vapor-deposited surface of a 12 μm-thick silicon oxide vapor-deposited PET (SiO ₂ -PET) film having a thickness of 200 μm. The surface of the single-sided coated paper was subjected to corona (7 kW) treatment. Further, the PET surface of this laminate and a CPP film having a thickness of 30 μm were similarly sand laminated to a thickness of 13 μm. At this time, P
The ET surface was not subjected to anchor coat treatment, but was subjected to 6 kW corona treatment. Obtained laminate: coated paper / corona treated / A11 + LD
13 μm / SiO ₂ -PET 12 μm / Corona treatment / A1
The adhesive strength between each layer of 1 + LD 13 μm / CPP 30 μm was measured. The results are shown in Table 3. Good adhesive strength was obtained for each layer. Also, there was little smoke emission.

[Example 8] Using a composition of 70% by weight of the ethylene-hexene 1 copolymer (A11) of the present invention and 30% by weight of a high-pressure radical method low density polyethylene (LDPE), a resin temperature of 320 ° C was used. Line speed 150m / mi
n, laminating thickness 13 μm, basis weight 200 g single-sided coated paper and 15 μm thick ethylene-vinyl acetate copolymer saponified (EVOH) film were sand laminated. still,
The surface of the single-sided coated paper was subjected to corona (7 kW) treatment. Further, the EVOH surface of this laminate and a CPP film having a thickness of 30 μm were similarly sand-laminated to a thickness of 13 μm. At this time, the EVOH surface was not subjected to anchor coating treatment, but was subjected to 6 kW corona treatment. Obtained laminate: coated paper / corona treated / A11 + LD
13 μm / EVOH 15 μm / Corona treatment / CPP30
The adhesive strength between each layer of μm was measured. The results are shown in Table 3. Good adhesive strength was obtained for each layer. Also, there was little smoke emission.

[Example 9] An ethylene-1-hexene copolymer (A12) was used in place of the ethylene-1-hexene copolymer (A11) of Example 7, and aluminum oxide was vapor-deposited as the base material layer (IV). A laminate was obtained in the same manner as in Example 7 except that PET (Al ₂ O ₃ -PET) was used, and its adhesive strength was measured. The results are shown in Table 3. Good adhesive strength was obtained for each layer. Also, there was little smoke emission.

Example 10 Ethylene of Example 8-1-
Instead of the hexene copolymer (A11), ethylene-1-
A laminate was obtained in the same manner as in Example 8 except that the hexene copolymer (A12) was used, and the adhesive strength thereof was measured. The results are shown in Table 3. Good adhesive strength was obtained for each layer.
Also, there was little smoke emission.

[0094]

[Table 3]

Comparative Example 1 B1: High-pressure LDPE was used instead of the composition comprising 75% by weight of the ethylene-hexene 1 copolymer (A11) of the present invention and 25% by weight of high-pressure radical polymerization low-density polyethylene. The same procedure as in Example 1 was carried out except that it was omitted. The adhesive strength between the base material layer (III) / resin layer (I) and the adhesive strength between the resin layer (I) / sealant layer (II) were weak as compared with the examples. The results are shown in Table 4.

Comparative Example 2 Instead of a composition comprising 75% by weight of the ethylene-hexene 1 copolymer (A11) of the present invention and 25% by weight of high-pressure radical polymerization low density polyethylene, B2: solution method Ziegler LLDPE was used. When the same procedure as in Example 1 was carried out except that it was used, a large amount of smoke was generated. In addition, the contact portion of the cooling roll at the protruding portion was often soiled. The adhesive strength between the base material layer (III) / resin layer (I) and the adhesive strength between the resin layer (I) / sealant layer (II) were weak as compared with the examples. The results are shown in Table 4.

[0097]

[Table 4]

[Comparative Example 3] B1: High-pressure LDPE was used in place of a composition comprising 70% by weight of the ethylene-hexene 1 copolymer (A11) of the present invention and 30% by weight of high-pressure radical polymerization low-density polyethylene. The same procedure as in Example 5 was carried out except that The adhesive strength between the layers of the obtained laminate was measured. The results are shown in Table 5. The adhesive strength between the base material layer (III) / resin layer (I) 1 is weak, and the adhesive strength to the vapor deposition surface (resin layer (I) 1 / base material layer (IV)) is slightly weak,
In addition, the adhesive strength between the PET surface not using the anchor coat and the laminated LDPE (base material layer (IV) / resin layer (I) 2) and adhesive strength between the resin layer (I) 2 / sealant layer (II) are It was weak. The results are shown in Table 5.

[Comparative Example 4] Instead of a composition comprising 70% by weight of the ethylene-hexene 1 copolymer (A11) of the present invention and 30% by weight of high-pressure radical polymerization low density polyethylene, B2: solution method Ziegler LLDPE was used. The same procedure as in Example 5 was carried out except that it was used. The adhesive strength between the layers of the obtained laminate was measured. The results are shown in Table 5. Substrate layer (II
The adhesion strength between I) / resin layer (I) 1 is weak, and the adhesion strength to the vapor deposition surface (resin layer (I) 1 / base material layer (IV))
PET is slightly weaker and PET without anchor coat
The adhesive strength between the surface and the laminated LDPE (base material layer (IV) / resin layer (I)) and between the resin layer (I) and the sealant layer (II) were weak. In addition, the smoke generated during lamination was relatively large.

[Comparative Example 5] B1: High-pressure LDPE was used in place of a composition comprising 80% by weight of the ethylene-hexene-1 copolymer (A11) of the present invention and 20% by weight of high-pressure radical polymerization low-density polyethylene. The same procedure as in Example 7 was carried out except that it was omitted. The adhesive strength between the layers of the obtained laminate was measured. The results are shown in Table 5. Adhesive strength to the vapor-deposited surface (resin layer (I) 1 / base material layer (IV)) is slightly weak, and the adhesive strength between the PET surface and the laminated LDPE, which has been corona-treated but does not use an anchor coat, and the resin layer The adhesive strength between (I) 2 / sealant layer (II) was weak.

[Comparative Example 6] Commercially available low-density polyethylene (B1) was applied as the resin layer (I) 1, and the resin layer (I) 2 was used.
Example 7 was repeated except that the solution method Ziegler LLDPE (B2) was used instead of the ethylene-hexene 1 copolymer (A11). The adhesive strength between the layers of the obtained laminate was measured. The results are shown in Table 5. Adhesive strength to the vapor-deposited surface (resin layer (I) 1 / base material layer (IV)) is slightly weak, and the adhesive strength between the PET surface and the laminated LDPE, which has been corona-treated but does not use an anchor coat, and the resin layer The adhesive strength between (I) 2 / sealant layer (II) was weak. In addition, there was a relatively large amount of smoke during laminating.

[0102]

[Table 5]

[Comparative Example 7] B1: High pressure LDPE was used instead of a composition comprising 80% by weight of the ethylene-hexene 1 copolymer (A11) of the present invention and 20% by weight of high density radical polymerization low density polyethylene. The same procedure as in Example 8 was carried out except that it was omitted. The adhesive strength between the layers of the obtained laminate was measured. The results are shown in Table 6. Adhesive strength (resin layer (I) 1 / base material layer (IV)) of EVOH that is not corona-treated is weak, and PET surface and corona-treated PET anchor-coated laminate LD
The adhesive strength between PEs was weaker than the example. Further, the adhesive strength between the resin layer (I) 2 / sealant layer (II) was weak.

[Comparative Example 8] B2: solution method Ziegler LLDPE was used in place of a composition comprising 70% by weight of the ethylene-hexene 1 copolymer (A11) of the present invention and 30% by weight of high density radical polymerization low density polyethylene. The same procedure as in Example 8 was carried out except that it was used. The adhesive strength between the layers of the obtained laminate was measured. The results are shown in Table 6. The adhesion strength (resin layer (I) 1 / base material layer (IV)) of the part not subjected to corona treatment to EVOH is weak, and between the PET surface and corrugated but not using the anchor coat and the laminated LDPE. The adhesive strength was weaker than that of the example. Further, the adhesive strength between the resin layer (I) 2 / sealant layer (II) was weak. Also, there was much smoke.

[0105]

[Table 6]

[0106]

As described above, the packaging material having the laminated structure of the present invention has excellent adhesive strength between the base material and the resin layer and has little odor, even without using an anchor coating agent. Even if it is used as a container or packaging material, the quality of the contents does not deteriorate. Further, at least one surface of the base material layer (III) made of at least one material selected from the group consisting of thermoplastic resin, paper, non-woven fabric and woven fabric satisfies the above requirements (a) to (d). A packaging material in which a resin layer (I) made of a resin material containing an ethylene (co) polymer (A) and a CPP layer are directly bonded to each other has further tear strength, impact resistance, molding processability, heat seal strength, and heat resistance. It is also excellent in gas barrier properties. In addition, the LDPE layer, which has been conventionally required, becomes unnecessary, and the number of layers can be reduced by one. Further, in the method for producing a packaging material of the present invention, the resin material (I) containing the ethylene (co) polymer (A) can be directly extrusion laminated on the CPP layer (II) without using an anchor coating agent, and It is possible to produce a packaging material having high adhesive strength with less smoke generated during molding.

[Brief description of drawings]

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

FIG. 2 shows an ethylene (co) polymer (A according to the present invention.
It is a graph which shows the elution temperature-elution amount curve of 1).

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

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshimasa Saito             2-3-2 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa               Japan Polyolefin Co., Ltd.             Research and Development Center (72) Inventor Ippei Kagaya             2-3-2 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa               Japan Polyolefin Co., Ltd.             Research and Development Center (72) Inventor Hiroshi Kasahara             2-3-2 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa               Japan Polyolefin Co., Ltd.             Research and Development Center F-term (reference) 3E086 AB01 AC07 AD01 BA04 BA15                       BB41 BB51 BB74 BB85 BB90                       CA01 CA27 CA28 CA31 DA08                 4F100 AA00E AB01E AB33D AK01C                       AK01D AK03A AK04A AK05A                       AK07B AK62A AK62K AL05A                       AT00C AT00D BA02 BA03                       BA04 BA05 BA07 BA10A                       BA10B BA10C BA10D BA10E                       BA13 DG10C EH232 EH66E                       EJ37C EJ37D GB15 GB23                       GB41 GB66 HB31C JA06A                       JA07A JA13A JA20A JK06                       JL02 JL12B JM02E YY00A

Claims (15)

[Claims] 1. A resin material containing 100 to 20% by weight of an ethylene (co) polymer (A) satisfying the following requirements (a) to (d) and 0 to 80% by weight of another polyolefin resin (B). A packaging material comprising a laminate in which a resin layer (I) composed of (1) and a sealant layer (II) composed of an unstretched polypropylene film are directly bonded. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10
25% of the total (c) molecular weight distribution (Mw / Mn) obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) is 1.5-4.5. The difference T ₇₅ -T ₂₅ between the elution temperature T ₂₅ and the temperature T _{75 at} which 75% of the total elutes, and the density d satisfy the following expression (equation 1) (equation 1) T ₇₅ -T ₂₅ ≤ -670 x d + 644 2. The packaging material according to claim 1, wherein the ethylene (co) polymer (A) further satisfies the following requirement (e). (E) The 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 obtained, which is obtained from the integral elution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) T ₇₅ -T ₂₅ and density d satisfy the following to satisfy the relation of (formula 2) (formula 2) d <when _{^{0.950g / cm 3 T 75 -T 25}} ≧ -300 × d + 285 d ≧ 0.950g / Cm ³ T ₇₅ −T ₂₅ ≧ 0 3. The packaging material has at least a first base material layer (III), and the first base material layer (III) / resin layer (I) /
The packaging material according to claim 1 or 2, which has a laminate in which a sealant layer (II) is laminated in this order. 4. The packaging material is a first base material layer (III).
And a second base material layer (IV), the first base material layer (III) /
The packaging material according to claim 1 or 2, which has a laminate in which a resin layer (I) / a second base material layer (IV) / a resin layer (I) / a sealant layer (II) are laminated in this order. 5. The third base layer (III) is at least one selected from the group consisting of paper, thermoplastic resin film, stretched film and printing film. The packaging material described in. 6. The second base material layer (IV) is at least one selected from the group consisting of a metal foil, a vapor deposition film of a metal and an inorganic compound, a thermoplastic resin, and a stretched film. The packaging material according to claim 4 or 5. 7. The other polyolefin resin (B)
Is a low-density polyethylene obtained by a high-pressure radical polymerization method, The packaging material according to any one of claims 1 to 6, wherein 8. The ethylene (co) polymer (A) is an ethylene (co) polymer (A1) further satisfying the following requirements (f) and (g):
A packaging material according to any one of 1 to 7. (F) Ortho-dichlorobenzene (ODC at 25 ° C)
B) Soluble content X (% by weight), density d and melt flow rate (MFR) satisfy the following relationship (Equation 3): d-0.008 log MFR ≧ 0.93 X <2.0 (Equation 3) 4) When d−0.008logMFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008logMFR)
² + 2.0 (g) Multiple peaks of elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF) 9. The ethylene (co) polymer (A) is an ethylene (co) polymer (A2) which further satisfies the following requirements (h) and (i):
The packaging material according to any one of items 1 to 7. (H) The number of peaks of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) is one. (I) One or two melting point peaks, and the highest melting point T _m1 and density d Satisfies the following relationship (Equation 5) (Equation 5) T _m1 ≧ 150 × d−17 10. The ethylene (co) polymer (A2)
Further satisfies the following requirement (j): The packaging material according to claim 9. (J) Melt tension (MT) and melt flow rate (MFR) satisfy the relationship of the following (Equation 6) (Equation 6) log MT ≦ −0.572 × log MFR + 0.
Three 11. The ethylene (co) polymer (A) comprises:
The package according to any one of claims 1 to 10, which is produced by a catalyst containing an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table. material. 12. The packaging material according to claim 1, wherein the halogen concentration in the resin material containing the ethylene (co) polymer (A) is 10 ppm or less. 13. The resin material containing the ethylene (co) polymer (A) contains substantially no additive, and the resin material containing the ethylene (co) polymer (A) according to claim 1. Packaging material. 14. A resin material containing 100 to 20% by weight of an ethylene (co) polymer (A) and 0 to 80% by weight of another polyolefin resin (B) satisfying the following requirements (a) to (d). A method for producing a packaging material, which comprises laminating a resin layer (I) composed of (1) and a sealant layer (II) composed of an unstretched polypropylene resin by a laminating method. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10
25% of the total (c) molecular weight distribution (Mw / Mn) obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) is 1.5-4.5. The difference T ₇₅ -T ₂₅ between the elution temperature T ₂₅ and the temperature T _{75 at} which 75% of the total elutes, and the density d satisfy the following expression (equation 1) (equation 1) T ₇₅ -T ₂₅ ≤ -670 x d + 644 15. A resin layer (I) made of the resin material
15. The method for producing a packaging material according to claim 14, wherein the additive is not substantially mixed with the composition.