JP2001225428A - Laminated sheet and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet having transparency, flexibility, heat resistance, pinhole resistance, heat sealability, ESCR resistance, steam impermeability and aroma retention and a method of manufacturing the same. SOLUTION: The laminated sheet has a first layer comprising (i) a resin material based on high density polyethylene with a density of 0.94 g/cm3 or more and a second layer comprising (ii) a resin material based on linear low density polyethylene with a density of below 0.94 g/cm3 and is manufactured by a multilayer inflation method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated sheet mainly composed of a polyethylene resin, and has transparency, flexibility, heat resistance, pinhole resistance, heat sealability, ESCR resistance, and the like.
Excellent in non-water vapor permeability, fragrance retention, low odor, hygiene, etc., has recyclability, and is applied to containers and packaging materials such as foods, beverages, detergents, drugs, medical infusions, cosmetics, and bath salts. The present invention relates to a laminated sheet, a manufacturing method thereof, and a container using the laminated sheet.

[0002]

2. Description of the Related Art In general, inexpensive and versatile polyethylene has been used for containers and packaging materials such as containers and packaging materials for foods, beverages, detergents, medicines, medical infusions, cosmetics, bath salts, and the like. And single-layer films and laminated sheets of polyolefin resins such as polypropylene.

[0003] Such a single-layer film, a laminated sheet and the like are required to be easily heat-sealed and easily obtained in a container form. Also, such a single-layer film,
The container obtained from the laminated sheet etc. has transparency for confirming the contents and confirming whether or not foreign matter is mixed therein; flexibility for filling and packing the contents; filling at high temperature, boiling treatment and retort sterilization. It is required to have heat resistance for preventing the occurrence of pinholes due to vibration of the contents during transportation of products, and to have excellent ESCR resistance (environmental stress cracking resistance). . Also recently,
Containers and packaging materials are required to be easily recyclable and easily collected, and are required to satisfy the above-mentioned various performances and the recyclability and collection properties.

[0004] As a laminated sheet satisfying such performance, for example, JP-A-4-266759, JP-A-6-26659
JP-A-171039, JP-A-6-246886 and JP-A-8-309939 disclose low-density linear polyethylene, high-density polyethylene, high-pressure low-density polyethylene, or a mixture thereof in two or three layers. Laminated laminated sheets have been proposed.

However, these laminated sheets are insufficient in transparency, heat seal strength, and pinhole resistance, and have not sufficiently satisfied the above-mentioned various properties required for containers and packaging materials. Also, these laminated sheets have poor drawdown resistance, and therefore, when subjected to thermoforming (vacuum forming, hot plate forming, press forming, pressure forming, etc.),
Defects such as wrinkles, uneven thickness and perforation are likely to occur on molded products,
It was difficult to manufacture containers by thermoforming.

[0006]

Accordingly, an object of the present invention is to provide a laminate having transparency, flexibility, heat resistance, pinhole resistance, heat sealability, ESCR resistance, non-water vapor permeability, and fragrance retention. It is an object of the present invention to provide a sheet and a method for producing the same, and further to provide a laminated sheet having low odor, having hygiene properties, and being excellent in recyclability, and a method for producing the same. Another object of the present invention is to provide a laminated sheet which is excellent in thermoformability and is suitable for thermoforming, and a method for producing the same.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the conventional problems, and as a result, have attained the above-mentioned object with a laminated sheet made of a specific resin combination. That is, the laminated sheet of the present invention has a first layer made of a resin material (i) mainly composed of high-density polyethylene having a density of 0.94 g / cm ³ or more, and a density of 0.94 g / cm ³ or more.
and a second layer made of a resin material (ii) containing linear low-density polyethylene of less than g / cm ³ as a main component.

The thickness of the laminated sheet is 40 μm to 1 m.
m, and the thickness of each of the I-th layer and the II-th layer is 2
It is desirable to be in the range of 0 to 500 μm. Further, the laminated sheet of the present invention is desirably used as a sheet for thermoforming. Further, it is preferable that a recycled resin layer (III) made of a blended resin of the resin material (i) and the resin material (ii) obtained by recycling the laminated sheet is further provided. Further, it is desirable that the laminated sheet of the present invention further has a barrier layer (IV).

It is preferable that the linear low-density polyethylene satisfies the following requirements (a) to (d). (A) Density of 0.86 g / cm ³ or more, 0.94 g / c
m less than ^3, (b) a melt flow rate of 0.01 to 50 g / 10
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5; (d) a total of 25 obtained from an integrated elution curve of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF). The difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which% elutes and the temperature T _{75 at} which 75% of the total elutes satisfy the following (Equation 1): (Equation 1) T ₇₅ -T ₂₅ ≦ -670 × d + 644

The linear low-density polyethylene further satisfies the following requirements (e) and (f) (A1):
Desirably, it 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)

The linear low-density polyethylene further satisfies the following requirements (g) and (h) (A2)
Desirably, it is a linear low density polyethylene. (G) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF), and T ₇₅ -T ₂₅ and the density d satisfy the relationship of the following (Equation 4). 4) T ₇₅ −T ₂₅ ≧ −300 × d + 285 (h) Having 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) 5) T _ml ≧ 150 × d−17 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. . Further, the resin material (i
It is desirable that the additive compounded in i) is an additive that does not substantially migrate to the contacted object, or that the additive is not compounded in the resin material (ii). The halogen concentration of the resin material (ii) is desirably 10 ppm or less.

Further, the container of the present invention is characterized in that the laminated sheet of the present invention is formed by any one of extrusion molding, injection molding, hollow molding, compression molding and thermoforming. And Further, the inner bag for a bag-in-box of the present invention is characterized by being made of the laminated sheet of the present invention.
Further, the molded article of the present invention is characterized by comprising the laminated sheet of the present invention. Further, the molded article of the present invention is a container obtained by molding the laminated sheet of the present invention by any one of extrusion molding, injection molding, blow molding, compression molding, and thermoforming. Features. Further, the molded article of the present invention is an inner bag for a bag-in-box made of the laminated sheet of the present invention.

[0014] The method for producing a laminated sheet according to the present invention comprises:
The laminated sheet is manufactured by air-cooled inflation molding. Further, in the method for producing a laminated sheet of the present invention, the innermost layer of a hollow tube obtained by air-cooling inflation molding of at least the resin material (i) and the resin material (ii) is formed from the resin material (i). It is desirable that the first layer be formed. Further, in the method for producing a laminated sheet of the present invention, a hollow tube obtained by air-cooling inflation molding of at least the resin material (i) and the resin material (ii) is sandwiched and crushed to form a laminated sheet of three or more layers. It is desirable.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The resin material (i) mainly composed of high-density polyethylene (hereinafter, referred to as HDPE) for forming the I-th layer is a resin mainly composed of HDPE and blended with another polyethylene resin as required. As HDPE in the present invention,
Various materials having a density of 0.94 g / cm ³ or more can be used. Specifically, a homopolymer composed of only ethylene, a copolymer composed of ethylene and another monomer (for example, an α-olefin such as propylene, 1-butene, and 1-hexene), or a copolymer composed of ethylene and 2
Examples include a multi-component copolymer composed of at least one kind of monomer.

When the density of HDPE is less than 0.94 g / cm ³ , the resulting laminated sheet has a stiffness (Young's modulus), gas barrier properties (non-water vapor permeability, fragrance retention, moisture resistance), heat resistance, etc. Is impaired. The melt flow rate of HDPE (hereinafter referred to as MFR) is preferably 0.01 to
50 g / 10 min, more preferably 0.05 to 30 g / 1
The range is 0 minute, more preferably 0.1 to 10 g / 10 minutes. If the MFR (190 ° 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 laminated sheet tends to decrease.

The HD in the resin material (i) forming the first layer
The mixing ratio of PE is 50 to 100% by weight, preferably 70 to 100% by weight. HDPE ratio is 50
If the amount is less than the weight percentage, the moisture resistance, non-water vapor permeability, and fragrance retention of the laminated sheet are reduced.

The other polyethylene resin used for the resin material (i) for forming the layer I is not particularly limited, but may be a linear low-density polyethylene having a density of less than 0.94 g / cm ³ (hereinafter referred to as “polyethylene resin”). LLDPE), a high-pressure radical method ethylene-based polymer, and the like. Among them, LLDP
E is preferred. LLDPE is ethylene and carbon number 3 ~
20, preferably a copolymer with an α-olefin having 3 to 8 carbon atoms.

The MFR of LLDPE is generally 0.01 to
50 g / 10 min, preferably 0.05 to 30 g /
It is 10 minutes, more preferably 0.5 to 10 g / 10 minutes. When the MFR is less than 0.01 g / 10 min, the fluidity (sheet formability) is reduced, and when it exceeds 50 g / 10 min, the strength and the like are reduced.

The proportion of the other polyethylene resin in the resin material (i) is less than 50% by weight, preferably 5% by weight.
３０30% by weight. If the proportion of the other polyethylene-based resin exceeds 50% by weight, the moisture-proof property and rigidity of the laminated sheet decrease.

The high-pressure radical polymerization ethylene polymer includes low-density polyethylene (LDPE) by high-pressure radical polymerization, ethylene / vinyl ester copolymer, ethylene and α, β-unsaturated carboxylic acid or a derivative thereof. And the like.

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 / 10 min, more preferably 0.1 to 10 g
/ 10 minutes. Within this range, the melt tension is in an appropriate range, and the moldability is improved. The density of LDPE is 0.91 to 0.94 g / cm.
³ , more preferably 0.91 to 0.935 g / cm ³
Range. Within this range, the melt tension is in an appropriate range, and the moldability is improved. The melt tension of LDPE is 1.5 to 25 g, preferably 3 to 25 g.
20 g, more preferably 3 to 15 g. Also, L
The molecular weight distribution Mw / Mn of the DPE 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.

The copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof includes 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 resin material (ii) containing linear low-density polyethylene as a main component and forming the second layer is a resin material containing linear low-density polyethylene as a main component and optionally other polyethylene-based resins. It is.

Linear low density polyethylene (LLDPE)
Is a copolymer having a density of less than 0.94 g / cm ³ obtained by copolymerizing ethylene and α-olefin, and ethylene and α-olefin having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. It is a copolymer with olefin. As the α-olefin having 3 to 20 carbon atoms, propylene, 1-
Butene, 4-methyl-1-pentene, 1-pentene, 1
-Hexene, 1-octene and the like are used. (A) L
The structural unit derived from the α-olefin having 3 to 20 carbon atoms in LDPE is 1 to 7 mol%, preferably 1 to 7 mol%.
It is 5 mol%, more preferably 2-3 mol%. When the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 7
If it exceeds mol%, the impact resistance, creep resistance, and heat seal strength decrease, and if it is less than 1 mol%, transparency decreases. The linear low-density polyethylene in the present invention is not particularly limited as long as it is as described above, but specific (A) linear low-density polyethylene satisfying the following requirements (a) to (d) is particularly preferable.

The (a) density of the (A) linear low-density polyethylene in the present invention is 0.86 g / cm ³ or more and 0.94 or more.
g / cm ³ , preferably 0.89 to 0.935 g
/ Cm ³ , more preferably 0.90 to 0.93 g / c
m ³ . If the density is less than 0.86 g / cm ³ , rigidity (lumbar strength) and heat resistance may be reduced. If the density is 0.94 g / cm ³ or more, the transparency of the laminated sheet may be impaired.

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 10 g / 10 min. 10 g / min. MFR 0.01g
If it is less than / 10 minutes, the moldability is poor, and if it exceeds 50 g / 10 minutes, the impact resistance and the like of the laminated sheet may be poor.

The (c) molecular weight distribution (Mw / Mn) of the linear low density polyethylene (A) in the present invention is 1.5 to 1.5.
The range is 4.5, preferably 2.0 to 4.0, and more preferably 2.5 to 3.0. If Mw / Mn is less than 1.5, the moldability is poor, and if Mw / Mn exceeds 4.5, impact resistance and the like may be poor. Here, the molecular weight distribution (Mw / Mn) of the linear low-density polyethylene was obtained by weight-average molecular weight (Mw) and number-average molecular weight (Mn) by gel permeation chromatography (GPC).
It can be determined by calculating their ratio (Mw / Mn).

The linear low-density polyethylene (A) in the present invention is obtained, for example, from the integrated elution curve of the elution temperature-elution amount curve (TREF) by the 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 according to the present invention further comprises (A1) a linear low-density polyethylene satisfying the requirements (e) and (f) described below, or (g) and ( Preferably, it is 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 filtrate is collected by filtering through a Teflon filter. This filtrate, which is a sample solution, was subjected to infrared spectroscopy to measure the asymmetric stretching vibration wave number of methylene 2925c.
The absorption peak intensity around m ^-1 is measured, and the sample concentration is calculated from a calibration curve created in advance. From this value, the ODCB-soluble content at 25 ° C. is determined.

The ODCB-soluble component at 25 ° C. is a high branching degree component and a low molecular weight component contained in linear low-density polyethylene, which causes a decrease in heat resistance and a sticky surface of a molded product, and causes a problem of hygiene. 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.

Here, as shown in FIG. 1, (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). on the other hand,
The ethylene copolymer shown in FIG.
EF) is a linear low-density polyethylene having substantially one peak in an elution temperature-elution amount curve obtained by EF), and is a conventional typical metallocene-based catalyst.
An α-olefin copolymer corresponds to this.

As shown in FIG. 3, (A2) the linear low-density polyethylene of the present invention has one peak of an elution temperature-elution amount curve obtained by (g) continuous heating elution fractionation (TREF), In addition, T ₇₅ -T ₂₅ and the density d satisfy the relationship of the following (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 (1) 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 among them satisfy the relationship of the following (formula 5). Things. (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.

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 of (1), the formability of a laminated sheet or the like is improved.

As shown in FIG. 3, (A2) the linear low-density polyethylene has one TREF peak, but the conventional typical metallocene catalyst-based ethylene copolymer has the above formula (formula (2)). 4) is not satisfied, and is distinguished from a conventional typical metallocene-based catalyst-based ethylene copolymer.

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, but preferably an organic cyclic compound having at least a conjugated double bond. 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 the linear low-density polyethylene (A) in the present invention, it is particularly desirable to polymerize with a catalyst obtained by mixing the following compounds a1 to a4. a1: Compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr (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, and tetrabutoxy titanium , Tetrabutoxy hafnium and the like, and especially Z such as tetrapropoxy zirconium and tetrabutoxy zirconium.
r (OR) ₄ compounds are preferred, and two or more of these may be used in combination. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonato ligand or derivative thereof include tetra (2,4-pentanedionato) zirconium. , Tri (2,4-pentanedionato)
Zirconium chloride, di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride zirconium, di (2,4-pentanedionato) diethoxide zirconium, di (2,4- Pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n
-Butoxide zirconium, di (2,4-pentanedionato) dibenzyl zirconium, di (2,4-pentanedionato) dineofylzirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) die Zirconium toxide, zirconium di (dibenzoylmethanato) di-n-propoxide, zirconium di (dibenzoylmethanato), zirconium di (n-butoxide), zirconium diethoxide zirconium, di (benzoylacetonate) ) Di-n-propoxide zirconium, di (benzoylacetonate)
And di-n-butoxide zirconium.

The general formula Me of the catalyst component a2^TwoR^Four _m(O
R^Five)_nX^Two _zmn In the formula of the compound represented by^Two Is the period
Represents a group I-III element of the table, lithium, sodium,
Potassium, magnesium, calcium, zinc, boron,
Aluminum and the like. R^FourAnd R^Five Is charcoal
A hydrocarbon group having a prime number of 1 to 24, preferably a carbon number of 1 to 1
2, more preferably 1 to 8, specifically
Group, ethyl group, propyl group, isopropyl group, butyl
Alkyl groups such as vinyl groups; alkene groups such as vinyl groups and allyl groups
Nyl group: phenyl group, tolyl group, xylyl group, mesityl
An aryl group such as a group, an indenyl group or a naphthyl group;
Jyl, trityl, phenethyl, styryl, ben
Such as a duhydryl group, a phenylbutyl group and a neofuyl group
Aralkyl groups and the like. These have branches
Is also good. X^Two Is fluorine, iodine, chlorine and bromine, etc.
Represents a halogen atom or a hydrogen atom. However
Then X ^Two Is Me when hydrogen is a hydrogen atom^Two Is boron, aluminum
Only in the case of Group III elements in the periodic table
Things. Z is Me^Two And m and m
And n satisfy the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively.
Is an integer, and 0 ≦ m + n ≦ z.

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

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

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

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

Specific examples of the organic cyclic hydrocarbon compound of the component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7- C5-C24 cyclopolyene or substituted cyclopolyene such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadiene Examples include enylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

The modified organoaluminum oxy compound containing an Al—O—Al bond of the catalyst component a4 is obtained by reacting an alkylaluminum compound with water to obtain a modified organoaluminum oxy compound usually called aluminoxane. The molecule usually contains 1 to 100, preferably 1 to 50 Al-O-Al bonds. The modified organic aluminum oxy compound may be linear or cyclic.

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

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

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

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

The process for producing (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, which substantially does not contain a solvent. In a state where oxygen, water, etc. are cut off, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, etc. 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 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, 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, it is not necessary to use an acid neutralizer as in the past, and the chemical stability and hygiene are excellent, and especially, food packaging materials and the like. It is possible to provide a laminated sheet suitably used in the field of (1).

The mixing ratio of (A) the linear low-density polyethylene in the resin material (ii) for forming the second layer is from 50 to 1
00% by weight, preferably 70 to 100% by weight. (A) 50% by weight of linear low density polyethylene
If it is less than 1, the heat resistance, the pinhole resistance, the heat sealing property, the ESCR resistance, and the mechanical strength of the laminated sheet decrease.

Examples of other polyethylene polymers that can be blended with the resin material (ii) include a high / medium / low pressure method using a Ziegler type catalyst or the like, and other known methods such as an ethylene homopolymer, ethylene and a C3 to C3 polymer. 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 with a density of 0.91 to 0.94 g /
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 refers to 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.

Further, the ultra low density polyethylene (VLDPE) using the Ziegler type catalyst has a density of 0.86 to 0.86.
0.91 g / cm ³ , preferably 0.88 to 0.905
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.

The resin material (i) in the present invention may contain known additives and fillers. Further, in the resin material (ii), by using (A) linear low-density polyethylene produced using a catalyst containing no halogen, and by not adding additives such as an antioxidant and a neutralizing agent, A clean molded body can be provided.

In the present invention, the resin material (ii) may contain an antioxidant, an antiblocking agent, a lubricant, an antistatic agent, an antifogging agent, an ultraviolet absorber, an organic or inorganic pigment, a nucleating agent, A known additive such as a cross-linking agent is not blended, or even if the additive is blended in the resin composition, the blended additive does not substantially transfer to the contacted object such as the contents. Desirably, it is an agent. In the present invention, an additive that elutes to the outside, for example, when the content is a liquid, an additive that is eluted in the liquid, an additive in which odor is transferred, or with time Since an additive that is unevenly distributed on the film surface is not included in the resin material (ii), it is possible to provide a sanitary and clean laminated sheet or container with less odor.

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 above. 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 laminated sheet.

The laminated sheet of the present invention comprises the first layer I composed of the resin material (i) containing HDPE as a main component, and the resin material (ii) containing the (A) linear low-density polyethylene as a main component. And a second layer.

The thickness of the laminated sheet of the present invention is preferably 40 μm to 5 mm from the viewpoint of ease of use. Also,
The thickness of each layer of the I layer and the II layer of the laminated sheet of the present invention depends on the properties of each layer (the I layer: non-water vapor permeability, fragrance retention, etc.
Layer II: 20 layers in order to sufficiently exhibit heat resistance, pinhole resistance, heat sealability, ESCR resistance, etc.)
It is desirable to select within a range of up to 2.5 mm.

Other layers may be interposed between the II-th layer and the I-th layer. Other layers include an adhesive resin layer for more firmly bonding the second layer and the first layer.

The laminated sheet of the present invention may further have a recycled resin layer (III) composed of a resin material (i) and a resin material (ii) obtained by recycling the laminated sheet. . Here, the blended resin obtained by recycling the laminated sheet is a defective product of the laminated sheet, a collected product of the container composed of the laminated sheet,
It is a mixed resin obtained by pulverizing burrs and the like generated in a finishing stage after processing into a container or the like. Thus, the laminated sheet of the present invention can use a recycled blended resin, and has good recyclability.

The laminated sheet of the present invention may further have a barrier layer (IV). By providing the barrier layer (IV), gas barrier properties (non-water vapor permeability, fragrance retention, moisture resistance) are further improved. The barrier layer (IV)
Examples of the film include plastic films or sheets of polypropylene resin, polyamide resin, polyester resin, saponified ethylene-vinyl acetate copolymer, polyvinylidene chloride, polycarbonate, etc. (stretched products, printed materials, deposited materials of metals, etc.). Etc., or a metal foil or a metal plate such as aluminum, iron, copper, or an alloy containing these as a main component, cellophane, paper, or woven fabric without departing from the spirit of the present invention. Cloth, non-woven fabric and the like may be used in some cases.

The layer structure of the laminated sheet includes I / II, I
/ III / II, I / II / III, I / II / IV, I / IV / II and the like. Specifically, sLL / HD, sLL + LD /
HD, sLL / HD + LL, sLL + LD / HD + L
L, sLL / RC / HD, sLL + LD / RC / HD,
sLL + LD / RC + LL / HD, sLL / HD / RC
+ HD, sLL / adhesive / barrier layer (EVOH, P
A, PEs, OPP, etc.) / Adhesive / HD. (Where LL: conventional linear low density polyethylene,
sLL: (A) linear low-density polyethylene in the present invention, LD: high-pressure radical method low-density polyethylene, HD:
High-density polyethylene, RC: recycled blend resin, EVOH: saponified ethylene-vinyl acetate copolymer, PA: polyamide resin, PEs: polyester resin, OPP: biaxially oriented polypropylene, adhesive: acid-modified polyethylene. )

The forming of the laminated sheet of the present invention can be performed by various methods. For example, an air-cooled inflation method, a water-cooled inflation method, a T-die method, and the like are suitable, and an air-cooled inflation method is particularly preferable in terms of economy, formability, and the like.

The production of the laminated sheet by the air-cooled inflation molding can be carried out by a conventional air-cooled inflation film manufacturing apparatus.
It is performed by extruding through a circular die from an extruder at a temperature of 0 to 250 ° C., contacting with air blown out from an air-cooled air ring, quenching, solidifying, taking out with a pinch roll, and winding it around a frame. In addition to air-cooled inflation molding, water-cooled inflation molding,
It can be manufactured by a T-die method or the like, and a sheet having excellent transparency, low-temperature impact resistance, and the like can be obtained.

In the air-cooled inflation molding method, it is preferable that the innermost layer is formed of the resin material (i) mainly composed of high-density polyethylene of the I-th layer. According to such a method, the inner surface becomes HDPE, so that the workability is improved due to the excellent antiblocking property.

It is also possible to form a laminated sheet of three or more layers by sandwiching a hollow tube obtained by air-cooling inflation molding of at least the resin material (i) and the resin material (ii). As a method of obtaining such a laminated sheet, 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 inner layer resin material, A method in which a hollow tube formed by extruding each resin material through a circular die is brought into contact with air blown from an air-cooled air ring to cool and solidify, and then crushed by a heated pinch roll is used. According to such a manufacturing method, a thick laminated sheet can be easily obtained.

By manufacturing the laminated sheet by the air-cooled inflation molding method as described above, the resin is uniformly crystallized due to the slow cooling by the air cooling without the unevenness unlike the laminated sheet obtained by the T-die method. A strong laminated sheet, low temperature molding is possible, additive-free molding is possible, and a laminated sheet that does not adversely affect the contacted object is obtained. Blow-up ratio (BUR) can be adjusted and quality can be controlled. Compared to the T-die method, there is no ear loss, high productivity, and excellent economic efficiency.
By crushing by multilayering with a pinch roll,
An advantage is obtained that a sheet having twice the thickness can be formed at a time, and the thickness can be homogenized.

Examples of the molded article of the present invention include bags (bags), containers, bottles, tubes, and the like made of the laminated sheet of the present invention.
Trays, cups and the like. These molded articles are obtained by molding the laminated sheet of the present invention by any one of extrusion molding, injection molding, hollow molding, compression molding and thermoforming. The molding method is not particularly limited. Further, the laminated sheet can be made into a bag shape by heat sealing and used as a pouch.

Containers, which are the main applications of the molded article of the present invention, include bottles, cups, pouches, trays, and bag-in-boxes used for foods, beverages, detergents, drugs, medical infusions, cosmetics, bath salts, and the like. Bags, bags, pouches, squeeze tubes and the like are included.

The laminated sheet of the present invention can be produced by a vacuum forming method,
It is suitable as a sheet used when manufacturing a container by a thermoforming method such as a pressure forming method. This is because the laminated sheet of the present invention has excellent drawdown resistance, and wrinkles, uneven thickness,
This is because defects such as holes are unlikely to occur.

The container has an inner layer made of a resin material (ii) whose main component is the (A) linear low-density polyethylene.
It is desirable to be a layer II. No. with heat sealability
By using the II layer as the inner layer, the moldability of the container is improved.
Also, a second resin material comprising a halogen-free (A) resin material (ii) using a linear low-density polyethylene or a resin material (ii) containing no additive that elutes to the outside.
If the layer is the inner layer of the container, there is little odor transfer and the container is excellent in hygiene.

Other embodiments of the container include a stand pouch and an inner bag for a bag-in-box. Another embodiment is a medical container. In the inner bag for bag-in-box or the medical container, at least the inner layer of the inner bag or the container has a heat-sealing property.
It is desirable to be a layer II. Also, a resin material using (A) a linear low-density polyethylene containing no halogen (ii)
If the second layer made of the resin material (ii) that does not contain an additive that elutes to the outside or the outside is the inner layer of the inner bag or container, a clean inner bag or container is obtained. The inner bag for a bag-in-box or a medical container may be a laminated sheet of two or more layers, or (A) a barrier property such as linear low density polyethylene / adhesive / barrier resin / adhesive / high density polyethylene. It is formed from a suitable embodiment of the above-mentioned laminated sheet using a resin or the like.

[0083]

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

The test method in this example is as follows. [Density] Based on JIS K6760. [MFR] Based on JIS K6760. [Mw / Mn] GPC (150C type manufactured by Waters)
And 135 ° C. ODCB was used as a solvent. The column used was Shodex HT806M. [TREF] With the column 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)

<Evaluation of laminated sheet> [Heat seal strength] Heat seal tester manufactured by Tester Sangyo Co., Ltd. (seal bar width 1 mm, seal pressure 2 kg / c)
m ² ), the innermost layer (Layer II) surfaces of the laminated sheet are sealed at a sealing temperature of 165 ° C. for 1 second, and a room temperature of 23 ° C.
After adjusting the condition for 24 hours at 50% humidity,
Cut into strips with a width of 300 mm and 300 mm with a tensile tester
The seal was peeled off at a rate of / min, and the maximum load was measured. [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 value] According to ASTM D1822, MD
(Extrusion direction) was measured.

<Evaluation of Container> [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 breakage △: 1-2 breakage bags ×: 3 or more breakage bags

Various components used in Examples and Comparative Examples are as follows. (1) High-density polyethylene ethylene / 1-butene copolymer (HDPE-1) MFR = 1.0 g / 10 min, density = 0.956 g / cm
^3. Nippon Polyolefin Co., Ltd. (2) High density polyethylene Ethylene / 1-butene copolymer (HDPE-2) MFR = 1.5 g / 10 min, density = 0.951 g / cm
^3. Nippon Polyolefin Co., Ltd.

(3) 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 that the molar ratio is maintained at a predetermined value.
Tylene copolymers (LLDPE-1 and LLDPE-
2) was obtained. The 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-3) was obtained. The physical properties are shown in the table.

3) Ethylene catalyzed by a general metallocene catalyst
Hexene-1 copolymer (LLDPE-4) Purified toluene was placed in a pressure reactor equipped with a stirrer and purged with nitrogen, then 1-hexene was added, and bis (n-
A mixture of (butylcyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) was mixed with (Al /
(Zr molar ratio = 500), and the temperature was raised to 80 ° C. to prepare a metallocene catalyst. Then, add ethylene,
While continuously polymerizing ethylene, the polymerization was carried out while maintaining the total pressure at 6 kg / cm ³ to produce an ethylene / hexene-1 copolymer (LLDPE-4). The physical properties are shown in Table 1.

4) Commercial linear low density polyethylene (LLD)
PE-5) Physical properties are shown in Table 1.

[0094]

[Table 1]

(4) High pressure method low density polyethylene: HP-
LDPE-1 MFR = 0.3 g / 10 min, density = 0.923 g /
cm ³ (5) High pressure method low density polyethylene: HP-LDPE-2 MFR = 1.0 g / 10 min, density = 0.924 g /
cm ³ , manufactured by Nippon Polyolefin Co., Ltd. (6) Medium density polyethylene: MDPE-1 MFR = 0.2 g / 10 min, density = 0.938 g /
cm ³

[Examples 1, 3-9, Comparative Examples 1-4, Reference Examples 1-2] Using a two-layer inflation molding machine (two 40 mmφ extruders) manufactured by Tommy Machine Industry Co., Ltd., a molding lip gap of 3 mm was used. Under the condition of a molding temperature of 200 ° C., a resin material for each layer shown in Tables 2 to 4 was prepared by mixing a predetermined amount of an antioxidant (Irganox 1076, Irgafos 168) and calcium stearate (neutralizing agent). , Width 3
A laminated sheet having a thickness of 00 mm and a layer thickness configuration shown in Tables 2 to 4 was produced. Further, the second layer of the laminated sheet was heat-sealed to produce a container having a content of 500 ml. The laminated sheet and the container were evaluated. The results are shown in Tables 2 to 4. Example 2 A resin sheet for each layer shown in Table 2 was molded in the same manner as in Example 1 without blending the antioxidant and calcium stearate, and a laminated sheet and a container were manufactured and evaluated. Table 2 shows the results.

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

As is clear from the results shown in Tables 2 and 3, the laminated sheets of the examples are excellent in heat sealability, pinhole resistance, non-water vapor permeability, transparency and mechanical strength. . The containers of the examples had sufficient heat resistance and drop strength. In particular, a container using LLDP-1, LLDP-2 and LLDP-3 containing almost no halogen for the inner layer (Layer II) has a low odor and is excellent in hygiene. , LLDPE-2 containing no acid neutralizing agent)
The container used for the layer) was more excellent in hygiene.

On the other hand, as is clear from the results in Table 4, the laminated sheet and the container of Comparative Example 1 were inferior in non-water vapor permeability and heat resistance because HDPE was not used for the I-th layer. The laminated sheet and the container of Comparative Example 2 also had H
Since no DPE was used, the non-water vapor permeability and the heat resistance were poor.

The laminated sheet and the container of Comparative Example 3 were made of II
Since the layer (A) did not use linear low-density polyethylene, the heat sealability and the pinhole resistance were poor. Further, the tensile impact strength and the drop strength were inferior. In addition, since the high-pressure method low-density polyethylene was used for the inner layer (Layer II), the odor was severe and the hygiene was poor. The laminated sheet and the container of Comparative Example 4 had a low mixing ratio of HDPE of the first layer and LDPE of the second layer.
Heat resistance, heat seal strength, tensile impact strength, and drop strength were poor. Also, the odor was intense and the hygiene was poor.

[0103]

As described above, the laminated sheet of the present invention comprises the first layer made of the resin material (i) mainly composed of high density polyethylene having a density of 0.94 g / cm ³ or more,
Since it has a second layer made of a resin material (ii) mainly containing linear low-density polyethylene having a density of less than 0.94 g / cm ³ , transparency, flexibility, heat resistance, and pinhole resistance , Heat sealability, ESCR resistance, non-water vapor permeability,
Excellent scent retention.

The thickness of the laminated sheet is 40 μm to 5 m.
m and the thicknesses of the I-th layer and the II-th layer are each 2
If it is in the range of 0 to 2.5 μm, it is easy to use and the properties of each layer (Layer I: non-water vapor permeability, fragrance retention, etc .; Layer II: heat resistance, pinhole resistance, heat sealability, ESCR resistance) Properties, etc.). Further, the laminated sheet of the present invention has excellent drawdown resistance, and thus can be suitably used as a sheet for thermoforming.

If a recycled resin layer (III) comprising a blended resin of the resin material (i) and the resin material (ii) obtained by recycling the laminated sheet is further provided, the recycled blended resin Can be used, and the recyclability is improved. Further, the laminated sheet of the present invention further comprises a barrier layer (IV)
, The gas barrier properties (non-water vapor permeability, fragrance retention, moisture resistance) are further improved.

If the linear low-density polyethylene satisfies the following requirements (a) to (d), the heat resistance, heat sealability, mechanical strength, rigidity, moldability and the like of the laminated sheet are further improved. improves. When the linear low-density polyethylene is (A1) a linear low-density polyethylene that further satisfies the requirements (e) and (f), the heat resistance, hygiene, and rigidity of the laminated sheet are further improved. I do. Also,
If the linear low-density polyethylene further satisfies the above requirements (g) and (h) (A2), the laminated sheet has heat resistance, heat seal strength, and low-temperature heat sealability. Further improve. When the (A2) linear low-density polyethylene further satisfies the requirement (i), the formability of the laminated sheet 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 laminated sheet, heat sealing properties, heat blocking Properties and heat resistance are further improved. Further, if the additive blended in the resin material (ii) is an additive that does not substantially migrate to the contacted object, or if the additive is not blended in the resin material (ii), the odor is small, A laminated sheet having hygiene properties can be obtained. In addition, when the halogen concentration in the second layer is 10 ppm or less, it is possible to provide a laminated sheet having excellent chemical stability and hygiene, and particularly suitably used in the field of food packaging materials and the like.

Further, since the molded article of the present invention comprises the laminated sheet of the present invention, transparency, flexibility, heat resistance, pinhole resistance, heat sealability, ESCR resistance, water vapor transmission resistance, fragrance retention Excellent in nature. Further, the container which is an embodiment of the molded article of the present invention is obtained by molding the laminated sheet of the present invention by any one of extrusion molding, injection molding, hollow molding, compression molding and thermoforming. , Transparency, flexibility, heat resistance, pinhole resistance, heat sealability, ES resistance
Excels in CR properties, water vapor transmission resistance, and fragrance retention. Further, since the inner bag for a bag-in-box, which is an example of the molded article of the present invention, is made of the laminated sheet of the present invention, transparency, flexibility, heat resistance, pinhole resistance, heat sealability, and heat resistance are improved. E
Excellent SCR property, water vapor transmission resistance, and fragrance retention.

The method for producing a laminated sheet of the present invention
Since the method is a method of manufacturing the laminated sheet by air-cooling inflation molding, a laminated sheet having transparency, flexibility, heat resistance, pinhole resistance, heat sealability, ESCR resistance, non-water vapor permeability, and fragrance retention is obtained. It can be manufactured with good economy and formability. In the method for producing a laminated sheet of the present invention, at least the innermost layer of a hollow tube obtained by air-cooling inflation molding of the resin material (i) and the resin material (ii) is made of the resin material (i). When the first layer is used, workability is improved due to excellent anti-blocking properties. Further, in the method for producing a laminated sheet of the present invention, a hollow tube obtained by air-cooling inflation molding of at least the resin material (i) and the resin material (ii) may be sandwiched to form a laminated sheet having three or more layers. And a thick sheet can be easily obtained.

[Brief description of the drawings]

FIG. 1 is a graph showing an elution temperature-elution amount curve of (A1) linear low-density polyethylene in the present invention.

FIG. 2 is a graph showing an elution temperature-elution amount curve of an ethylene copolymer with a metallocene catalyst.

FIG. 3 is a graph showing an elution temperature-elution amount curve of (A2) linear low-density polyethylene in the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 105: 26 B29K 105: 26 B29L 22:00 B29L 22:00 F-term (Reference) 3E086 AD01 AD03 AD04 AD05 AD06 BA04 BA15 BB02 BB15 BB22 BB41 BB51 BB90 CA01 CA11 CA28 CA29 CA35 4F100 AA05B AH08B AK04 AK04J AK05A AK05C AK08 AK08J AK63B JAJCBAC BAB BAB BAB BAB BAB BAB BAB BAB BAB BAB BAB BAB BAB BAB BAB BAB BAB JD04 JJ03 JK13 JK14 JL08B JL12 JL16C JN01 YY00A YY00B 4F208 AA04E AA05 AA08 AB04 AG01 AG03 AH55 AR15 AR17 LW02 LW26 LW45 MB01 MB22 MG04 MG22 MG23 MG24 MJ32 MW45 4J002 BB03W BB03X BB05W BB05X BB06W BK00X FD010 GF00 GG02 4J100 AA02P AA03Q AA04Q AA07Q AA16Q AA17Q AA19Q AG02Q AG04Q AJ02Q AL03Q AL05Q AL08Q AL10Q BC04Q CA04 DA04 DA11 DA39 DA43 JA58

Claims (18)

[Claims] 1. A layer I made of a resin material (i) whose main component is a high-density polyethylene having a density of 0.94 g / cm ³ or more, and a linear low-density polyethylene having a density of less than 0.94 g / cm ^3. A laminated sheet having a second layer made of a resin material (ii) as a main component. 2. The laminated sheet has a thickness of 40 μm to 5 mm, and the thickness of each of the first and second layers is 20 to 20 μm.
The laminated sheet according to claim 1, wherein the thickness is in a range of 2.5 mm. 3. The laminated sheet according to claim 1, which is a thermoforming sheet. 4. A recycled resin layer (III) comprising a blend resin of a resin material (i) and a resin material (ii) obtained by recycling a laminated sheet. 4. The laminated sheet according to any one of 1 to 3. 5. The laminated sheet according to claim 1, further comprising a barrier layer (IV). 6. The laminated sheet according to claim 1, wherein the linear low-density polyethylene satisfies the following requirements (a) to (d). (A) Density of 0.86 g / cm ³ or more, 0.94 g / c
m less than ^3, (b) a melt flow rate of 0.01 to 50 g / 10
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5; (d) a total of 25 obtained from an integrated elution curve of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF). The difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which% elutes and the temperature T _{75 at} which 75% of the total elutes satisfy the following (Equation 1): (Equation 1) T ₇₅ -T ₂₅ ≦ -670 × d + 644 7. The laminated sheet according to claim 6, wherein the linear low-density polyethylene is (A1) a linear low-density polyethylene that further satisfies the following requirements (e) and (f). (E) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by weight), the density d and the melt flow rate (MFR) satisfy the 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) 8. The laminated sheet according to claim 6, wherein the 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 9. The laminated sheet according to claim 8, 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 10. The linear low-density polyethylene is an organic cyclic compound having at least a conjugated double bond and an organic cyclic compound having at least a conjugated double bond.
The laminated sheet according to any one of claims 1 to 9, wherein the laminated sheet is produced in the presence of a catalyst containing a Group IV transition metal compound. 11. An additive compounded in the resin material (ii) is an additive that does not substantially migrate to a contacted object, or no additive is compounded in the resin material (ii). The laminated sheet according to any one of claims 1 to 10, wherein 12. The laminated sheet according to claim 1, wherein the halogen concentration of the resin material (ii) is 10 ppm or less. 13. A molded article comprising the laminated sheet according to any one of claims 1 to 12. 14. The laminated sheet according to claim 1, wherein the laminated sheet is an extrusion molding method, an injection molding method, a hollow molding method,
A molded article characterized by being a container molded by any one of a compression molding method and a thermoforming method. 15. A molded article, which is an inner bag for a bag-in-box made of the laminated sheet according to any one of claims 1 to 12. 16. A method for producing a laminated sheet according to claim 1, wherein the laminated sheet according to claim 1 is produced by air-cooled inflation molding. 17. An inner layer of a hollow tube obtained by air-cooling inflation molding of at least the resin material (i) and the resin material (ii) is a first layer made of the resin material (i). The method for producing a laminated sheet according to claim 16, characterized in that: 18. A laminated sheet having three or more layers by sandwiching and crushing a hollow tube obtained by air-cooling inflation molding of at least the resin material (i) and the resin material (ii). A method for producing the laminated sheet according to the above.