JP2001341249A - Clean extrusion laminate, its manufacturing method and container using extrusion laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a clean extrusion laminate and method for manufacturing the same as well as a container using the extrusion laminate suitable for fields required for a clean container or the like of food, medical care, electronic material or the like having excellent tearing strength, impact resistance, low temperature heat sealability, transparency, moldability or the like. SOLUTION: The clean extrusion laminate comprises a resin material containing (A) an ethylene (co)polymer of 100 to 10 wt.%, and (B) another polyethylene resin of 0 to 90 wt.%. The material has a density of 0.86 to 0.97 g/cm3, an MFR of 0.01 to 50 g/10 min, a molecular weight distribution of 1.5 to 4.5, and satisfies a difference T75-T25 of a temperature T25 for dissolving 25% of the entirety obtained from an integrated dissolving curve of a dissolving temperature-dissolving amount curve by a TREF and a temperature T75 for dissolving 75% of the entirety and a density difference (d) of a relation of T75-T25<=-670×d+644, in such a manner that an additive for transferring a material to be contacted is not compounded in the resin material and a halogen content in the resin material is 10 ppm or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an extruded laminate used in fields requiring clean packaging materials, containers and the like for foods, medicals, electronic materials, etc., and more particularly, to an extruded laminate which is free from impurities and elution, and is tear-free. The present invention relates to a clean extruded laminate excellent in strength, impact resistance, low-temperature heat sealability, transparency and the like, a method for producing the same, and a container using the extruded laminate.

[0002]

2. Description of the Related Art Conventionally, paper containers and packaging materials for packaging materials such as milk and dairy products, which are packaging materials conforming to the ministerial ordinance No. 52 of milk and the like, have been manufactured using high-pressure radical process low-density polyethylene. And manufactured by an extrusion lamination method or the like. However, high-pressure low-density polyethylene has a problem in that tear strength, impact resistance, stiffness and the like are inferior. In recent years, more stringent low-temperature heat-sealing properties and heat resistance have been demanded in order to improve productivity, and there has been a demand for an alternative to high-pressure radical method low-density polyethylene.

As an alternative to the high-pressure radical method low-density polyethylene, linear low-density polyethylene, high-density polyethylene and the like can be considered. However, linear low-density polyethylene is excellent in tear strength, impact resistance, etc., but is inferior in moldability, low-temperature heat sealability, etc., and high-density polyethylene is excellent in heat resistance, mechanical strength, etc., but is transparent. However, there is a problem that the properties, tear strength, impact resistance, low-temperature heat sealability, and the like are inferior.

In the molding of linear low-density polyethylene and high-density polyethylene by ionic polymerization,
Since the molding temperature is higher than that of the high-pressure radical method low-density polyethylene, it was necessary to add an antioxidant to prevent the deterioration of the resin. Further, since a halogen element such as chlorine is present as a catalyst residue, it is necessary to add a halogen absorber (acid neutralizer) such as calcium stearate and hydrotalcite. Therefore, these linear low-density polyethylenes and high-density polyethylenes are difficult to comply with ministerial ordinances for milk, etc., because they contain additives that migrate to the contacted object such as contents. Also, the low-temperature heat sealability was not satisfactory.

As a material having excellent low-temperature heat sealability, a linear low-density polyethylene produced by a metallocene catalyst can be cited, and has been spotlighted as a packaging material. However, such a low-density linear polyethylene using a general metallocene catalyst also has a problem in cleanliness at the time of molding because additives such as the antioxidant, the halogen absorber, and the lubricant are used. In addition, in general, even when a halogen absorber is used, there is a problem that the halogen element cannot be completely removed and the halogen element remains in the resin.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a container having excellent tear strength, impact resistance, low-temperature heat sealability, transparency, moldability, etc., and clean food, medical and electronic materials. Etc., in particular, Ministry of Health and Welfare Notification 52
It is an object of the present invention to provide a clean extruded laminate suitable for a food container or the like conforming to the above item, a method for producing the same, and a container using the extruded laminate.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, they have found that no additives are blended or that the blended additives substantially migrate to the contacted object. A resin using a resin material containing an ethylene (co) polymer satisfying a specific parameter, or a polyethylene material such as a high-pressure radical polymerization-processed low-density polyethylene, which satisfies a specific parameter blended with a non-additive. The present inventors have found that the above object can be achieved by using an extruded laminate obtained by extruding and laminating the composition on a substrate, or using the extruded laminate as a container, a bag, or the like, thereby completing the present invention.

That is, the extruded laminate of the present invention comprises (A) 100 to 10% by weight of an ethylene (co) polymer satisfying the following requirements (a) to (d):
(B) a resin material containing 0 to 90% by weight of another polyethylene-based resin, and an additive which is not mixed with the resin material or which does not substantially migrate to a contacted object; Halogen content in resin material is 10pp
m is formed by extrusion lamination of a resin composition having a particle size of m or less. (A) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 100 g / 10 minutes,
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5;
(D) Difference between the temperature T _{25 at} which 25% of the whole is eluted and the temperature T _{75 at} which 75% of the whole is eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous temperature elution fractionation method (TREF) T ₇₅ −T ₂₅ and density d satisfy the relationship of the following (Equation 1) (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644

Further, the (A) ethylene (co) polymer is an ethylene (co) polymer which further satisfies the following requirements (e) and (f): It is a laminate. (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 (A) ethylene (co) polymer further comprises (A2) an ethylene (co) polymer satisfying the following requirements (g) and (h): It is a laminate. (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) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (h) One or two melting point peaks And the highest melting point T _ml and density d satisfy the relationship of the following (Equation 5) (Equation 5) T _ml ≧ 150 × d−17 Also, the ethylene (co) polymer (A2) is And a clean extruded laminate characterized by further satisfying the following requirement (i). (I) The melt tension (MT) and the melt flow rate (MFR) satisfy the following (Equation 6). (Equation 6) logMT ≦ −0.572 × logMFR + 0.3 Further, (A) ethylene (co) A clean extruded laminate characterized in that the polymer is produced in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the Periodic Table. . Further, the clean extruded laminate is characterized in that the substrate is at least one of paper, plastic, and metal foil.

The container of the present invention is a container or a bag using the above-mentioned clean extruded laminate. Further, the paper container of the present invention has at least a paper layer and / or a barrier layer and a heat seal layer, and the heat seal layer comprises the above-mentioned specific resin composition of the present invention as an innermost layer. Things. Further, the paper container of the present invention is laminated in the order of plastic layer (outermost layer) / paper layer / adhesive layer / barrier layer / heat seal layer (innermost layer), and at least one of the polyolefin layer, the adhesive layer and the heat seal layer. It is characterized in that seeds are formed from the specific resin composition of the present invention. Further, a medical container or medical bag of the present invention is characterized by using the above-described extruded laminate.

The method for producing a clean extruded laminate is characterized in that at least the base material of the present invention satisfies the following requirements (a) to (d): (A) an ethylene (co) polymer 100 to 1
A resin material containing 0% by weight and (B) 0 to 90% by weight of another polyethylene resin, and an additive that does not contain an additive in the resin material or that does not substantially migrate to a contacted object. A resin composition having a halogen content in the resin material of 10 ppm or less blended at a molding temperature of 240 to
It is characterized by extrusion lamination in the range of 330 ° C. (A) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 100 g / 10 minutes,
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5;
(D) Difference between the temperature T _{25 at} which 25% of the whole is eluted and the temperature T _{75 at} which 75% of the whole is eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous temperature elution fractionation method (TREF) T ₇₅ −T ₂₅ and density d satisfy the relationship of the following (Equation 1) (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The (A) ethylene (co) polymer in the present invention is a homopolymer of ethylene, or ethylene and C3 to C20,
Preferably, it is an ethylene / α-olefin copolymer obtained by copolymerizing an α-olefin having 3 to 12 carbon atoms. As the α-olefin having 3 to 20 carbon atoms, propylene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-
Dodecene and the like. Further, the content of these α-olefins is desirably generally selected in a range of 30 mol% or less, preferably 3 to 20 mol% or less.

The (a) density of the ethylene (co) polymer (A) in the present invention is in the range of 0.86 to 0.97 g / cm ³ , preferably 0.89 to 0.95 g / cm ³ .
If the density is less than 0.86 g / cm ³ , rigidity (lumbar strength) and heat resistance will be poor. In addition, the density is 0.97
If it exceeds g / cm ³ , tear strength, impact resistance and the like will be insufficient.

In the present invention, (A) the ethylene (co) polymer (b) melt flow rate (hereinafter referred to as MFR)
Is from 0.01 to 100 g / 10 min, preferably from 0.1 to 100 g / 10 min.
The range is 50 g / 10 min, more preferably 1.0 to 30 g / min. When the MFR is less than 0.01 g / 10 minutes,
Moldability is poor, and if it exceeds 100 g / 10 minutes, tear strength, impact resistance, etc. are poor.

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

The ethylene (co) polymer (A) in the present invention can be obtained, for example, from the integrated elution curve of the elution temperature-elution amount curve (TREF) as shown in FIG. the difference T ₇₅ -T ₂₅ and the density d of the temperature T ₇₅ to 25 percent of the total obtained 75% of the total temperature T ₂₅ eluting elutes is, 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) is added so that the sample concentration becomes 0.05% by weight, and heated and dissolved at 140 ° 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.

In the present invention, the (A) ethylene (co) polymer further satisfies the following requirements (e) and (f): (A1) an ethylene (co) polymer, or (g) And (A2) an ethylene (co) polymer satisfying the requirements of (h).

In the (A1) ethylene (co) polymer of the present invention, (e) the amount X (% by weight) of the ODCB-soluble component at 25 ° C., the density d and the MFR are represented by the following (formula 2) and (formula 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 matter at 25 ° C. is a high branching degree component and a low molecular weight component contained in the ethylene (co) polymer, which causes a decrease in heat resistance and a sticky surface of a molded product, and a problem of hygiene. It is desirable that this content be low because it causes blocking of the inside of the molded article and the like. O
The amount of DCB 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.

In the present invention, the (A1) ethylene (co) polymer is prepared by (f) a continuous heating elution fractionation method (TRE).
In the elution temperature-elution amount curve obtained by F), a plurality of peaks are present. It is particularly preferred that the plurality of peak temperatures be between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the degree of crystallinity, and improves the heat resistance and rigidity of the laminate, the container, and the like.

Here, as shown in FIG. 1, the (A1) ethylene (co) polymer was subjected to a continuous heating elution fractionation method (TR).
In the elution temperature-elution amount curve obtained by EF), a specific ethylene / α-olefin copolymer has a plurality of peaks substantially. On the other hand, the ethylene copolymer shown in FIG.
This is an ethylene / α-olefin copolymer having substantially one peak in the elution amount curve, and corresponds to a conventional typical metallocene catalyst-based ethylene copolymer.

As shown in FIG. 3, the (A2) ethylene (co) polymer in the present invention has one peak of the elution temperature-elution amount curve obtained by (g) continuous heating elution fractionation method (TREF). , T ₇₅ -T ₂₅ and density d satisfy the relationship of the following (Equation 4). (Equation 4) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 T ₇₅ −T ₂₅ and the density d If the relationship of the above (Equation 4) is not satisfied, the heat seal strength and the heat resistance will be inferior.

The (A2) ethylene (co) polymer of the present invention has (h) one or two melting point peaks, and the highest melting point T _ml and density d of the following (formula 5) It satisfies the relationship. (Formula 5) _Tml ≧ 150 × d−17 If the melting point T _m1 and the density d do not satisfy the relationship of the above (Formula 5), the heat resistance will be poor.

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

As shown in FIG. 3, the (A2) ethylene (co) polymer has one TREF peak as shown in FIG. Formula (4) is not satisfied, and is distinguished from a conventional typical metallocene-based catalyst-based ethylene copolymer.

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

In the production of the ethylene (co) polymer (A) in the present invention, it is particularly desirable to polymerize with a catalyst obtained by mixing the following compounds a1 to a4. a1: Compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr (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 compound 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 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 organolithium compounds such as methyllithium and ethyllithium; organomagnesium 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, propylcyclopentadiene, butylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1-methyl-3- Ethylcyclopentadiene, 1-methyl-3-propylcyclopentadiene, 1-methyl-3-butylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-
C5-C24 cyclopolyene or substituted cyclopolyene such as 1-indene, 4,7-dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentane Examples include dienyl silane, biscyclopentadienyl silane, triscyclopentadienyl silane, monoindenyl silane, bisindenyl silane, and trisindenyl silane.

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.

[0041] As the boron compound, decaborane, dicarbamoyl nona _{borane, Ag [CB 11 H 1 2} ], Ph 3 C [C 2
B ₉ H ₁₂ ], Ph ₃ C [Co (C ₂ B ₉ H ₁₂ ) ₂ ], Ph ₃ [C
B ₁₁ H ₁₂ ], Ph (CH ₂ ) ₂ NH [C ₂ B ₉ H ₁₂ ], Ph
(CH ₂ ) ₂ NH [CB ₁₁ H ₁₂ ], Ph (CH ₂ ) ₂ NH [Co
(C ₂ B ₉ H ₁₁ ) ₂ ].

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 method for producing the ethylene (co) polymer (A) according to the present invention is carried out by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, etc., in the presence of the catalyst, substantially in the absence of a solvent. In a state where oxygen, water, etc. are substantially turned off, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane It is produced in the presence or absence of an inert hydrocarbon solvent exemplified as above. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to
To 200 ° C, more preferably 50 to 110 ° C,
The polymerization pressure is usually from normal pressure to 70 kg / cm ^{2 in} the case of the low and medium pressure method.
G, preferably normal pressure to 20 kg / cm ² G, the case of high pressure process typically 1500 kg / cm ² G or less.
The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high-pressure method, it is usually 1 minute to 30 minutes, preferably about 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a single-stage polymerization method, as well as a multi-stage polymerization method of two or more stages in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other. As a particularly preferred production method, a method described in JP-A-5-132518 is exemplified.

The ethylene (co) polymer (A) in the present invention has a halogen concentration of at most 10 ppm, preferably at most 5 ppm by using a catalyst having no halogen such as chlorine in the above-mentioned catalyst components. , More preferably substantially 2 ppm or less (ND: Non-D
etect). By using such an ethylene (co) polymer which is free of halogen such as chlorine and has a low low-density component, there is no need to use an acid neutralizing agent (halogen absorbing agent) as in the prior art, and chemical It is possible to provide a clean extruded laminate excellent in stability and hygiene and particularly suitably used in the field of food packaging materials and the like, and a container using the extruded laminate.

As the other polyethylene resin (B) in the present invention, an ethylene (co) polymer obtained by a high-pressure radical polymerization method, a Ziegler-type catalyst, a Phillips-type catalyst, a metallocene-based catalyst, or the like, a high / medium / low pressure method. And other examples include a homopolymer of ethylene and a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms by a known method. Particularly, low-density polyethylenes obtained by radical polymerization are preferred. Further, in polyethylenes obtained by ionic polymerization of a Ziegler catalyst, etc.,
It is desirable to use a resin which has been sufficiently dehalogenated.

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

The MFR of the LDPE is 0.01 to 10
0 g / 10 min, preferably 0.1 to 50 g / 10 min, more preferably 1.0 to 30 g / 10 min.
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 0.1 to 0.94 g / cm ³ .
It is in the range of 91 to 0.935 g / cm ³ . Within this range, the melt tension is in an appropriate range, and the moldability is improved. The melt tension of LDPE is:
The amount is 5 to 25 g, preferably 3 to 20 g, and more preferably 3 to 15 g. Further, the molecular weight distribution Mw /
Mn is 3.0 to 12, preferably 4.0 to 8.0.

The above-mentioned ethylene / vinyl ester copolymer means ethylene-based vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, which is produced by high-pressure radical polymerization. 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 100 g / 10 minutes,
Preferably it is in the range of 0.1 to 50 g / 10 min, more preferably 1.0 to 30 g / 10 min.

The copolymer of ethylene with 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.

Ethylene homopolymers or ethylene and carbon atoms of 3 by a high / medium / low pressure method using the Ziegler type catalyst, film Lips type catalyst, metallocene catalyst or the like (hereinafter referred to as Ziegler type catalyst etc.) and other known methods. Examples of the copolymer with α-olefins having a density of 0.92 to 0.97 g / cm ³ include:
Linear low-density polyethylene (LLDPE) having a density of 0.91 to 0.94 g / cm ³ , a density of 0.86 to 0.91
g / cm ³ of very low density polyethylene (VLDPE), a density of 0.86~0.91g / cm ³ Ethylene-propylene copolymer rubber, and ethylene-propylene-diene copolymer rubber ethylene-alpha-olefin Copolymer rubbers can be mentioned.

LLDPE using the Ziegler-type catalyst or the like
Is ethylene • α having a density of 0.91 to 0.94 g / cm ³ , preferably 0.91 to 0.93 g / cm ^3.
-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.

The ultra low density polyethylene (VLDPE) using the Ziegler type catalyst or the like has a density of 0.86
０．９0.91 g / cm ³ , preferably 0.88 to 0.90
An ethylene / α-olefin copolymer in the range of 5 g / cm ³ , which 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 clean extruded laminate of the present invention comprises (A)
It is made of a resin material containing 100 to 10% by weight of an ethylene (co) polymer and 0 to 90% by weight of another polyethylene resin (B). When (A) the ethylene (co) polymer is less than 10% by weight or (B) the other polyethylene-based resin exceeds 90% by weight, flexibility, tear strength, heat fusibility, chemical resistance, and low-temperature heat sealing. There is a possibility that characteristics such as properties may be impaired.

The present invention also relates to the present invention, wherein 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 crosslinking agent, etc. Known additives are not blended, or, even if additives are blended in the resin composition,
The blended additive is characterized in that it is an additive that does not substantially migrate to the contacted object such as the contents. In the present invention, an additive that elutes to the outside, for example, when the content is a liquid, an additive that is eluted in the liquid, an additive in which odor is transferred, or with time Additives and the like that are unevenly distributed on the film surface, and the additive is not contained in the resin material, thereby reducing odor, sanitary, and a clean extruded laminate,
Containers and bags 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 deteriorate the contacted object (contents, etc.)
Further, it is an additive that can be added within a range that does not substantially impair the properties of the clean extruded laminate of the present invention. Common inorganic fillers include calcium carbonate, talc, silica, clay, carion, alumina, aluminum hydroxide, magnesia, magnesium hydroxide, calcium sulfate, calcium sulfite, barium sulfate, aluminum silicate, calcium silicate, sodium silicate, silicate potassium,
Examples include magnesium carbonate, barium carbonate, 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 are appropriately selected for the purpose of the present invention depending on the function, application, and the like.

The clean extruded laminate of the present invention is produced by using a halogen-free catalyst, and the (A) ethylene (co) polymer having a low low molecular weight component is added to an antioxidant, an acid neutralizer and the like. Conventional additives are not blended, or the additives to be blended are additives that do not substantially affect the contents to be contacted and the contents, so that they conform to the ministerial ordinance of milk, dairy products such as milk, Bags used in food fields such as fruit juice, tea, sake, etc.
It is suitably used in containers, infusion bags, medical fields for containers, and the like.

The substrate used in the present invention includes a film or a sheet, a plate, and the like. For example, a plastic film or sheet of a polypropylene resin, a polyamide resin, a polyester resin, a saponified ethylene-vinyl acetate copolymer, polyvinylidene chloride, polycarbonate, etc. (stretched products, printed materials, deposited materials of metal, etc., etc.) Metal films or metal plates, cellophane, paper, woven fabric, non-woven fabric, etc. of aluminum, iron, copper, and alloys containing these as main components.

Specific examples of the laminate include SLL / paper, SL
L / Paper / SLL, SLL / OPP, SLL / OPP / S
LL, SLL / PA, SLL / PA / SLL, SLL /
ONY, SLL / ONY / SLL, SLL / PEs, S
LL / PEs / SLL, SLL / OPEs, SLL / O
PEs / SLL, SLL / EVOH, SLL / EVOH
/ SLL, SLL / nonwoven fabric, SLL / Al foil, SLL +
HDPE / paper / SLL. (Where SL
L: (A) ethylene (co) polymer of the present invention, OP
P: biaxially oriented polypropylene, PA: polyamide, ON
Y: biaxially stretched polyamide, PEs: polyester, OP
Es: biaxially oriented polyester, EVOH: saponified ethylene-vinyl acetate copolymer, Al foil: aluminum foil, H
DPE: high density polyethylene)

[0061] In the clean extruded laminate of the present invention, it is preferable that the substrate is composed of a substrate selected from at least one of paper, plastic, and metal foil. Although the reason is not clear, the ethylene (co) polymer of the present invention has practically sufficient adhesive strength even by directly laminating the above-mentioned substrate. This is a phenomenon not seen in conventional linear low-density polyethylene, high-density polyethylene and the like. In particular, in the case of laminating these conventional resins on a barrier base material such as a polyester resin, a polyamide resin, or an aluminum foil, generally, an anchor coating agent, an ethylene- (meth) acrylic acid copolymer, An adhesive such as an acid-modified polyolefin is required. The ethylene (co) polymer of the present invention can be applied without using these adhesives. Therefore, the ethylene (co) polymer or the composition thereof of the present invention can serve not only as the innermost heat seal layer but also as an adhesive between the substrates. Therefore, all layers can be configured in a clean state. Containers or bags using the above-mentioned clean extruded laminate are particularly suitable for liquor containers such as alcohol, and paper containers for storing odor-sensitive contents such as natural water.
Odors such as polyodors and additives are not transferred to the contents, and the commercial value can be improved.

The paper container of the present invention has at least a paper layer and / or a barrier layer and a heat seal layer,
The specific ethylene (co) of the present invention is used as the heat seal layer.
It is preferable that the resin composition using the polymer is constituted by the innermost layer. Further, it is desirable that the paper container is laminated from the outside in the order of outermost layer (plastic) / paper layer / adhesive layer / barrier layer / heat seal layer. Examples of the plastic layer include polyolefin-based resins, polyamide-based resins, polyester-based resins, and the like.Especially inexpensive, versatile polyolefin-based resins, especially low-density polyethylene, linear low-density polyethylene, high-density polyethylene, Polypropylene resins or mixtures thereof can be used, but specific ethylene (co) of the present invention can be used.
It is preferably formed of a polymer.

The resin constituting the adhesive layer includes acid-modified polyolefin, ethylene and (meth) acrylic acid,
Copolymers with unsaturated carboxylic acids such as maleic acid, maleic anhydride and itaconic acid or derivatives thereof, low-density polyethylene, linear low-density polyethylene, specific ethylene (co) polymers of the present invention or compositions thereof Can be used. In particular, the specific ethylene (co) polymer of the present invention or a composition thereof is preferable. Examples of the barrier substrate include polyamide resins, polyester resins, saponified ethylene-vinyl acetate copolymers, polyvinylidene chloride resins, inorganic vapor-deposited plastic films, and metal foils such as aluminum foil.

Examples of the specific configuration of the paper container include PE / paper / SLL / EVOH / SLL and PE / paper /
SLL / AL / SLL, paper / PE / AL / SLL, SL
L / paper / SLL / VM-PET / SLL, etc., any one of the outermost layer, the adhesive layer, and the heat seal layer may be made of SLL, or SLL / paper / SLL /
EVOH / SLL, SLL / paper / SLL / AL / SL
L, paper / SLL / EVOH / SLL, paper / SLL / AL
/ SLL, SLL / paper / SLL / VM-PET / SLL
S for the outermost layer, adhesive layer and heat seal layer.
The configuration using LL may be used. (here,
PE: polyethylene, SLL: (A) ethylene (co) polymer in the present invention, EVOH: saponified ethylene-vinyl acetate copolymer, AL: aluminum foil, VM-PE
T: indicates metal-deposited polyester)

In the medical container or medical bag of the present invention, a laminate of two or three or more layers, linear low-density polyethylene / adhesive / barrier resin / adhesive / linear low-density polyethylene SLL A barrier resin such as / EVOH / SLL or the like is formed from a suitable embodiment of the above-mentioned laminate. By using the extruded laminate and having the same configuration as that of BIB, a clean container having excellent low-temperature heat sealability can be provided.

The production of the clean extruded laminate of the present invention
Forming temperature of 240 on base materials such as paper, plastic and foil
It is manufactured by extrusion lamination in the range of from 330 to 330C, preferably from 260 to 320C, and more preferably from 280 to 310C. In particular, when laminating at a relatively low temperature of about 300 ° C. or less, it is desirable that the molten resin on the surface to be bonded to the substrate is oxidized with air, ozone, or the like. Also, it is desirable that the bonding surface of the base material be subjected to a surface treatment such as a corona discharge treatment. If the molding temperature is lower than 240 ° C., the adhesive strength may not be sufficient,
If the temperature is higher than 330 ° C., deterioration of the resin and the like are not preferred.

The amount of ozone treatment depends on the type of substrate, conditions, etc.
5g / Nm ^Three× 1Nm^Three/ Hr ~
100g / Nm^Three× 20Nm^Three/ Hr, preferably
10g / Nm^Three× 1.5 Nm^Three/ Hr-70g / Nm^Three× 1
0Nm^Three/ Hr, more preferably 15 g / Nm^Three× 2N
m^Three/ Hr ~ 50g / Nm^Three× 8Nm^Three/ Hr range
Selected. The corona discharge treatment amount is 1 to 300 w minutes.
/ M^Two, Preferably 5 to 200 w min / m^Two,further
Preferably 10-100 min / m^TwoIs selected in the range
It is desirable. In particular, ozone treatment and corona discharge treatment
By using them together, it is possible to dramatically improve the adhesive strength.
Can be. Extrusion laminating directly on the substrate, especially as described above
By doing so, it has practically sufficient adhesive strength
Therefore, it is not necessary to use an anchor coat agent and use a solvent.
There is no pollution of working environment due to use. Also, antioxidants,
It has economic advantages such as no need for additives such as acid absorbers.
I do.

[0068]

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

The test method 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) [Heat seal temperature] Since the heat seal temperature changes when the form of the laminate is different, the stretched nylon (ON
y # 15) / Low density polyethylene (LDPE) 25μ /
The configuration of 25 μm of the resin of the present invention was used as a standard sample for heat sealing temperature. A 15-μm-thick nylon base material was subjected to high-pressure LDPE under anchor coating, and the temperature immediately below the T-die was 3
Extrusion lamination was performed at 20 ° C. to a thickness of 25 μm. Further, a heat-sealing layer made of the resin of the present invention is further formed thereon at 280 ° C. for 25 minutes.
It was extrusion laminated with a μm. All line speeds are 100m
/ Min. From now on, heat seal width 15mm,
A test piece having a length of 80 mm is cut out. The test pieces were heat-sealed for 1.0 second and heat-sealed at a pressure of 2.0 kgf.
/ Cm ² , and then with a pulling speed of 30.
A tensile test was performed at 0 mm / min, and the heat seal strength (kg
f / 15 mm width). Heat sealing is performed by changing the sealing temperature at several points, and the heat sealing strength is determined by a tensile test as described above. A graph of the sealing temperature and the heat sealing strength is created, and the heat sealing strength is 3 kgf /
The sheet temperature at which the width became 15 mm was determined, and this temperature was used as the heat sealing temperature. [Substrate Adhesive Strength] Each laminated body assuming a container or the like is formed, and a test piece having a heat seal width of 15 mm and a length of 80 mm is cut out from this. The bonding strength was measured for each bonding surface.

[Halogen concentration] The halogen concentration was measured by a fluorescent X-ray method. When chlorine of 10 ppm or more was detected, this was taken as an analytical value. When it is less than 10 ppm, it is measured with a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd.
(Non-Detect), which is not substantially included.

[Evaluation of Sensory Odor] Each sample resin was prepared by applying a resin temperature of 310 ° C. immediately below the T-die and a line speed of 100 m.
/ Min on 30μ thick aluminum (AL) substrate
The laminated body was formed by sealing a bag having a side of about 20 cm on three sides from the laminate, cured in an oven at 70 ° C. for 3 hours, and further cured at room temperature for 24 hours. Evaluation method is one-to-one
Was given, and one point was added to the one with the strongest smell, and 0.5 points were added to both sides when the ranking was unknown. Finally, all the scores were totaled, and those with a small score were judged as having a good odor. The odor was determined based on the total score of the sensory test by 15 or more panelists. Tables 6 and 7 show the determination results. [Objective Odor Evaluation (S-ODI: Standarddiz)
ed Odor Index method)] Each of the sample resins was subjected to a resin temperature 310 immediately below the T-die.
Extrusion lamination (30 μm) on a 38 μm-thick polyester substrate not subjected to corona treatment at a temperature of 100 ° C. and a line speed of 100 m / min, peeled off the substrate after one day and night, and precisely weighed 6 g into a vial. And filled. Headspace (HS) sampler conditions are 150 ° C x 60
The substance was identified and quantified by gas chromatography / mass spectroscopy (GC-MS). Among the obtained results, the numerical values of the substances considered to contribute to the odor were divided by the threshold value of the odorous substance provided by the Japan Environmental Health Center (S-ODI = concentration of each substance / threshold value of each substance).
This operation is performed in order to reflect the contribution of a substance that is perceived as an odor even in a small amount in the data. Further, these numerical values were added to obtain a value of Σ (S-ODI). The smaller the value, the lower the odor. The results are shown in Table 8.

Various resin components used in the examples are as follows. (A11) The ethylene copolymer was polymerized by the following method. [Preparation of solid catalyst] To a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ), 75 g of indene and 88 g of methylbutylcyclopentadiene were added, and 90 ° C. 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the
The reaction was performed at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration 2.5 mmol /
3200 ml) and stirred for 2 hours. Next, 2000 g of silica (manufactured by Grace, # 952, surface area: 300 m ² / g), which had been calcined at 450 ° C. for 5 hours, was added, followed by stirring at room temperature for 1 hour, followed by nitrogen blowing and drying under reduced pressure at 40 ° C. A solid catalyst (a) having good properties was obtained.

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

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

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

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

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

(MLL) Ethylene-hexene-1 copolymer using a general metallocene catalyst Purified toluene was placed in a pressure reactor equipped with a stirrer replaced with nitrogen, then 1-hexene was added, and bis (n-butyl) was further added. After adding a mixed solution of (cyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) (Al / Zr molar ratio = 500), the temperature was raised to 80 ° C. to prepare a metallocene catalyst. Then, ethylene was added, and polymerization was performed while maintaining the total pressure at 6 kg / cm ³ while continuously polymerizing ethylene.
An ethylene / hexene-1 copolymer (mLL) was produced. The physical properties are shown in Table 1.

(B1) Commercially available branched low density polyethylene (LDPE) by high pressure radical polymerization method: density: 0.918 g / cm ³ , MFR: 7.
0 g / 10 min (B2) Linear low density polyethylene (LLDPE) density with commercially available Ziegler catalyst: 0.910 g / cm ³ , MFR:
10g / 10min

[0080]

[Table 1]

[Example 1] As shown in 2, the ethylene copolymer (A11) 70 parts by weight and the LDPE (B1) 3
After mixing by dry blending with a tumbler mixer without adding an antioxidant and a halogen absorber (calcium stearate), the mixture was pelletized at 170 ° C. The above resin composition was laminated on a nylon / LDPE laminated substrate at 280 ° C., and the heat sealing temperature was measured. On the other hand, the above resin composition was laminated on an aluminum foil (# 30AL) base material at a temperature directly below the T-die at 310 ° C. at a line speed of 100 m / min, and the organoleptic odor was evaluated. The results are shown in Tables 2 and 6. In addition, similarly, a laminated polyethylene terephthalate (PET) substrate was peeled off, and S-ODI was evaluated. Table 2 shows the results.
8 is shown.

Example 2 The same operation as in Example 1 was carried out, except that A11 was used instead of A11, and the results are shown in Table 2.

Example 3 The same operation as in Example 1 was performed except that the ethylene polymer was changed to A2 instead of A11. The results are shown in Table 2.

Example 4 A composition having the ratio shown in Table 3 (A11 / B1 = 70/30) was applied to a surface of 150 g of paperboard at 285-295 ° C.
With coco corona treatment 40W · min / m ² · ozone treatment 50g / m
^A 15 μm coat (outermost layer) was used in combination with ³ × 3 m ³ / h. Next, the same composition was treated on the opposite surface with corona treatment at 6 kW to 315-
AL # 7 (barrier layer) as a sand substrate was laminated at 320 ° C with a thickness of 20 µm (adhesive layer). Incidentally, a corona treatment of 40 W · min / m ² was used on the paper side. The A11 / B1 = 70/30 composition was further applied to the AL surface of the laminate at 280 to 290 ° C.
A 30 μm coating (sealing layer) was performed while performing ozone treatment at 50 g / m ³ × 3 m ³ / h. Line speed is 150m /
min. Using this laminate, one side is about 25cm
Make a tetrahedral container, fill it with mineral water,
After sealing, the plate was placed in an atmosphere at 70 ° C. for 6 hours, and after curing at room temperature for 24 hours, the taste was checked. The results are shown in Table 3.

Example 5 A composition having a ratio shown in Table 3 (A11 / B1 = 70/30) was applied to a surface of 150 g of paperboard at 285-295 ° C.
Corona treatment at 40 W / min / m ² and ozone treatment at 50 g / m ³
A coating of 15 μm (outermost layer) was used in combination with × 3 m ³ / h. Next, the same composition was treated on the opposite surface with corona treatment at 6 kW to 315-
EVOH # 15 (barrier layer) was laminated as a sand substrate at 320 ° C. with a thickness of 20 μm (adhesive layer). still,
EVOH used a corona-treated surface. EV of this laminate
A11 / B1 = 70/30 composition was further added to the OH surface at 280-290.
° C, corona treatment 40W · min / m ² · ozone treatment 50g / m
30 μm coating (seal layer) was performed while ³ × 3 m ³ / h.
The line speed was 150 m / min. Using this laminate, a tetrahedral container having a side of about 25 cm was prepared, filled with mineral water, sealed, placed in a 70 ° C. atmosphere for 6 hours, further cured at room temperature for 24 hours, and taste was checked. The results are shown in Table 3.

Example 6 Using 150 g of paperboard as a base material,
The compositions having the ratios (A12 / B1 = 70/30) shown in Table 3 were 315 to 3
20μm thick at 20 ℃ (adhesive layer), as a sand substrate
Using SiO ₂ VM-PET # 12 (barrier layer), it was laminated on the deposition surface. Incidentally, a corona treatment of 40 W · min / m ² was used on the paper side. The PET surface of this laminate was further coated with a 30 μm composition of A12 / B1 = 70/30 at 280 to 290 ° C., corona treatment 40 W · min / m ² , ozone treatment 50 g / m ³ × 3 m ³ / h (sealing layer). )did. Line speed is 150m / min
Met. Using this laminate, a tetrahedral container having a side of about 25 cm was prepared, filled with mineral water, sealed, placed in a 70 ° C. atmosphere for 6 hours, further cured at room temperature for 24 hours, and taste was checked. The results are shown in Table 3.

Example 7 Table 3 shows the results on the surface of 150 g of paperboard.
The composition at the indicated ratio (A2 / B1 = 70/30) was subjected to 285-295 ° C.
Corona treatment at 40 W / min / m^Two・ Ozone treatment 50g / m^Three
× 3m^Three/ H combined to form a 15 μm coat (outermost layer). Next
On the opposite side, the composition shown in Table 3 (A2 / B1 = 70/30)
The product was made to have a thickness of 20 μm (adhesive layer) at 315 to 320 ° C.
SiO as a sand substrate_TwoUsing VM-PET # 12 (barrier layer),
Laminated on the wearing surface. The paper side has a corona treatment of 40 W
・ Min / m^TwoWas used in combination. A2 / B1 is added to the PET surface of this laminate.
= 70/30 composition at 280-290 ° C, corona treatment 40W
Min / m^Two・ Ozone treatment 50g / m ^Three× 3m^Three/ 3 while doing
Coating (seal layer) of 0 μm was performed. Both line speeds
It was 150 m / min. Using this laminate, one side
Make a 25cm tetrahedral container and add mineral water
After sealing, leave in an atmosphere of 70 ° C. for 6 hours,
After curing at room temperature for 24 hours, the taste was checked. Table 3 shows the results
Shown in The taste was particularly good.

Comparative Example 1 The same operation as in Example 1 was performed except that the ethylene polymer was changed to mLL instead of A11. The results are shown in Table 4. Although the heat sealing temperature and the odor are not inferior to those of the examples, they contain halogen and have a problem in cleanliness.

Comparative Example 2 The same operation as in Example 1 was performed except that the ethylene polymer was changed to B2 instead of A11. The results are shown in Table 4. Heat sealing temperature is slightly inferior. In addition, both S-ODI and functional odor were inferior to the examples,
In addition, smoke was slightly generated during molding, and there was a problem in cleanliness.

Comparative Example 3 The same operation as in Example 3 was performed, except that the composition was changed to B1 alone. The results are shown in Table 4. Poor heat seal temperature. Further, both the S-ODI and the sensory odor were inferior to those of the examples, and the amount of smoke generated during molding was rather large, and there was a problem in cleanliness.

Comparative Example 4 The same operation as in Example 4 was performed except that the composition was changed to B1 alone. Table 5 shows the results. Both the adhesive layer and the seal layer had poor adhesive strength to the aluminum substrate.

Comparative Example 5 The composition was prepared in the form of mLL / B1 = 70 /
Except that the setting was 30, the same operation as in Example 4 was performed.
Table 5 shows the results. The adhesive strength to the aluminum substrate was slightly inferior.

Comparative Example 6 The same operation as in Example 4 was performed except that the composition was changed to B1 alone. Table 5 shows the results. Both the adhesive layer and the seal layer had poor adhesion to the EVOH substrate of the barrier layer.

Comparative Example 7 The composition was prepared in the form of mLL / B1 = 70 /
Except that the setting was 30, the same operation as in Example 4 was performed.
Table 5 shows the results. For the EVOH substrate of the barrier layer,
Both the adhesive layer and the seal layer had poor adhesion.

Comparative Example 8 The composition was prepared in the form of mLL / B1 = 70 /
Except that the setting was 30, the same operation as in Example 5 was performed.
Table 5 shows the results. The adhesion layer was inferior to the silica-deposited surface, and the seal layer was inferior to the polyester (PET) surface.

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

[Table 5]

[0100]

[Table 6]

[0101]

[Table 7]

[0102]

[Table 8]

[0103]

As described above, in the clean extruded laminate of the present invention, (A) the ethylene (co) polymer 1 which satisfies the above-mentioned requirements (a) to (d) is used as a base material.
00 to 10% by weight and (B) other polyethylene resin 0
And a resin material containing no more than 90% by weight, and an additive that does not contain an additive in the resin material or that does not substantially migrate to a contacted object, and that the halogen content in the resin material is 10 ppm. A clean extruded laminate characterized in that the following resin composition is formed by extrusion lamination, excellent in tear strength, impact resistance, low-temperature heat sealability, transparency, moldability, etc. It is suitable for fields requiring clean containers such as medical and electronic materials, especially for food containers and the like that comply with ministerial ordinances such as milk.

Further, if the (A) ethylene (co) polymer is an (A1) ethylene (co) polymer which further satisfies the above requirements (e) and (f), a clean extruded laminate is provided. In addition, the heat resistance, hygiene and rigidity of the container are further improved. Further, if the (A) ethylene (co) polymer further satisfies the requirements (g) and (h) of (A2) ethylene (co) polymer, the above-mentioned clean extruded laminate,
The heat resistance, heat seal strength, and low temperature heat sealability of the container are further improved.

The ethylene (co) polymer (A) may be an ethylene (α) -α-olefin in the presence of a catalyst containing at least a conjugated double bond-containing organic cyclic compound and a transition metal compound of Group IV of the periodic table. If it is a linear ethylene copolymer obtained by copolymerizing, mechanical properties such as a clean extruded laminate, heat sealing properties, heat blocking properties,
Heat resistance is further improved.

The extruded laminate, which is one aspect of the clean of the present invention, is excellent in tear strength, impact resistance, low-temperature heat sealability, transparency, moldability, etc., and is suitable for cleaning foods, medical supplies, electronic materials and the like. It is suitable for a field requiring a special container or the like, particularly for a food container or the like which complies with a ministerial ordinance such as milk.

Further, the method for producing a clean extruded laminate according to the present invention comprises: (A) 100 to 10% by weight of an ethylene (co) polymer satisfying the requirements (a) to (d);
(B) an additive containing 0 to 90% by weight of another polyethylene-based resin, wherein the compounded additive does not substantially migrate to the contacted object, or the additive is not compounded, and halogen is contained. Since it is a method of molding a resin material having a concentration of 10 ppm or less at a low molding temperature of 240 to 330 ° C., it is excellent in tear strength, impact resistance, low-temperature heat sealability, transparency, molding processability, etc. It is possible to obtain a clean extruded laminate suitable for fields requiring clean containers and the like for medical and electronic materials and the like, particularly for food containers and the like that comply with ministerial ordinances such as milk.

[0108]

[Brief description of the drawings]

FIG. 1 is a graph showing an elution temperature-elution amount curve of an ethylene (co) polymer (A1) 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 the (A2) ethylene (co) polymer in the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/04 C08L 23/04 // B29K 23:00 B29K 23:00 105: 08 105: 08 105: 22 105: 22 B29L 31:56 B29L 31:56 (72) Inventor Tatsuyuki Kamiya 2-3-2, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Polyolefin Co., Ltd. Research and Development Center (72) Inventor Yuichi Orikasa Japan Polyolefin Co., Ltd., Research and Development Center, 2-3-2 Yaiko, Kawasaki-ku, Kawasaki, Kanagawa Prefecture (72) Inventor Masahiro Wakayama 2-3-2, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Polyolefin Co., Ltd. Inside the R & D Center (72) Inventor Takumi Araki 2-3-2 Nikko, 2-chome, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Fin Technology Co., Ltd. R & D Center

Claims (11)

[Claims] 1. An ethylene (co) polymer 1 which satisfies the following requirements (a) to (d) at least on a substrate:
00 to 10% by weight and (B) other polyethylene resin 0
And a resin material containing no more than 90% by weight, and an additive that does not contain an additive in the resin material or that does not substantially migrate to a contacted object, and that the halogen content in the resin material is 10 ppm. A clean extruded laminate characterized in that the following resin material layer is formed by extrusion lamination. (A) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 100 g / 10 minutes,
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5;
(D) Difference between the temperature T _{25 at} which 25% of the whole is eluted and the temperature T _{75 at} which 75% of the whole is eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF) T ₇₅ −T ₂₅ and density d satisfy the relationship of the following (Equation 1) (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644 2. The ethylene (co) polymer (A) further satisfies the following requirements (e) and (f) (A1):
2. An ethylene (co) polymer.
A clean extruded laminate as described. (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) 3. The ethylene (co) polymer (A) further satisfies the following requirements (g) and (h) (A2):
2. An ethylene (co) polymer.
A clean extruded laminate as described. (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) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (h) One or two melting point peaks And the highest melting point T _ml and density d satisfy the relationship of the following (Equation 5) (Equation 5) T _ml ≧ 150 × d−17 4. The (A2) ethylene (co) polymer,
The clean extruded laminate according to claim 3, further satisfying 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 5. The (A) ethylene (co) polymer produced in the presence of a catalyst containing at least an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table. The clean extruded laminate according to any one of claims 1 to 4, wherein: 6. The clean extruded laminate according to claim 1, wherein the base material is at least one of paper, plastic, and metal foil. 7. A container or bag using the clean extruded laminate according to any one of claims 1 to 6. 8. A heat-sealing layer comprising at least a paper layer and / or a barrier layer and a heat-sealing layer.
The paper container as described. 9. The paper container according to claim 7, wherein the paper container is laminated in the order of plastic layer / paper layer / adhesive layer / barrier layer / heat seal layer. 10. A medical container or medical bag using the extruded laminate according to claim 6. 11. An ethylene (co) polymer 1 (A) which satisfies the following requirements (a) to (d) at least on a substrate:
00 to 10% by weight and (B) other polyethylene resin 0
And a resin material containing no more than 90% by weight, and an additive that does not contain an additive in the resin material or that does not substantially migrate to a contacted object, and that the halogen content in the resin material is 10 ppm. Molding temperature 2
A method for producing a clean extruded laminate, wherein extrusion lamination is performed at a temperature in the range of 40 to 330 ° C. (A) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 100 g / 10 minutes,
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5;
(D) Difference between the temperature T _{25 at} which 25% of the whole is eluted and the temperature T _{75 at} which 75% of the whole is eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF) T ₇₅ −T ₂₅ and density d satisfy the relationship of the following (formula 1) (formula 1) T ₇₅ −T ₂₅ ≦ −670 × d + 6
44