JP2002052669A - Laminate and pouch using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in curl resistance, rigidity, low temperature heat sealability, steam barrier properties, aroma retention, sanitariness and heat resistance and having high heat seal strength and thrust strength, and a pouch using the same. SOLUTION: The laminate has a first layer I based on linear low density polyethylene or a high-pressure radical ethylenic polymer with a density of 0.94 g/cm3 or less, a second layer II comprising a polyolefinic resin material (ii) with an elastic modulus in bending of 2,500 kgf/cm2 or more and a third layer III comprising a resin (iii) based on a linear low density polyethylene resin with a density of 0.94 g/cm3 or less, and the second layer II is provided between the first and third layers I and III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to pouches such as standing pouches and retort pouches used for detergents, cosmetics, foodstuffs and the like, and laminates suitable for the pouches. Excellent barrier properties, fragrance retention, hygiene, heat resistance, pinhole resistance,
The present invention relates to a laminate having high heat seal strength and a pouch using the laminate.

[0002]

2. Description of the Related Art Conventionally, liquid detergents, shampoos, rinses, edible oils, seasonings and the like have been used in containers provided with spouts. Recently, for the purpose of resource saving, refill products containing replenishing contents such as standing pouches (for example, self-standing bags with bottom gussets) have been sold separately for the purpose of reusing containers. As other forms of the pouch, a retort pouch for retort foods, a pouch with a drinking spout used for drinking jelly and the like are also known.

Such a pouch includes a single-layer film made of high-density polyethylene, linear low-density polyethylene, low-density polyethylene, or a laminate of high-density polyethylene and low-density polyethylene, or a linear low-density polyethylene. Is used. These pouches are required to be easily heat-sealed, have a high heat-sealing strength, and be easily formed into a bag shape. In recent years, pouches obtained from such single-layer films, laminated films, and the like are required to have higher performance and lower cost. Excellent; hygienic so that taste and quality do not change due to transfer of low molecular weight components from the pouch, and odor does not transfer to the contents from the pouch; pinholes are not generated by vibration during product transportation Therefore, it is required to have a sufficient piercing strength.

[0004] Further, the standing pouch is further required to have sufficient rigidity (waist) necessary for self-support. Furthermore, recently, from the viewpoint of resource saving and environmental protection, containers and packaging materials have been required to be easily recyclable and easily collected. It has been demanded.

[0005]

However, the above-mentioned single-layer film of high-density polyethylene is inferior in heat sealability, and a pouch made of linear low-density polyethylene or a single-layer film of low-density polyethylene is rigid (lumpy). Lack and lack of independence. Further, a laminated film composed of high-density polyethylene and linear low-density polyethylene or low-density polyethylene has a problem that curling occurs, handling is poor, and workability is poor. Also recently,
From the viewpoints of resource saving and environmental protection, containers and packaging materials are required to simultaneously satisfy the above-mentioned various performances and required performances such as recyclability and easy recovery.

Accordingly, an object of the present invention is to provide a laminate having excellent heat seal strength, excellent in curl resistance, rigidity, low temperature heat sealability, water vapor barrier property, fragrance retention, hygiene, heat resistance, pinhole resistance. Another object of the present invention is to provide a body and a pouch using the same, and further provide a laminate excellent in recyclability and a pouch using the same.

[0007]

According to the present invention, there is provided a laminate comprising a resin material (i) mainly composed of a linear low-density polyethylene having a density of 0.94 g / cm ³ or less or a high-pressure radical polymerization ethylene polymer. I) layer, I layer and III layer
The layer has a flexural modulus of 2500 kgf /
a ^second layer made of a polyolefin-based resin material (ii) having a density of 0.94 g / cm ³ or less, and a resin material (ii) mainly containing a linear low-density polyethylene having a density of 0.94 g / cm ³ or less.
It is characterized by comprising at least three layers of the third layer consisting of i). Further, the flexural modulus is 2500 kgf / cm ²
The polyolefin resin material (ii) described above desirably contains, as a main component, a medium / high density polyethylene and / or polypropylene resin having a density of 0.93 g / cm ³ or more. Further, the heat sealing strength when the third layers are heat-sealed under the conditions of a heat sealing pressure of 1 kg / cm ² and a heat sealing time of 1 second is 3 kg / 15 m.
It is desirable that the heat sealing temperature to be m is in the range of 85 to 125 ° C.

Further, the thickness of the laminate is 10 μm to 0.5 m.
m, and the thickness of each of the I-th layer, the II-th layer and the III-th layer is preferably in the range of 3 μm to 0.4 mm. Further, the laminate of the present invention preferably further has a barrier layer (IV) bonded to the third layer. Further, any one of the first layer, the second layer and the third layer is
A recycled resin layer (V) formed of a blended resin of the resin material (i), the resin material (ii) and the resin material (iii) obtained by recycling the laminate, or made of the blended resin, It is desirable that it is further provided.

The linear low-density polyethylene is preferably (A) a linear low-density polyethylene satisfying the following requirements (a) to (d). (A) a density of 0.86 to 0.94 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 relationship of the following (formula 1) (formula 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644

The (A) linear low-density polyethylene is desirably (A1) a linear low-density polyethylene which 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 relationship of the following (Formula 2) and (Formula 3) (Formula 2) d−0.008 log MFR ≧ 0.93 X <2.0 (Equation 3) d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008)
(logMFR) ² +2.0 (f) Presence of multiple peaks in elution temperature-elution amount curve by continuous heating elution fractionation method (TREF)

It is preferable that the (A) linear low-density polyethylene is (A2) a linear low-density polyethylene that further satisfies the following requirements (g) and (h). (G) elution temperature by continuous Atsushi Nobori elution fractionation (TREF) - it is one peak of elution curve and the T ₇₅ -T ₂₅ and density d is, satisfy the relation of the following (Equation 4) ( (H) T ₇₅ −T ₂₅ ≧ −300 × d + 285 (h) One or two melting point peaks, and the highest melting point T _ml and density d satisfy the relationship of the following (Formula 5) ( Formula 5) T _ml ≧ 150 × d−17 Further, it is desirable that the (A2) linear low-density polyethylene further satisfies the following requirement (i). (I) Melt tension (MT) and melt flow rate (MFR) satisfy the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR + 0.3

The linear low-density polyethylene is preferably produced in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. . In addition, the resin material (ii
It is desirable that the additive blended in i) is an additive that does not substantially migrate to the contacted object, or that the additive is not blended in the resin material (iii). The halogen concentration of the resin material (iii) is desirably 10 ppm or less. Further, the pouch of the present invention is characterized in that the laminate of the present invention is formed into a bag shape with the third layer inside.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The resin material (i) containing a polyethylene resin as a main component for forming the first layer is a linear low-density polyethylene having a density of 0.94 g / cm ³ or less or a high-pressure radical ethylene polymer as a main component. And other polyethylene-based resins if necessary. Examples of the polyethylene resin used for the resin material (i) include a linear low-density polyethylene obtained by a Ziegler-type catalyst, a Philips-based catalyst, a metallocene-based catalyst, and the like;
Examples include linear low-density polyethylene and high-pressure radical-method ethylene-based polymers.

[0014] Linear low-density polyethylene obtained by Ziegler type catalyst such as a density of 0.94 g / cm ³ or less, preferably in the range of 0.86~0.935g / cm ^3, more preferably, 0.89 to 0.935 g / cm ³
Range. If the density exceeds 0.94 g / cm ³ , curling may occur. The melt flow rate (hereinafter referred to as MFR) is generally 0.01 to 50 g / 10 min, preferably 0.5 to 30 g / 10 min, and more preferably 0.5 to 10 g / min. MFR 0.01g
If it is less than / 10 minutes, the fluidity (moldability of the laminate due to inflation) is reduced, and if it exceeds 50 g / 10 minutes, the strength and the like are reduced.

High-pressure radical polymerization ethylene polymers include low-density polyethylene (LDPE) by high-pressure radical polymerization, ethylene / vinyl ester copolymer, copolymer of ethylene with α, β-unsaturated carboxylic acid or a derivative thereof. Polymers.

M of the above low density polyethylene (LDPE)
FR is 0.01 to 50 g / 10 min, preferably 0.0 to 50 g / 10 min.
5 to 30 g / min, more preferably 0.1 to 10 g / 1
The range is 0 minutes. Within this range, the melt tension is in an appropriate range, and the moldability is improved. Also,
When the MFR exceeds 20 g / 10 minutes, the strength of the laminate becomes insufficient. The density of LDPE is 0.91 to 0.91.
0.94 g / cm ³ , more preferably 0.912 to
It is in the range of 0.935 g / cm ³ . Within this range, the melt tension is in an appropriate range, and the moldability is improved. LDPE melt tension is 1.5 ~
25 g, preferably 3 to 20 g, more preferably 3 to
15 g. Also, the molecular weight distribution Mw / Mn of LDPE
Is from 3.0 to 12, preferably from 4.0 to 8.0.

The above-mentioned ethylene / vinyl ester copolymer refers to ethylene-based vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate produced by a high-pressure radical polymerization method. And a copolymer with a vinyl ester monomer such as vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate. Also, 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0
A copolymer consisting of 49.5% by weight is preferred. In particular,
The content of vinyl ester is in the range of 3 to 30% by weight, preferably 5 to 25% by weight. The MFR of the ethylene / vinyl ester copolymer is 0.01 to 50 g / 10 min, preferably 0.05 to 30 g / min, and more preferably 0.1 to 30 g / min.
The range is 1 to 10 g / 10 minutes.

Examples of the copolymer of ethylene and α, β-unsaturated carboxylic acid or a derivative thereof include ethylene
(Meth) acrylic acid or its alkyl ester copolymer is mentioned, and as these comonomers, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, methacrylic acid Propyl, isopropyl acrylate, isopropyl methacrylate, n-acrylate
Butyl, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate,
Stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate and the like can be mentioned. Of these, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl. In particular, the content of the (meth) acrylate is 3 to
It is in the range of 30% by weight, preferably 5 to 25% by weight.
The MFR of a copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof has a MFR of 0.01 to 50 g / 10 min, preferably 0.05 to 30 g / 10 min, and more preferably 0.1 to 10 g / min. 10 minutes.

The layer I is a layer mainly composed of a polyethylene resin. At least one kind of polyethylene, the same or different from the linear low-density polyethylene used for the layer III, or a high-pressure radical method polyethylene is used. Although it is used, high-density polyethylene or the like can be blended as long as curling does not occur.

The resin material (ii) forming the second layer is
Flexural modulus is 2500kgf / cm ^Two Must be at least
is there. The flexural modulus is preferably 3500 kgf / c
m^TwoAbove, more preferably 4500 kgf / cm^Two that's all
It is. The flexural modulus is 2500 kgf / cm^Two Less than
Means that the rigidity (waist) of the laminate decreases,
Automatic filling performance will be reduced. Where the resin material
The flexural modulus of (ii) is based on JIS K7203.
Measured.

The above flexural modulus is 2500 kgf / cm ^2.
As the resin material (ii) described above, a resin material containing a medium / high-density polyethylene and / or a polypropylene resin as a main component, and optionally containing another polyolefin resin may be mentioned. The medium density polyethylene and the high density polyethylene have a density of 0.1.
Various types can be used as long as they are 93 g / cm ³ or more. Specifically, a homopolymer composed of only ethylene, ethylene and another monomer (for example, α-olefin such as propylene, 1-butene, and 1-hexene)
Or a multi-component copolymer composed of ethylene and two or more monomers.

The density of the medium / high density polyethylene is 0.
If it is less than 93 g / cm ³ , the resulting laminate will have poor waist strength (rigidity), water vapor barrier properties, fragrance retention, moisture resistance, heat resistance, and the like. In addition, MF of medium and high density polyethylene
R (190 ° C.) is preferably 0.01 to 50 g / 10
Min, more preferably from 0.05 to 30 g / min, even more preferably from 0.1 to 10 g / min. MFR (19
(0 ° C.) is less than 0.01 g / 10 minutes, there is a problem in workability, and if it exceeds 50 g / 10 minutes, the strength of the laminate tends to decrease.

As the polypropylene resin, homopolypropylene, propylene / ethylene block copolymer,
Propylene-ethylene random copolymer, propylene
α-olefin block copolymers, propylene / α-olefin random copolymers, and the like. Further, the MFR (based on JIS K 6758) of the polypropylene resin is preferably in the range of 0.1 to 50 g / 10 min, more preferably 0.1 to 20 g / min. MFR 0.1g
If it is less than / 10 minutes, there is a problem in workability, and if it exceeds 50 g / 10 minutes, the strength of the laminate tends to decrease.

In the resin material (ii) forming the second layer,
The compounding ratio of the high-density polyethylene and / or polypropylene resin is 50 to 100% by weight, and preferably 70 to 100% by weight. If these proportions are less than 50% by weight, the rigidity (lumbar), water vapor barrier properties, and fragrance retention of the laminate are reduced.

The resin material (iii) mainly composed of linear low-density polyethylene forming the third layer has a density of 0.9.
It is mainly composed of linear low-density polyethylene having a density of 4 g / cm ³ or less, and other polyethylene-based resins are blended as required.

The linear low-density polyethylene is composed of ethylene and α
A copolymer having a density of 0.94 g / cm ³ or less, obtained by copolymerizing an olefin, and a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms; It is united. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, and 1-hexene.
Octene or the like is used. The structural unit derived from an α-olefin having 3 to 20 carbon atoms in LLDPE is:
It is 1 to 7 mol%, preferably 1 to 5 mol%, more preferably 2 to 3 mol%. When the constitutional unit derived from an α-olefin having 3 to 20 carbon atoms exceeds 7 mol%, the impact resistance, creep resistance, and heat seal strength decrease, and when it is less than 1 mol%, the transparency decreases. Can be seen.

The linear low-density polyethylene in the present invention is not particularly limited as long as it is as described above. preferable.

The (A) density of the linear low density polyethylene (A) in the present invention is 0.86 to 0.94 g / cm ³ ,
Preferably, it is in the range of 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 , rigidity (lumbar strength) and heat resistance may be reduced. If the density exceeds 0.94 g / cm ³ , the pinhole resistance, tear strength, impact resistance, and the like may be insufficient.

The (B) MFR of the linear low density polyethylene (A) in the present invention is from 0.01 to 50 g / 10 min, preferably from 0.05 to 30 g / 10 min, more preferably from 0.1 to 50 g / 10 min. 10 g / 10 min. MFR is 0.0
If it is less than 1 g / 10 minutes, the fluidity (moldability of the laminate) is reduced, and if it exceeds 50 g / 10 minutes, the strength is reduced.

The (c) molecular weight distribution (Mw / Mn) of the linear low density polyethylene (A) in the present invention is from 1.5 to 1.5.
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, moldability is poor, and if Mw / Mn exceeds 4.5, pinhole resistance, tear strength, impact resistance, and the like are poor. Here, the molecular weight distribution of the linear low-density polyethylene (Mw / M
n) is gel permeation chromatography (G
PC), the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined, and the ratio (Mw / Mn) is calculated.

The linear low-density polyethylene (A) in the present invention is obtained from, for example, an integrated elution curve of elution temperature-elution amount curve (TREF) by continuous heating elution fractionation method (TREF) as shown in FIG. The temperature T _{25 at which} 25% of the total elutes
The difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ the entire 75% is eluted When, and satisfies the following relationship (Equation 1). When the equation _{(1) T 75 -T 25 ≦ -670} × d + 644 T 75 -T 25 and density d do not satisfy the relation of the equation (1) becomes as low-temperature heat-sealing property is inferior.

The method of measuring TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) has been added so that the sample concentration becomes 0.05% by weight, and heated and dissolved at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, while flowing ODCB through this column at a constant flow rate, the column temperature was raised to 50 ° C.
The sample is sequentially eluted while heating at a constant rate of / 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 copolymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. According to the TREF analysis, a change in the elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, so that a relatively fine peak which cannot be detected by the fractionation method can be detected.

The (A) linear low-density polyethylene of the present invention further satisfies the requirements of (e) and (f) described later, (A1) a linear low-density polyethylene, or (g) and (g) It is preferably any one of (A2) linear low-density polyethylene satisfying the requirement of h).

In the present invention, (A1) the amount X of the ODCB-soluble component at 25 ° C. of the linear low-density polyethylene X
(Weight%), the density d and the MFR satisfy the relationship of the following (Equation 2) and (Equation 3). (Equation 2) When d−0.008 log MFR ≧ 0.93, X <2.0 (Equation 3) When d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008)
log MFR) ² +2.0, preferably X <1.0 d−0.008 log MFR <0.93, d <0.008 log MFR <0.93, X <7. 4 × 10 ³ × (0.9300−d + 0.008
log MFR) ² +2.0, more preferably X <0.5 d-0.008 log MFR ≧ 0.93, X <0.5 d−0.008 log MFR <0.93, X <5 0.6 × 10 ³ × (0.9300−d + 0.008
log MFR) ² +2.0.

Here, the amount X of the ODCB-soluble component at 25 ° C. is measured by the following method. Sample 0.5
g in 20 ml ODCB at 135 ° C. for 2 hours,
After completely dissolving the sample, cool it to 25 ° C. After leaving this solution at 25 ° C. overnight, the solution is filtered through a Teflon (registered trademark) filter to collect a filtrate. The filtrate, which is a sample solution, is measured for the absorption peak intensity near the wave number of 2,925 cm ^-1 of asymmetric stretching vibration of methylene using an infrared spectrometer, and the sample concentration is calculated based on a previously prepared calibration curve. From this value, the ODCB-soluble content at 25 ° C. is determined.

The ODCB-soluble component at 25 ° C. is a high branching degree component and a low molecular weight component contained in linear low-density polyethylene. This content is desirably small, because it causes blocking of the inner surface of the molded body.
The amount of ODCB solubles is affected by the α-olefin content and molecular weight of the entire copolymer, ie, density and MFR. Therefore, these indices density, MFR and OD
The fact that the amount of the CB-soluble component satisfies the above relationship indicates that the uneven distribution of the α-olefin contained in the whole copolymer is small.

The (A1) linear low-density polyethylene according to the present invention can be obtained by (f) continuous heating elution fractionation (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 (A2) linear low-density polyethylene according to the present invention has one peak in the elution temperature-elution amount curve obtained by (g) the continuous heating elution fractionation method (TREF), and the T
₇₅ -T ₂₅ and density d is one which satisfies the following relationship (Equation 4). When the equation _{(4) T 75 -T 25 ≧ -300} × d + 285 T 75 -T 25 and density d do not satisfy the relation of the equation (4) will heat seal strength and heat resistance are poor.

The (A2) linear low-density polyethylene of the present invention has (h) one or two melting point peaks, and the highest melting point T _ml and the density d are expressed by the following formula (5). Is satisfied. (Formula 5) _Tml ≧ 150 × d−17 If the melting point Tm1 and the density d do not satisfy the relationship of the above (Formula 5), the heat resistance will be poor.

Further, among the linear low-density polyethylenes (A2), linear low-density polyethylenes that further satisfy the following requirement (i) are preferable. (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 (2), the formability of the laminate and the like becomes good.

Here, as shown in FIG. 2, (A1) linear low-density polyethylene was subjected to a continuous heating elution fractionation method (TR).
The peak is substantially a specific linear low-density polyethylene (ethylene / α-olefin copolymer) having a plurality of peaks in the elution temperature-elution amount curve obtained by EF). Also,
(A2) As shown in FIG. 1, the linear low-density polyethylene has one TREF peak, but satisfies the above (Equation 4) and the like, and is an ethylene copolymer produced by a conventional typical metallocene catalyst. Is distinguished from On the other hand, FIG.
Is a linear low-density polyethylene having substantially one peak by a conventional typical metallocene-based catalyst (ethylene
α-olefin copolymer) continuous heating elution fractionation method (TR
3 shows an elution temperature-elution amount curve obtained by EF).

The linear low-density polyethylene (A) in the present invention is not particularly limited to a catalyst, a production method and the like as long as the above-mentioned parameters are satisfied. And Periodic Table No.
A linear ethylene (co) polymer obtained by (co) polymerizing ethylene and an α-olefin in the presence of a catalyst containing a Group IV transition metal compound is preferred. 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 (A) the linear low-density polyethylene 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 (where Me ¹ represents zirconium, titanium, or hafnium, and R ¹ and R ³ each represent a carbon number) 1 to
24 hydrocarbon groups, R ² is a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand,
A benzoylacetonate ligand or a derivative thereof, X ¹ represents a halogen atom, p, q and r each represent 0 ≦ p
≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4) a2: a compound represented by the general formula Me ² R ⁴ _m (OR ⁵ ) _n X ² _zmn (In the formula, Me ² is an element in Groups I to III of the periodic table, R ⁴
And R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, X
² represents a halogen atom or a hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a Group III element of the periodic table), z represents a valence of Me ² , and m and n represent A is an integer satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z. A3: Organic cyclic compound having a conjugated double bond a4: Al—O—Al bond Containing modified organoaluminum 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, and the types of these transition metals are limited. It is not limited to this, and a plurality of them can be used, but it is particularly preferable that the copolymer contains zirconium 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, and more preferably 1 to 8 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group;
Alkenyl groups such as vinyl group and allyl group; phenyl group,
Aryl groups such as tolyl, xylyl, mesityl, indenyl and naphthyl; benzyl, trityl,
And aralkyl groups such as phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofuyl group. These may have branches. R ² is 2,
It shows a 4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine. p and q are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q
An integer satisfying the range of + r ≦ 4 is an integer.

Examples of the compounds represented by the general formula of the above-mentioned catalyst component a1 include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodiconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrabutoxy titanium , Tetrabutoxy hafnium, etc., and especially Z such as tetrapropoxy zirconium, 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 ² R ⁴ _m (O
R ⁵ ) _n X ^{2 In} the formula of the compound represented by _zmn , Me ² represents a group I-III element of the periodic table, and lithium, sodium,
Potassium, magnesium, calcium, zinc, boron,
Aluminum and the like. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 1 to 8, specifically alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, Aryl groups such as a xylyl group, a mesityl group, 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. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, 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 2 or more and having a total carbon number of 4 to 24, preferably 4 to 12; wherein the cyclic hydrocarbon compound is partially a hydrocarbon residue of 1 to 6 (typically, carbon A cyclic hydrocarbon compound substituted with an alkyl group or an aralkyl group of the formulas 1 to 12; two or more, preferably 2 to 4, more preferably 2 to 2, conjugated double bonds.
One or more rings having three rings and a total carbon number of 4
An organosilicon compound having a cyclic hydrocarbon group of from 24 to 24, preferably 4 to 12; said cyclic hydrocarbon group being partially substituted by 1 to 6 hydrocarbon residues or 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-dimethylindene, butylcycloheptadiene, 1-methyl-3-propylcyclopentadiene and indene, 1-methyl-3-butylcyclopentadiene and indene, propylcyclopentadiene, 1-
Methyl-3-ethylcyclopentadiene, 1,2,4-
Trimethylcyclopentadiene cycloheptatriene,
C5-C24 cyclopolyene or substituted cyclopolyene such as methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadiene Examples include enylsilane, monoindenylsilane, bisindenylsilane, trisindenylsilane, and methylcyclopentadientinemethylsilane.

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

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

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

The above catalyst may be used by mixing and contacting a1 to a4, but it is preferable to use the catalyst by supporting it on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or the particulate polymer carrier (a5) include a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate 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 method for producing (A) the linear low-density polyethylene according to 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, wherein substantially no solvent is present. In a state where oxygen, water, etc. are cut off, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; It is produced in the presence or absence of an inert hydrocarbon solvent exemplified in (1). 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. As a particularly preferred production method, a method described in JP-A-5-132518 is exemplified.

The (A) linear low-density polyethylene of the present invention is produced using a catalyst which does not contain halogen such as chlorine in the above-mentioned catalyst components, so that the halogen concentration is at most 10 ppm or less, preferably at most 10 ppm. Is 5 ppm
Hereinafter, it is more preferably substantially free of (ND: 2p
pm or less). By using such a halogen-free linear low-density polyethylene such as chlorine, there is no need to use an acid neutralizer as in the past, and the chemical stability and hygiene are excellent, and especially, food packaging materials, etc. The laminated body suitably utilized in the field of (1) can be provided.

The compounding ratio of the linear low-density polyethylene in the resin material (iii) forming the layer III is 50 to 100% by weight, preferably 70 to 100% by weight. When the ratio of the linear low-density polyethylene is less than 50% by weight, the heat resistance, puncture resistance, low-temperature heat sealability, heat seal strength, and mechanical strength of the laminate are reduced.

Other polyethylene-based polymers that can be blended with the resin material (iii) include high-, medium-, low-pressure methods using a Ziegler-type catalyst and the like, and other known methods such as ethylene homopolymers, ethylene and C3-C3. And an ethylene-based (co) polymer obtained by a high-pressure radical polymerization method.

The high, medium and medium using the Ziegler type catalyst and the like
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 density polyethylene, density 0.91-0.94g
/ Cm ³ linear low density polyethylene (LLDPE), density 0.86-0.91 g / cm ³ very low density polyethylene (VLDPE), density 0.86-0.91 g / c
m ³ of ethylene-propylene copolymer rubber, ethylene-
Ethylene / α-olefin copolymer rubber such as propylene / diene copolymer rubber can be mentioned.

The LLDPE using the Ziegler type catalyst is defined as ethylene • α-density having a density of 0.91 to 0.94 g / cm ³ , preferably 0.91 to 0.93 g / cm ^3.
An olefin copolymer, wherein the α-olefin has 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and specifically includes propylene, 1-butene, 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
It is an ethylene / α-olefin copolymer in the range of g / cm ³ and is a polyethylene having properties intermediate between LLDPE and ethylene / α-olefin copolymer rubber (EPR, EPDM).

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.

In the present invention, the resin material (i) and the resin material (iii) are made of the same or different resin materials, and the density is not particularly limited, but the resin material (i) and the resin material ( When iii) and the resin material (ii) are the same type of resin material, it is preferable that their densities have a relationship of resin material (i) and resin material (iii) <resin material (ii). . The resin material (i) and the resin material (ii) may be blended with known additives, fillers and the like. As the resin material (iii), use is made of (A) a linear low-density polyethylene produced using a halogen-free catalyst, and no additives such as an antioxidant and a neutralizing agent are added to the resin material (iii). Thereby, a clean molded body can be provided.

In the present invention, an antioxidant, an anti-blocking agent, a lubricant,
No known additives such as an antistatic agent, an antifogging agent, an ultraviolet absorber, an organic or inorganic pigment, a nucleating agent, and a cross-linking agent are added, or additives are added to the resin composition. Even so, it is desirable that the compounded additive is an additive that does not substantially migrate to the contacted object such as the contents. In the present invention, an additive that elutes or oozes out to the outside, for example, when the content is a liquid, an additive that is eluted in the liquid, an additive that transfers odor, or Additives that are unevenly distributed on the film surface with time are not contained in the resin material (iii), so that the odor is reduced, the sanitary and clean laminate is reduced,
A container can be provided.

In the present invention, the additive which does not substantially migrate to the contacted object is a filler such as an organic or inorganic filler, which does not degrade the contacted object and has the properties of the resin sheet of the present invention. Is an additive that can be added within a range that does not essentially inhibit the As inorganic fillers, calcium carbonate, talc, silica, clay, carion, alumina,
Aluminum hydroxide, magnesia, magnesium hydroxide, calcium sulfate, calcium sulfite, barium sulfate, aluminum silicate, calcium silicate, sodium silicate, potassium silicate, magnesium carbonate, barium carbonate,
Examples include calcium oxide, titanium oxide, zinc oxide, mica, glass flake, zeolite, diatomaceous earth, perlite, permiculite, shirasu balloon, glass microsphere, fly ash, and glass beads.
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. These fillers can be blended for the purpose of improving the rigidity of the laminate.

The laminate of the present invention has a density of 0.94 g / c
a layer I made of a resin material (i) containing a linear low-density polyethylene or a high-pressure radical polymerization-based ethylene polymer having a m ³ or less, and a flexural modulus of 2500 kgf /
a ^second layer made of a polyolefin resin material (ii) having a density of 0.94 g / cm ³ or less, and a ^third layer made of a resin material (iii) containing linear low-density polyethylene having a density of 0.94 g / cm ³ or less. It has.

When the laminate of the present invention is formed into a container, it is important to form a layer corresponding to the innermost layer of the container with the third layer. In particular, the characteristics of each layer (the first layer: curl prevention, the second layer: rigidity, water vapor barrier properties, fragrance retention,
Layer: low-temperature heat-sealing property, heat-sealing strength, piercing strength, hygiene) and, when used as a standing pouch, efficiently exhibit independence. It is necessary that the layer II is provided. Other layers may be interposed between the II layer and the I layer or between the II layer and the III layer. Other layers include an adhesive resin layer for more firmly bonding the layer II with the layers I and III on both sides thereof.

In the laminate of the present invention, the third layers are heat-sealed at a heat-sealing temperature of 120 ° C. and a heat-sealing pressure of 1 kg / cm.
^2. It is desirable that the heat sealing strength (hereinafter referred to as 120 ° C. heat sealing strength) when heat sealing is performed under the condition of a heat sealing time of 1 second is in the range of 2.5 to 6 kg / 15 mm.

Here, the heat sealing strength at 120 ° C. is specifically measured as follows. Using a heat seal tester (seal bar width 1 mm), the third layers of the laminate were sealed at a seal temperature of 120 ° C. and a seal pressure of 1 kg / c.
and one second heat sealed m ^{2, and} the room temperature 23 ° C. and a humidity of 50
% For 24 hours, cut out the heat-sealed part into a strip with a width of 15 mm, and 300 mm / mi using a tensile tester.
At n, the heat-sealed portion is peeled off, and the maximum load is measured.

The laminate of the present invention has a heat seal strength of 3 k when the third layers are heat-sealed under the conditions of a heat seal pressure of 1 kg / cm ² and a heat seal time of 1 second.
g / 15 mm (hereinafter, 3
kg load heat sealing temperature) is 85-125 ° C
Is desirably within the range. When the heat-sealing temperature under a 3 kg load is less than 85 ° C., the heat resistance is poor, and when it exceeds 125 ° C., the high-speed filling property is poor.

Here, the 3 kg load heat sealing temperature is:
Specifically, it is measured as follows. Using a heat seal tester (seal bar width 1 mm), the third
The layers were heat-sealed at a heat-sealing temperature of 80 ° C. and a heat-sealing pressure of 1 kg / cm ² for 1 second, and the room temperature was 23 ° C.
After adjusting the condition for 24 hours at a humidity of 50%, the heat-sealed portion was cut out into a strip having a width of 15 mm, and the heat-sealed portion was cut out with a tensile tester at 30%.
The heat-sealed portion is peeled at 0 mm / min, and the maximum load (heat-sealing strength) is measured. The above measurement was repeated while increasing the heat sealing temperature by 5 ° C., and 8
5,90,95,100,105,110,115,1
The heat seal strength at 20, 125 and 130 ° C. is measured. A heat seal temperature-heat seal strength curve was created by plotting the heat seal strength against the heat seal temperature, and the heat seal strength was 3 kg from this curve.
Read the heat seal temperature at / 15 mm.

The thickness of the laminate of the present invention varies depending on the purpose and application, but is generally in the range of 10 μm to 0.5 mm, preferably 30 μm to 0.3 mm, more preferably 50 μm to 0.3 mm. Preferably, it is selected in the range of 2 mm. The thickness of each of the first, second and third layers of the laminate of the present invention is 3 μm to 0.4 mm, preferably 10 μm to 0.2 mm / 20, respectively.
It is preferable to select from the range of μm to 0.2 mm / 10 μm to 02 mm. In addition, the thickness ratio of each layer (the first layer / the first layer)
(II layer / III layer) is preferably 1 to 10/1 to 20/1 to 20.

The laminate of the present invention may have a barrier layer (IV) adhered to the first layer. By providing the barrier layer (IV), the water vapor barrier property and the fragrance retention property are further improved. Further, the barrier layer (IV) is used for reinforcing the laminate, a protective layer,
It can also serve as a printing layer and a light-shielding layer, and also as a heat-resistant layer for maintaining the shape of the laminate during heat sealing.

As the barrier layer (IV), for example, a plastic film or sheet of polypropylene resin, polyamide resin, polyester resin, saponified ethylene-vinyl acetate copolymer, polyvinylidene chloride, polycarbonate, etc. (stretched thereof) Objects, printed matter, and secondary processed films and sheets of deposited materials such as metals), aluminum, iron, copper, and metal foils such as alloys containing these as main components. Alternatively, a metal plate, cellophane, paper, woven fabric, nonwoven fabric, or the like may be used in some cases without departing from the spirit of the present invention.

Any one of the I-th, II-th, and III-th layers is formed of a resin material (i), a resin material (ii), and a resin material (iii) obtained by recycling a laminate. May be formed of a blend resin. Further, the laminate of the present invention may further include a recycled resin layer (V) made of the blend resin. Here, the blended resin obtained by recycling the laminate is a defective resin of the laminate, a recovered pouch made of the laminate, a mixed resin obtained by grinding burrs and the like generated in a finishing stage after processing into a pouch or the like. That is. Thus, the laminate of the present invention can use a recycled blended resin, and has good recyclability.

Examples of the above laminate include I / II / III,
I / IV / II / III, IV / I / II / III, I / V / II / III
, I / V / II / V / III, I / adhesive / V / adhesive / I
Embodiments such as I / III are mentioned. More specifically, LD
/ HD / LL, LD / HD + LL / LL, LD + LL /
HD / LL, LD / HD / LL + LD, LD / HD + L
L / LL + LD, LD / RC / HD / LL, RC / LD
/ HD / LL, LD / RC / LL, LD / RC + HD /
LL, LD / RC + HD / HD / LL, LD / adhesive /
Barrier layer (EVOH, PA, PEs, OPP, etc.) / Adhesive / HD / LL etc. (here, HD: high-density polyethylene, LD: high-pressure radical polymerization low-density polyethylene, LL: linear low-density polyethylene) , RC: recycled blend resin, EVOH: saponified ethylene-vinyl acetate copolymer, PA: polyamide resin, P
Es: polyester resin, OPP: oriented polypropylene resin, adhesive: acid-modified polyethylene resin).

The laminate of the present invention has no curl and is excellent in rigidity (lumpy), so that it can be suitably used for a standing pouch requiring self-sustainability. In addition, since the laminate of the present invention can exhibit sufficient heat sealing strength even at a relatively low heat sealing temperature, a pouch or the like can be manufactured by low-temperature heat sealing. The generation of odor and the like is small, and the quality of the contents is not deteriorated.

The laminate of the present invention can be produced by various methods, but is preferably produced by molding the I, II and III layers by coextrusion. . As a molding method, for example, it can be manufactured with high productivity by a multilayer inflation molding method, a multilayer cast molding method, or the like. Among them, a multilayer inflation molding method is suitably used in terms of economy, moldability, and the like.

The production of a sheet by the multilayer blown molding method can be performed by a conventional air-cooled blown film production apparatus.
Extruded through a circular die from an extruder at a temperature of 250 ° C., contacted with air blown from an air-cooled air ring, quenched, solidified, and taken out with a pinch roll.
It is performed by winding it around a frame.

In addition to the air-cooled inflation molding, it can be produced by a water-cooled inflation molding, a T-die method or the like, and a sheet having excellent transparency, low-temperature impact resistance and the like can be obtained.

Further, a hollow tube obtained by multilayer inflation molding of at least the resin material (i), the resin material (ii), and the resin material (iii) is sandwiched and crushed to form a laminate of five or more layers. Is also possible. As a method of obtaining such a laminate, a method of crushing a hollow tube formed by extruding each resin material through a circular die with a pinch roll at a temperature higher than the melting point of the resin material of the inner layer, A hollow tube formed by extruding each resin material through a circular die,
A method of contacting with air blown from an air-cooled air ring to cool and solidify, and then squeezing it with a heated pinch roll, or the like is used. According to such a manufacturing method, an inexpensive laminate can be obtained efficiently and economically.

By manufacturing the laminate by the multilayer inflation molding method as described above, the resin is uniformly crystallized due to slow cooling by air cooling without unevenness unlike the laminate obtained by the T-die method, and the strength is reduced. It becomes a strong laminate,
Additive-free molding can be performed from where low-temperature molding is possible, and a laminate that does not adversely affect the contacted object is obtained.
The blow-up ratio (BUR) can be adjusted and the quality can be controlled. Compared with the T-die method, there is no ear loss, high productivity and excellent economic efficiency. The thickness of the sheet can be formed at a time, and the thickness can be made uniform.

The pouch of the present invention comprises the laminate of the present invention
The bag was heat-sealed so that layer III was on the inside. Examples of the type of pouch include a self-standing standing pouch, a retort pouch for a retort food having a barrier layer made of aluminum foil, a pouch with a spout for drinking and drinking, and more specifically, a flexible spout pouch, a dual chamber pouch, Dispenser pouches and the like. Also, as the shape of the pouch,
Gazette bags, four-sided seal bags, three-sided seal bags stuck on the palms,
Bags in which the upper and lower portions of a cylindrical film are sealed by an inflation method are exemplified.

As the heat sealing method, a known method can be used, and examples thereof include an external heating method such as a heating bar, a heating knife, a heating wire and an impulse seal, and an internal heating method such as an ultrasonic seal and a dielectric heating seal. Can be

The pouch of the present invention, in particular, a standing pouch, is excellent in rigidity (waist) of the laminated body of the present invention, so that it is very excellent in independence, and can be reduced in thickness and weight. In addition, the pouch of the present invention can be produced by low-temperature heat sealing because the laminate of the present invention can exhibit sufficient heat sealing strength even at a relatively low heat sealing temperature, and the generation of odor and the like can be prevented. It does not deteriorate the quality of the contents.

Such pouches are used as food packaging materials such as edible oils, seasonings, dried products, processed foods, etc .; liquid detergents, shampoos,
It can be widely used as daily necessities packaging materials such as rinses; medical packaging materials such as infusion bags.

[0089]

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. [Measurement of T _ml by DSC] A sheet having a thickness of 0.2 mm was formed by hot pressing, and a sample of about 5 mg was punched out of the sheet. This sample was kept at 230 ° C. for 10 minutes and then cooled to 0 ° C. at 2 ° C./min. Then, again at 10 ° C./min.
C., and the temperature at the top of the highest temperature peak that appeared was defined as the highest peak temperature Tml. [TREF] With the column maintained at 140 ° C., a sample was injected into the column, the temperature was lowered to 25 ° C. at 0.1 ° C./min, and the polymer was deposited on glass beads. The concentration of the polymer eluted at each temperature after the temperature was raised 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 cmφ × 12 cm
L (filled with glass beads), sample concentration: 0.05% by weight)

[Melt tension (MT)] The stress when the melted polymer was stretched at a constant speed was determined by measuring with a strain gauge. The measurement sample was granulated and pelletized, and was manufactured by Toyo Seiki Seisakusho M
It measured using the T measuring device. The orifice used has a hole diameter of 2.09 mmφ and a length of 8 mm. The measurement conditions are a resin temperature of 190 ° C., a cylinder descending speed of 20 mm / min, and a winding speed of 15 m / min. [Chlorine concentration] It was measured by a fluorescent X-ray method. When chlorine of 10 ppm or more was detected, this was taken as an analysis value.
When it was less than 10 ppm, it was measured with a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd., and when it was 2 ppm or less, it was regarded as ND and was not substantially contained.

<Evaluation of Laminated Sheet> [Heat Seal Strength] Heat seal tester manufactured by Tester Sangyo Co., Ltd. (seal bar width 1 mm, seal pressure 1 kg / c)
m ² ), the third layers of the laminate are sealed with each other at a heat sealing temperature of 120 ° C. for 1 second, and the state is adjusted at a room temperature of 23 ° C. and a humidity of 50% for 24 hours. 300mm / min with a tensile tester
And the maximum load was measured. [3 kg load heat sealing temperature] Using a heat seal tester manufactured by Tester Sangyo Co., Ltd. (seal bar width: 1 mm, sealing pressure: 1 kg / cm ² ), the third layers of the laminate were separated from each other by:
Heat seal temperature 80 ° C, heat seal pressure 1kg / c
and one second heat sealed m ^{2, and} the room temperature 23 ° C. and a humidity of 50
% For 24 hours, cut out the heat-sealed part into a strip with a width of 15 mm, and 300 mm / mi using a tensile tester.
The heat seal portion was peeled off at n, and the maximum load (heat seal strength) was measured. The above measurement was repeated while increasing the heat seal temperature by 5 ° C., and 85, 90, 95, 100, 105, 11
The heat seal strength at 0, 115, 120, 125 and 130 ° C. was measured. A heat seal temperature-heat seal strength curve was created by plotting the heat seal strength against the heat seal temperature, and the heat seal temperature at a heat seal strength of 3 kg / 15 mm was read from this curve.

[Pinhole Resistance] A test piece having a width of 200 mm and a length of 300 mm was cut from the laminate in the flow direction during molding. The test piece was attached to a gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd., and after loading 3,000 strokes at room temperature, the number of pinholes in the test piece was measured. The same test was repeated three times, and the average value of the number of pinholes was obtained. [Water vapor transmission rate] Based on JIS K7129. [Haze] Based on ASTM D1003. [Tensile modulus] MD (extrusion direction) was measured in accordance with ASTM D882. [Tensile impact strength] According to ASTM D1822, MD
(Extrusion direction) was measured. [Curlability] The degree of curl in the TD direction of the laminate having a width of 300 mm was visually measured. ：: No curl Δ: Slight curl ×: Significant curl

<Evaluation of pouch> [Odor and hygiene]
After storage in an oven at 72 ° C. for 72 hours, the mixture was cooled to room temperature, 20 ml of the content was transferred to a porcelain container, and a sensory test was carried out for the presence or absence of suspended matter, odor and taste. ◎: Good ○: Relatively good △: Somewhat bad ×: Bad

[Heat Resistance] A container filled with 500 ml of distilled water was subjected to high-pressure steam sterilization at 121 ° C. for 20 minutes, and deformation was visually observed. ：: Not deformed △: Slightly deformed X: Notably deformed [Drop test] After adjusting the condition of a container filled with 500 ml of distilled water in a 5 ° C atmosphere for 24 hours, 10 containers were 1.2 m in height. And the number of containers that broke was checked. ○: No bag breakage △: 1 or 2 bag breaks ×: 3 or more bag breaks [Independence] A cylinder having a diameter of 200 mmφ and a height of 300 mm was produced and judged from the deflection of the upper opening when the cylinder was made independent. . ○: No deflection Δ: Slight deflection ×: Severe deflection

Various components used in Examples and Comparative Examples are as follows. [Linear low-density polyethylene] 1) (A1) A specific linear low-density polyethylene 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 as to maintain a predetermined molar ratio, and the
A tylene copolymer (LLDPE-1) was obtained. Also, LL
The same ethylene copolymer as DPE-1 and an additive
Was not used as LLDPE-3. These physical properties
Are shown in Table 1.

2) (A2) The specific linear low-density polyethylene was polymerized by the following method. Using the continuous fluidized-bed gas-phase polymerization apparatus, a polymerization temperature of 75
The copolymerization of ethylene and 1-hexene was performed at a temperature of 20 ° C. and a total pressure of 20 kgf / cm ² G. Continuously supplying the solid catalyst,
Polymerization is carried out by supplying ethylene, 1-hexene and hydrogen so as to maintain a predetermined molar ratio, and an ethylene copolymer (LL)
DPE-2) was obtained. The physical properties are shown in the table.

3) Ethylene-hexene-1 copolymer (M-LLDPE) using a general metallocene catalyst Purified toluene was placed in a pressurized reactor equipped with a stirrer purged with nitrogen, and then 1-hexene was added. Further screws (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 (M-LLDPE). The physical properties are shown in Table 1.

4) Physical properties of linear low-density polyethylene (Z-LLDPE) using a commercially available Ziegler-type catalyst are shown in Table 1.

[0101]

[Table 1]

[Polyethylene resin having a density of 0.94 g / cm ³ or less] High-pressure low-density polyethylene: HP-LDPE MFR = 2.0 g / 10 min, density = 0.923 g /
cm ³ [polyolefin resin having a flexural modulus of 2500 kgf / cm ² or more] (1) High-density polyethylene ethylene / 1-butene copolymer (HDPE: MFR =
1.5 g / 10 min, density = 0.951 g / cm ³ , flexural modulus = 11,000) (2) Ethylene / 1-butene copolymer (MDPE: MF)
R = 1.0 g / 10 min, density = 0.942 g / cm ³ ,
(3) Ethylene / propylene copolymer (PP: ethylene content = 3% by weight, flexural modulus = 12,500)

Examples 1-8, Comparative Examples 1-4 Antioxidants (Irganox 1076 = 0.1% by weight, Irgafos 168 = 0.1% by weight) and calcium stearate (neutralizing agent = 0.1%) (% By weight) and the three-layer inflation molding machine (40 mmφ) manufactured by Tommy Machine Industry Co., Ltd.
Using three extruders, molding was performed under the conditions of a molding lip gap of 3 mm and a molding temperature of 200 ° C. to produce a laminate having a width of 300 mm and a layer thickness configuration shown in Tables 2 to 4. Then, O-nylon (thickness: 15 μm, manufactured by Unitika Ltd.) was bonded by a dry lamination method using an adhesive (anchor coating agent: Toyo Morton TM-329).

Further, the third layers of the laminate were heated at a heat-sealing temperature of +3 kg + 5 ° C. and a pressure of 1 kg / cm.
^2. Heat-sealing was performed for 1 second to produce a standing pouch having a content of 500 ml, and the laminate and the pouch were evaluated. The results are shown in Tables 2 to 4.

[Embodiment 9] HDPE of layer II of Embodiment 1
Was replaced with a polypropylene resin (PP) to produce a laminate and a pouch in the same manner as in Example 1, and the results of the evaluation are shown in Table 3. [Example 10] In the same manner as in Example 1, the HDPE of the second layer in Example 1 was replaced with MDPE, and the recycled resin (RC) obtained by pulverizing the laminate manufactured in Example 1 was used as the I layer, as in Example 1. And pouches were produced, and the results of the evaluation are shown in Table 3. [Embodiment 11] The HDPE of the second layer of Embodiment 1 was replaced with MDPE
And a pouch was produced in the same manner as in Example 1 except that the LLDPE of the third layer was replaced with LLDPE-3 containing no antioxidant. The evaluation results are shown in Table 3.

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

As is evident from the results in Tables 2 and 3, the laminates of Examples were excellent in curling properties, heat sealing properties, pinhole resistance, water vapor barrier properties, transparency and mechanical strength. I understand. Further, the container of the embodiment is
It had sufficient heat resistance and drop strength. In particular, LLDPE free of halogen and containing no additives
The pouch using -3 as the inner layer (the third layer) had less odor and was excellent in hygiene.

On the other hand, as is clear from the results in Table 4, the laminate and pouch of Comparative Example 1 had a density of 0.9 in the third layer.
Since a linear low-density polyethylene of 4 g / cm ³ or less was not used, heat seal strength, pinhole resistance, tensile impact strength, and drop strength were poor. In addition, curling occurred slightly due to high density. Since the laminate and the pouch of Comparative Example 2 used HP-LDPE without using linear low-density polyethylene having a density of 0.94 g / cm ³ or less for the ^third layer, heat seal strength, pinhole resistance, and tensile impact were used. The strength and the drop strength were poor, and the odor was intense and the hygiene was poor. The laminate and the pouch of Comparative Example 3 also used HP-LDPE instead of linear low-density polyethylene having a density of 0.94 g / cm ³ or less for the ^third layer, so that heat seal strength, pinhole resistance, and tensile impact were used. The strength and the drop strength were poor, and the odor was intense and the hygiene was poor. Also,
Due to the high density, curling was remarkable. Since the laminate and the pouch of Comparative Example 4 used LDPE for the second layer, they were inferior in heat resistance, drop strength, and independence.

[0111]

As described above, the laminate of the present invention is made of a resin material containing a linear low-density polyethylene or a high-pressure radical-process ethylene-based polymer having a density of 0.94 g / cm ³ or less. a layer I made of i), a layer II made of a polyolefin resin material (ii) having a flexural modulus of 2500 kgf / cm ² or more, and a density of 0.94 g
Having a third layer made of a resin material (iii) whose main component is a linear low-density polyethylene of not more than / cm ³ , wherein a second layer is provided between the first and third layers. Since it is a body, it is excellent in curl resistance, rigidity, low-temperature heat sealability, water vapor barrier property, fragrance retention, hygiene, heat resistance, and has high heat seal strength and piercing strength.

If the heat sealing temperature at which the heat sealing strength of the third layers is 3 kg / 15 mm is 85-125 ° C.
Heat resistance and high-speed filling properties are further improved. Further, the thickness of the laminate is 10 μm to 0.5 mm, and the first layer and the second layer
Layer and layer III each have a thickness of 3 μm to 0.4 mm
Within this range, the laminate will be easy to use and exhibit the properties of each layer sufficiently. Further, if the laminate of the present invention further has a barrier layer (IV),
The fragrance retention is further improved. Further, any one of the I-th layer, the II-th layer and the III-th layer is a resin blend of the resin material (i), the resin material (ii) and the resin material (iii) obtained by recycling the laminate. A recycled resin layer (V) formed or made of the blend resin
However, if it is further provided, it is possible to use a recycled blended resin, and since it is composed of the same type of resin material, the recyclability is improved.

If the linear low-density polyethylene is (A) a linear low-density polyethylene satisfying the following requirements (a) to (d), heat resistance, low-temperature heat sealability, The mechanical strength, rigidity, moldability and the like are further improved. Further, the (A) linear low-density polyethylene further satisfies the requirements (e) and (f) described above (A).
1) If it is a linear low-density polyethylene, the heat resistance, hygiene, and rigidity of a laminated body will further improve. Further, the linear low-density polyethylene further comprises the above (g) and (h)
If (A2) a linear low-density polyethylene that satisfies the requirement of (A2), the heat resistance and heat seal strength of the laminate are further improved. Further, the (A2) linear low-density polyethylene is:
Further, when the above requirement (i) is satisfied, the moldability of the laminate is further improved.

Further, the linear low-density polyethylene, an organic cyclic compound having at least a conjugated double bond, and
If it is a linear ethylene copolymer obtained by copolymerizing ethylene and α-olefin in the presence of a catalyst containing a Group IV transition metal compound, the mechanical properties of the laminate, heat sealing properties, heat blocking Properties and heat resistance are further improved.
Further, if the additive blended in the resin material (iii) is an additive that does not substantially migrate to the contacted object, or if the additive is not blended in the resin material (iii), the odor is small, A laminate having hygiene properties can be obtained. Further, when the halogen concentration of the resin material (iii) is 10p
When it is at most pm, a laminate having excellent chemical stability and hygiene properties and particularly suitably used in the field of food packaging materials and the like can be provided.

Further, since the pouch of the present invention is formed by molding the laminate of the present invention into a bag shape with the third layer inside, it has curl resistance, rigidity, low-temperature heat sealability, water vapor barrier, and the like. Excellent heat resistance, fragrance retention, hygiene, and heat resistance, and has high heat seal strength and piercing strength. In particular, when the shape of the standing pouch is used, the self-sustainability is excellent.

[Brief description of the drawings]

FIG. 1 is a graph showing an elution temperature-elution amount curve of the linear low density polyethylene (A) or (A2) according to the present invention.

FIG. 2 is a graph showing an elution temperature-elution amount curve of (A1) linear low density polyethylene (ethylene copolymer) in the present invention.

FIG. 3 is a graph showing an elution temperature-elution amount curve of linear low-density polyethylene (ethylene copolymer) with a metallocene catalyst.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 3E064 AA05 AA08 AA11 AB23 BA01 BA07 BA09 BA16 BA17 BA18 BA27 BA28 BA29 BA30 BA36 BA38 BA54 BA60 BB03 BC01 BC07 BC08 BC18 BC20 EA07 EA17 EA23 FA04 FA05 HN05 HN65 3E086 AD01 BA04 BB BB51 CA01 CA35 DA08 4F100 AK03B AK03D AK05B AK05D AK06A AK06E AK07B AK07D AK48G AK63A AK63C AK63E AK63K AL05B AL05D BA03 BA05 BA07 BA10A BA10C BA10E BA15 BA25 CA06 CA24 CB00 DA01 GB16 GB23 JA04A JA04C JA04E JA06A JA06C JA06E JA07A JA07C JA07E JA13A JA13B JA13C JA13D JA13E JA20A JA20C JA20E JB08A JB08C JB08E JD01A JD01E JD04 JJ03 JK01 JK04B JK04D JK06 JK07B JK07D JK14 JL00 JL04 JL12 JL16 JN01 YY00A YY00B YY00C YY00D YY00E

Claims (14)

[Claims] 1. A resinous material (i) comprising a linear low-density polyethylene having a density of 0.94 g / cm ³ or less or a high-pressure radical polymerization ethylene-based polymer as a main component.
Layer, a second layer made of a polyolefin resin material (ii) having a flexural modulus of 2500 kgf / cm ² or more, provided between the first and third layers, and a density of 0.94.
g / cm ³ or less of at least 3 of the third layer made of the resin material (iii) mainly containing linear low-density polyethylene.
A laminate comprising a layer. 2. The flexural modulus is 2500 kgf / cm.
^2. The laminate according to claim 1, wherein the polyolefin resin material (ii) having a density of ² or more contains a medium / high density polyethylene and / or polypropylene resin having a density of 0.93 g / cm ³ or more as a main component. . 3. The heat sealing pressure of the third layers is 1
Heat sealing strength is 3 kg / 15 mm when heat sealing under the conditions of kg / cm ² and heat sealing time of 1 second.
3. The laminate according to claim 1, wherein the heat sealing temperature is in the range of 85 to 125 ° C. 4. 4. The thickness of the laminate is 10 μm to 0.5 mm, and the thickness of each of the I, II and III layers is in the range of 3 μm to 0.4 mm. The laminate according to any one of claims 1 to 3. 5. The laminate according to claim 1, further comprising a barrier layer (IV) bonded to the first layer. 6. A resin material (i), a resin material (ii) and a resin material (iii) obtained by recycling any one of the first layer, the second layer and the third layer. The laminate according to any one of claims 1 to 5, wherein a recycled resin layer (V) formed of a blend resin or made of the blend resin is further provided. 7. The linear low density polyethylene according to claim 1, wherein the linear low density polyethylene satisfies the following requirements (a) to (d): (A) a linear low density polyethylene. The laminate according to item 1. (A) a density of 0.86 to 0.94 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 relationship of the following (formula 1) (formula 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644 8. The (A) linear low-density polyethylene,
Further, the following requirements (e) and (f) are satisfied (A
1) The laminate according to claim 7, wherein the laminate is a linear low-density polyethylene. (E) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by weight), the density d and the melt flow rate (MFR) satisfy the relationship of the following (Formula 2) and (Formula 3) (Formula 2) d−0.008 log MFR ≧ 0.93 X <2.0 (Equation 3) d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008)
(logMFR) ² +2.0 (f) Presence of multiple peaks in elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) 9. The (A) linear low-density polyethylene,
Further, the following requirements (g) and (h) are satisfied (A
2) The laminate according to claim 7, wherein the laminate is a linear low density polyethylene. (G) elution temperature by continuous Atsushi Nobori elution fractionation (TREF) - it is one peak of elution curve and the T ₇₅ -T ₂₅ and density d is, satisfy the relation of the following (Equation 4) ( (H) T ₇₅ −T ₂₅ ≧ −300 × d + 285 (h) One or two melting point peaks, and the highest melting point T _ml and density d satisfy the relationship of the following (Formula 5) ( Formula 5) T _ml ≧ 150 × d−17 10. The laminate according to claim 9, wherein the (A2) linear low-density polyethylene further satisfies the following requirement (i). (I) Melt tension (MT) and melt flow rate (MFR) satisfy the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR + 0.3 11. The linear low-density polyethylene comprises an organic cyclic compound having at least a conjugated double bond and a periodic table.
The laminate according to any one of claims 1 to 10, wherein the laminate is produced in the presence of a catalyst containing a Group IV transition metal compound. 12. The additive compounded in the resin material (iii) is an additive which does not substantially migrate to the contacted object, or the additive is not compounded in the resin material (iii). The laminate according to any one of claims 1 to 11, wherein 13. The laminate according to claim 1, wherein the halogen concentration of the resin material (iii) is 10 ppm or less. 14. A pouch, wherein the laminate according to any one of claims 1 to 13 is formed into a bag shape with the third layer inside.