JP4877768B2 - Laminated body and packaging bag using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate having an excellent seal strength and pressure-resistant strength, and allowing high-speed packing over a wide temperature range from low to high temperatures. <P>SOLUTION: The laminate consists of a layer of a resin composition A and a layer of a resin composition B, which overlie a substrate in this order. The resin compositions A, B each meet the following physical property. The resin composition A is composed of a copolymer of ethylene with a 3-20C &alpha;-olefin and HPLD and meets the conditions of: (A1) meeting specified peak temperature characteristics in the elution curve with TREF; (A2) having a density of 0.90-0.93 g/cm<SP>3</SP>; and (A3) having an MFR of 0.1-1,000 g/10 min. The resin composition B is composed of a copolymer of ethylene with a 3-20C &alpha;-olefin and HPLD and meets the conditions of: (B1) meeting specified elusion characteristics in the elusion curve with TREF; (B2) having a density of 0.88-0.92 g/cm<SP>3</SP>; and (B3) having an MFR of 1-100 g/10 min. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a laminate using a polyethylene resin composition and a packaging bag using the same. Specifically, when used as a sealing layer for packaging materials for liquids and mucilages in die roll type automatic filling machines, etc., a laminate capable of high-speed liquid filling in a wide temperature range from low temperature to high temperature and the same were used. It relates to packaging bags.

  Conventionally, packaging of liquids and mucilages, and liquids and mucilages containing solids such as fibers and powders as insoluble substances, various intermediate layers are laminated on the substrate as necessary, A laminated film obtained by laminating a sealant layer thereon is used. As such a laminated film, a packaging film is known in which a sealant layer is provided on a surface base material layer made of polyamide resin, polyethylene terephthalate resin, paper, aluminum foil, etc., and the heat sealability of this sealant layer is utilized. ing.

As a resin used for this sealant layer, for example, a random copolymer of ethylene / C _4-10 α-olefin having specific physical properties and high-pressure low-density polyethylene (hereinafter sometimes abbreviated as HPLD) may be used. A blend composition has been proposed (see Patent Document 1). Specifically, an ethylene-4-methyl-1-pentene random copolymer produced with an Mg-Ti catalyst has been proposed as the random copolymer, but the disadvantage is that the foaming start temperature of the lateral seal portion is low. There is.

Further, a blend composition of ethylene / C _3-18 α-olefin copolymer and HPLD exhibiting specific temperature rising elution fractionation (hereinafter sometimes abbreviated as TREF) characteristics has been proposed (Patent Document 2). reference). Specifically, linear low-density polyethylene (such as an ethylene / 1-hexene copolymer) produced with a metallocene catalyst has been proposed as the above-mentioned copolymer. Because it is sealed as a contaminant, the pressure and heat received from the heat sealer will cause a resin pool based on the peeling of the base material and the intermediate layer at the seal part (the sealant layer and the intermediate layer are raised in a bump shape) If a seal failure occurs due to generation, while the pressure and temperature of the sealer are lowered, a seal failure occurs due to insufficient low-temperature heat sealability and hot tackiness of the sealant layer, resulting in reduced seal strength, reduced pressure strength, and foreign matter inclusion Liquid leakage or the like is likely to occur, and as a result, the filling speed could not be increased.

Also, a blend composition of a random copolymer of ethylene / C _4-10 α-olefin having specific physical properties and HPLD has been proposed (see Patent Document 3). Specific examples of the random copolymer include linear low density polyethylene (ethylene / 1-hexene copolymer, ethylene / 1-butene copolymer, ethylene / 1-octene copolymer, etc.) produced with a metallocene catalyst. However, as in the case of the above-mentioned Reference Document 2, there is a drawback in that a seal failure is likely to occur due to insufficient low temperature heat sealability and hot tackiness. The reason for the poor heat sealability is that only one kind of linear low density polyethylene to be mixed with HPLD is used, and the distribution of components having different solubility characteristics in a solvent is narrow.

  In view of such a problem, a coextruded multilayer film for bonding in which a specific three-layer structure film composed of an inner layer, an intermediate layer, and an outer layer is coextruded on a base material layer has been proposed (see Patent Document 4). However, this laminated film has an advantage of excellent impact resistance, but has a problem that it cannot be filled with a liquid filling machine. Reference 4 shows a prescription in which a linear low density polyethylene produced using a Ziegler-based catalyst is blended in the inner layer, and a considerable amount of highly crystalline components are present in the linear low density polyethylene. This is considered to be the cause of the problem.

  In addition, a three-layer structure film has been proposed in which an intermediate layer having specific physical properties composed of a blend of linear low density polyethylene and HPLD is provided on the base material layer, and a normal sealant layer is provided on the outer layer (see Patent Document 5). ). However, the laminated film produced by this method is a bag-made product and has an advantage of having a high bag breaking strength, but has a problem that it is inferior in filling suitability in a liquid filling packaging machine. As described above, it is considered that the problem is caused by the narrow distribution of components having different solubility characteristics in the solvent.

Further, a packaging laminate having a three-layer structure in which a random copolymer of ethylene / C _3-10 α-olefin having specific thermal properties is used as an intermediate layer and a sealant layer and the thickness is specified has been proposed ( (See Patent Document 6). As the sealant layer, it is described that HPLD may be added to the random copolymer in an amount of 0 to 70% by weight, but no specific example is shown. This laminated film has the advantage that high-speed liquid filling suitability under certain conditions can be obtained, but there is a problem that high-speed liquid filling suitability cannot be obtained at a wide range of sealing temperatures. As described above, it is considered that the problem is caused by the narrow distribution of components having different solubility characteristics in the solvent.

  Therefore, it is necessary to adjust the setting conditions of the filling device in order to cope with various contents, differences in the base material, etc., but in the conventional one, the allowable range in each packaging material is narrow, and the filling conditions are changed each time. Problems such as the need to search are not solved.

Japanese Patent Publication No. 2-4425 JP-A-7-26079 JP-A-8-269270 JP-A-10-323948 Japanese Patent Laid-Open No. 11-10809 JP-A-11-254614

  In view of the above-mentioned problems, the object of the present invention is excellent in sealing strength when used in combination with a specific polyethylene-based resin composition in an intermediate layer and a sealing layer of a liquid or viscous packaging material, and from a low temperature. An object of the present invention is to provide a combination of polyethylene resin compositions that enables high-speed filling in a wide temperature range up to a high temperature.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition comprising an ethylene / α-olefin copolymer having a specific composition and physical properties and a high-pressure low-density polyethylene is liquid by extrusion laminating or the like. The present inventors have found that the above problems can be solved when used as an intermediate layer and a sealing layer of a viscous packaging material.

That is, the gist of the present invention is that a layer made of the resin composition A and a layer made of the resin composition B are laminated in this order on the base material, and the resin compositions A and B are respectively It exists in the laminated body characterized by satisfy | filling a physical property.
Resin composition A: a polyethylene resin composition comprising a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms and high-pressure low-density polyethylene (HPLD) and satisfying the following (A1) to (A3) .
(A1) In the elution curve obtained by temperature-temperature elution fractionation (TREF) using orthodichlorobenzene as a solvent, the following (Ai) to (Aiv) are satisfied.
(Ai) Number of peaks is 3 or more (Aii) Maximum peak temperature (Tha) is 85 to 100 ° C.
(Aiii) The minimum peak temperature (Tla) is 30 to 65 ° C.
(Aiv) The total amount of the eluate amount (Sla) having an elution temperature of 0 to (Tla + 6) ° C. and the eluate amount (Sha) having an elution temperature of (Tha-6) to 120 ° C. is 15 to 15% of the total eluate amount (Sta). 40% by weight
(A2) Density is 0.90 to 0.93 g / cm ³
(A3) Melt flow rate (MFR) 0.1 to 1000 g / 10 min Resin composition B: Comprising a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and HPLD, the following (B1) A polyethylene resin composition satisfying (B3).
(B1) In an elution curve obtained by TREF using orthodichlorobenzene as a solvent, the following (Bi) to (Biv) are satisfied.
(Bi) The proportion of eluate (S1b) having an elution temperature of 40 ° C. or lower is 45 to 65% by weight.
(Bii) The ratio of the eluate (S2b) having an elution temperature of 40 to 60 ° C. is 10 to 30% by weight.
(Biii) The ratio of the eluate (S3b) having an elution temperature of 60 to 80 ° C. is 10 to 35% by weight.
(Biv) The ratio of eluate (S4b) having an elution temperature of 80 ° C. or higher is 0 to 2% by weight (B2) The density is 0.88 to 0.92 g / cm ³
(B3) Melt flow rate (MFR) is 1 to 100 g / 10 min

Another gist of the present invention is that, in the resin composition A, the copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is 5 to 20 having a density of 0.87 to 0.90 g / cm ³ . Weight%, density 0.90-0.92 g / cm ³ 40-70 wt%, density 0.92-0.94 5-10 wt%, and HPLD density 0.91-0 The laminate is characterized by comprising 10 to 40% by weight of .93 g / cm ³ .

Another gist of the present invention is that the resin composition B has a density of 0.86 to 0.89 g / cm ³ as a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. It is characterized by comprising 5% to 35% by weight of one having a density of more than 0.89 to 0.91 g / cm ³ and 10 to 40% by weight having a density of 0.915 to 0.925 g / cm ³ as HPLD. It exists in the said laminated body.

  Another gist of the present invention resides in the above-described laminate, wherein the density of the resin composition A is higher than the density of the resin composition B.

  Another gist of the present invention resides in a packaging bag formed by folding the above laminate with the layer made of the resin composition B inside, and heat-sealing the layer.

  Another gist of the present invention resides in a bag in which the packaging bag is filled with a liquid or a viscous content.

  Another gist of the present invention resides in a bag in which the packaging bag is filled with a liquid having a temperature of 10 to 70 ° C. or a viscous content using a die roll type automatic liquid filling and packaging machine.

  Provided is a resin composition that enables high-speed filling in a wide temperature range from a low temperature to a high temperature when used in a heat seal layer of a liquid or viscous packaging material. Therefore, a useful packaging film can be produced by extrusion lamination, and a packaging material using the film is excellent in sealing strength and pressure strength.

  The laminate of the present invention is a laminate in which a layer made of the resin composition A and a layer made of the resin composition B are laminated in this order on a base material, and the characteristic part is the resin composition A , B composition. First, each component which comprises the resin composition A and its characteristic are demonstrated, and a base material and the lamination | stacking method are mentioned later.

The resin composition A is a polyethylene resin composition composed of an ethylene / α-olefin copolymer and HPLD, and has characteristics (A1), (A2), and (A3). In particular, the TREF characteristic defined by (A1) is a major feature of the present invention.
(Ethylene / α-olefin copolymer)
The α-olefin, which is a random copolymer of ethylene and α-olefin and used as a comonomer, is a 1-olefin having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms. is there. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- 1 etc. can be mentioned. Specific examples of such an ethylene / α-olefin copolymer include ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, and ethylene / 1-octene copolymer.

  The α-olefin used as a comonomer is not limited to one type, and a multi-component copolymer using two or more types like a terpolymer is also preferable. Specific examples include an ethylene / propylene / 1-butene terpolymer and an ethylene / propylene / 1-hexene terpolymer.

The ethylene / α-olefin copolymer preferably has a structural unit derived from ethylene as a main component, and the ethylene content is 50 to 99% by weight, more preferably 60 to 99% by weight, and still more preferably 70 to 99%. It is selected from the range of 99% by weight. Therefore, the α-olefin content is preferably selected from the range of 1 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 1 to 30% by weight. The ethylene content is determined by the ¹³ C-NMR spectrum analysis shown below.

  Measured in a sample (concentration: 300 mg / 2 mL) dissolved in orthodichlorobenzene using hexamethyldisiloxane as a standard substance at a temperature of 120 ° C., a frequency of 100 MHz, a spectral width of 20000 Hz, a pulse repetition time of 10 seconds, and a flip angle of 40 degrees. .

(Method for producing ethylene / α-olefin copolymer)
The ethylene / α-olefin copolymer used in the present invention can be easily produced, for example, by polymerization using a metallocene catalyst. The metallocene catalyst is (i) a transition metal compound of Group 4 of the periodic table (so-called metallocene compound) containing a ligand having a cyclopentadienyl skeleton, and (ii) a stable ionic state by reacting with the metallocene compound. A catalyst comprising an activatable cocatalyst and, if necessary, (iii) an organoaluminum compound, any known catalyst can be used.

(I) Metallocene compounds include, for example, JP-A-58-19309, JP-A-59-95292, JP-A-59-23011, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, JP-A-60-35209, JP-A-61-130314, JP-A-3-163888, etc., EP publication 420,436, US Pat. No. 5,055,438, international publication WO91 / 04257, International Publication WO92 / 07123, and the like.

  More specifically, bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (azurenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) ) Zirconium dichloride, (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadi) Enyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (3,5-dimethylpe Tadienyl) zirconium dichloride, methylenebis (indenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylene 1,2-bis (4-phenylindenyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) Zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (indenyl) zirconium dichloride, dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, Dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydride) Fluorenyl) zirconium dichloride, methylphenylsilylenebis [1- (2-methyl-4,5-benzo (indenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium Dichloride, dimethylsilylenebis [1- (2-methyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylsilylene Bis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl)] zirconium dichloride, diphenylsilylene Screw [1- ( 2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4- (phenylindenyl))] zirconium dichloride, dimethylsilylenebis [1- ( 2-ethyl-4- (phenylindenyl))] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azulenyl)] zirconium dichloride, dimethylgermylenebis (indenyl) zirconium dichloride, dimethyl Zirconium compounds such as germylene (cyclopentadienyl) (fluorenyl) zirconium dichloride can be exemplified. In the above, a compound in which zirconium is replaced with hafnium can be used similarly. In some cases, a mixture of a zirconium compound and a hafnium compound can be used.

The metallocene compound may be used by being supported on an inorganic or organic compound carrier. The support is preferably a porous oxide of an inorganic or organic compound, specifically, an ion-exchange layered silicate, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO. ZnO, BaO, ThO _{2 and the} like, or a mixture thereof.

(Ii) Examples of the cocatalyst used in the present invention include organoaluminum oxy compounds (aluminoxane compounds), ion-exchange layered silicates, Lewis acids, boron compounds, lanthanoid salts such as lanthanum oxide, tin oxide, and the like.

(Iii) Examples of organoaluminum compounds include trialkylaluminums such as triethylaluminum, triisopropylaluminum, and triisobutylaluminum; dialkylaluminum halides; alkylaluminum sesquihalides; alkylaluminum dihalides; alkylaluminum hydrides, organoaluminum alkoxides, and the like. Can be mentioned.

As the polymerization method, any method can be adopted as long as the catalyst component and each monomer come into efficient contact. Specific examples include a slurry method, a gas phase fluidized bed method and a solution method in the presence of these catalysts, or a high-pressure bulk polymerization method in which a pressure is 200 kg / cm ² or more and a polymerization temperature is 100 ° C. or more. . A preferable production method includes a high-pressure bulk polymerization method.

  Such an ethylene copolymer can be appropriately selected from those commercially available as metallocene polyethylene and used. Examples of commercially available products include “Affinity” manufactured by DuPont Dow, “Kernel” and “Harmolex” manufactured by Nippon Polyethylene. An ethylene-type copolymer can be used 1 type or in mixture of 2 or more types. In particular, as described later, an embodiment in which the characteristics of the polyethylene resin composition are controlled by using two or more ethylene / α-olefin copolymers having different densities or MFRs in combination is preferable. This is because the metallocene-catalyzed ethylene-based copolymer has a narrow crystallinity distribution, so that the TREF characteristics can be easily controlled by blending various copolymers.

  The ethylene / α-olefin copolymer is preferably produced using a metallocene catalyst, but can also be produced using a so-called Ziegler catalyst containing titanium and halogen. A metallocene catalyst and a Ziegler catalyst can also be mixed and used. The Q value of the ethylene / α-olefin copolymer is preferably 3.0 or less, particularly 2.5 or less. The weight average molecular weight of the ethylene / α-olefin copolymer is preferably about 50,000 to 80,000, particularly about 55,000 to 75,000. When the weight average molecular weight is smaller than this, the material strength is lowered and the heat sealability is deteriorated. On the other hand, if the weight average molecular weight is larger than this, the extrusion load and high-speed processability at the time of extrusion laminating deteriorate.

(High pressure method low density polyethylene: HPLD)
Another component constituting the resin composition A of the present invention is HPLD. Specifically, it is also referred to as a high pressure radical polymerization method low density polyethylene. HPLD has a high melt elasticity and is often used to improve neck-in particularly during extrusion lamination. The physical properties of HPLD in the present invention are not particularly specified, but the MFR is 0.2 to 80 g / 10 min, particularly 0.5 to 50 g / 10 min, and the density is 0.900 to 0.935 g / cm ³ , particularly 0. The thing of 91-0.93g / cm < ³ > is preferable.

Commercially available products include LC604 manufactured by Nippon Polyethylene (density 0.918 g / cm ³ , MFR 8 g / 10 min), LC600A manufactured by Nippon Polyethylene (density 0.919 g / cm ³ , MFR 7 g / 10 min), LC520 manufactured by Nippon Polyethylene. (Density 0.924 g / cm ³ , MFR 3.5 g / 10 min), L705 (density 0.919 g / cm ³ , MFR 7 g / 10 min) manufactured by Sumitomo Chemical Co., Ltd. and the like can be used.

(Physical properties of resin composition A)
The essential physical properties that the resin composition A of the present invention should have are the following (A1) to (A3). Hereinafter, this will be sequentially described.
(A1) Temperature rise elution fractionation (TREF) characteristics (A2) Density characteristics (A3) Melt flow rate (MFR) characteristics

(A1) Temperature rising elution fractionation (TREF) characteristics The resin composition A needs to have a specific crystallinity distribution derived from an elution curve obtained by TREF using orthodichlorobenzene as a solvent. Temperature rising elution fractionation (TREF) is a method in which a polymer is completely dissolved at a high temperature and then cooled to form a thin polymer layer on the surface of an inert carrier, and then the temperature is increased continuously or stepwise. This is a method in which the eluted component (polymer) is recovered by heating, the concentration is continuously detected, and the amount of the eluted component and the elution temperature are obtained. The graph drawn by the elution fraction (ratio with respect to the total elution amount) and elution temperature is an elution curve, and by this, the composition distribution (crystallinity distribution) of the polymer can be measured.

In the present invention, the resin composition A has the following four points (Ai) to (Aiv).
(Ai) Number of peaks is 3 or more (Aii) Maximum peak temperature (Tha) is 85 to 100 ° C.
(Aiii) The minimum peak temperature (Tla) is 30 to 65 ° C.
(Aiv) The total amount of the eluate amount (Sla) having an elution temperature of 0 to (Tla + 6) ° C. and the eluate amount (Sha) having an elution temperature of (Tha-6) to 120 ° C. is 15 to 15% of the total eluate amount (Sta). 40% by weight

<TREF measurement method>
Next, a specific method of TREF measurement will be described. The column temperature drop rate is adjusted to the rate required for crystallization of the crystalline component contained in the sample at each temperature, and the column temperature increase rate is adjusted to the rate at which dissolution of the eluted component at each temperature can be completed. It is necessary to determine the cooling rate and the heating rate of the column temperature through preliminary experiments. The measurement conditions are as follows.
Equipment: CFC-T102L manufactured by Dia Instruments
GPC column: Showa Denko AD-806MS (3 connected in series)
Solvent: orthodichlorobenzene (ODCB)
Sample concentration: 3 mg / mL
Injection volume: 0.4mL
Crystallization rate: 1 ° C./min Solvent flow rate: 1 mL / min Elution temperature:
0,5,10,15,20,25,30,35,40,45,49,52,55,58,61,64,67,70,73,76,79,82,85,88,91, 94,97,100,102,120,140 each temperature (℃)

<Data analysis of TREF>
An example of the differential elution curve obtained by TREF measurement is shown in FIG. The horizontal axis represents the elution temperature (° C.), and the vertical axis represents the relative differential mass. In FIG. 1, Tpa is the maximum peak temperature (° C), Tla is the minimum peak temperature (° C), Tha is the maximum peak temperature (° C), and Sla (low-temperature hatched portion) has an elution temperature of 0 to 0. The amount of eluate at (Tla + 6) ° C., Sha (high-temperature hatched portion) represents the amount of eluate at an elution temperature of (Tha-6) to 120 ° C. [FIG. 1] shows a TREF elution curve of the resin composition A obtained in Example 1 to be described later. The number of peaks as a whole is 3, and an example in which Tpa = 65 ° C., Tla = 34 ° C., Tha = 89 ° C. It is.

  The chromatogram of the eluted components at each elution temperature obtained by TREF measurement is processed by a data processing program attached to the apparatus, and the eluted amount (proportional to the area of the chromatogram) normalized so that the total is 100%. Desired. In addition, an integrated elution curve for the elution temperature is calculated. The integrated elution curve is differentiated with temperature to obtain a differential elution curve.

  Hereinafter, characteristics (Ai) to (Avii) relating to the TREF elution curve will be sequentially described.

(Ai) The number of peaks is 3 or more.

Apparently, it means a blend of three or more polyethylene resins having different crystallinity. Here, the peak means a peak in the differential elution curve obtained by smoothing and connecting intermittent data points. In addition, the determination of whether or not the value is maximum is obtained by connecting the dF / dT value obtained by the following equation to a certain temperature (T _n ) and the amount of elution (F _n ) at that temperature at intermittent data points. The maximum value shall be taken when the curve passes through zero value from positive to negative. At this time, the dF / dT value was calculated for a portion where the elution temperature was 20 ° C. or higher in consideration of the measurement accuracy.

dF / dT = (F _{n + 1} −F _n ) / (T _{n + 1} −T _n )
Note that smoothing is performed by the least square method. When the number of peaks is 3, the behavior of the blend of low crystal, medium crystal, and high crystal is relatively, and during heat sealing, the low crystal acts as a low-temperature sealing effect, and the medium crystal The product has an effect of an optimal balance effect in a suitable temperature range, and the highly crystalline product has a function of suppressing foaming, thereby expressing a stable sealing characteristic in a wide temperature range. When the number of peaks is 2 or less, it means that there are few components of low / medium / high, and the temperature range that can be sealed becomes narrow or the seal strength becomes weak at a specific seal temperature. .

(Aii) The maximum value (Tha) of the peak temperature is 85 to 100 ° C.

  Tha is preferably 85 to 95 ° C, more preferably 88 to 95 ° C. When Tha is less than 85 ° C., foaming occurs from a low temperature. On the other hand, when the temperature is 100 ° C. or higher, filling suitability at a low temperature cannot be obtained, and good pressure strength cannot be obtained. The peak temperature can be controlled by the type and amount of comonomer, and it is generally preferable to blend or polymerize an ethylene / α-olefin copolymer with the comonomer content adjusted to 3 to 6% by weight.

(Aiii) The lowest peak temperature (Tla) is 30 to 65 ° C.

  Tla is preferably 30 to 50 ° C, more preferably 30 to 40 ° C. When Tla is less than 30 ° C., foaming is likely to occur from a low temperature region, and when it is 65 ° C. or more, filling is impossible from a low temperature. The peak temperature can be controlled by the type and amount of the comonomer, and it is generally preferable to blend or polymerize a polyethylene resin with the comonomer content adjusted to 15 to 25% by weight.

(Aiv) The total amount of the eluate amount (Sla) having an elution temperature of 0 to (Tla + 6) ° C. and the eluate amount having an elution temperature of (Tha-6) to 120 ° C. (Sha) is 15 of the total eluate amount (Sta). ~ 40% by weight.

  That is, the amount of eluate between 0 ° C. and (Tla + 6) ° C. (Sla: hereinafter referred to as low temperature eluate amount) and the elution temperature between (Tha-6) ° C. and 120 ° C. The total amount of the effluent amount (Sha: hereinafter, sometimes referred to as the high temperature side effluent amount) is 15 to 40% by weight, preferably 15 to 30% by weight, more preferably 15%, based on the total effluent amount (Sta). ~ 25% by weight. If it is less than 15% by weight, the optimum temperature range of filling suitability is narrow, and if it exceeds 40% by weight, good pressure resistance cannot be obtained. By being in this range, the components that elute in the temperature range of (Tla + 6) to (Tha-6) do not become excessive and exist in an appropriate amount, which helps to keep the sealing temperature range wide.

(Av) In addition, it is preferable that the resin composition A of the present invention satisfies Sla / Sta ≧ 7% by weight and Sha / Sta ≧ 5% by weight.

  The amount of eluate on the low temperature side (Sla) is preferably 7% by weight or more, more preferably 10% by weight or more of the total amount of eluate (Sta). If Sla is less than 7% by weight, there may be a problem in filling suitability on the low temperature side. On the other hand, the amount of high-temperature eluate (Sha) is preferably 5% by weight or more, more preferably 6% by weight or more of the total amount of eluate. When Sha is less than 5% by weight, filling suitability on the high temperature side, foaming may occur, and defects in appearance may occur.

Sha which is a high temperature side eluate is mainly composed of a high density side component having a density of 0.925 to 0.940 g / cm ³ , and is selected from such components (ethylene / α-olefin copolymer). Sha can be changed by increasing or decreasing the amount of

Sla, which is a low temperature side eluate, is mainly composed of low density side components having a density of 0.880 to 0.890 g / cm ³ , and is selected from such components (ethylene / α-olefin copolymer). Sla can be changed by increasing or decreasing the amount of

(Avi) Furthermore, Tha-Tla = 30 to 60 ° C. is preferable.

  The difference between the maximum peak temperature (Tha) and the minimum peak temperature (Tla) is 30 to 55 ° C, preferably 40 to 55 ° C, more preferably 45 to 55 ° C. If it is less than 30 ° C., the optimum temperature range of filling suitability is narrow, and if it exceeds 55 ° C., there is a possibility that good pressure resistance cannot be obtained.

(Avii) (Sla-Sha) / Sta = -14 to 14% by weight is preferable.

  It is better that the difference between the eluate (Sla) having an elution temperature of 0 to (Tla + 6) ° C. and the eluate (Sha) having an elution temperature of (Tha-6) to 120 ° C. is small. Specifically, it is good to control so that it may become a narrow range of -14 to 14 weight% as a ratio with respect to all the eluates (STA). Preferably it is -10 to 10 weight%, More preferably, it is -7 to 7 weight%. Typically, the high temperature side eluate (Sha) and the low temperature side eluate (Sla) are preferably in the same amount. If it is less than −14% by weight, the optimum temperature range for filling suitability is narrow, and if it exceeds 14% by weight, good pressure resistance may not be obtained.

  Since the TREF data is generally additive, when the polyethylene resin composition of the present invention is produced by mixing several types of copolymers, the TREF data of individual copolymers and high-pressure method low-density polyethylene are used. Based on the above, it is possible to slightly increase / decrease the ratio of the mixture components after predicting the mixture ratio to be a desired TREF pattern.

(A2) Density characteristics The second characteristic of the resin composition A is density characteristics. That is, the density of the resin composition comprising the ethylene / α-olefin copolymer and HPLD needs to be 0.90 to 0.93 g / cm ³ . The density of the resin composition A is preferably 0.905 to 0.925 g / cm ³ , more preferably 0.905 to 0.92 g / cm ³ . If the density is higher than the above range, the low temperature heat sealability is poor. If the density is lower than the above range, it is not preferable because it tends to foam when sealed at a high temperature. Furthermore, in the present invention, the density of the resin composition A is preferably larger than the density of the resin composition B. In the case of the same or vice versa, it is difficult to obtain sufficient liquid filling suitability. The density difference in this case, preferably 0.01 g / cm ³ or more, more preferably 0.01~0.03g / cm ³ order. In addition, the measurement of the density was performed based on JIS-K6922-2: 1997 appendix (23 degreeC).

(A3) Melt flow rate (MFR) characteristic The 3rd characteristic of the resin composition A is a MFR characteristic. That is, the MFR of the resin composition comprising an ethylene / α-olefin copolymer and HPLD is 0.1 to 1000 g / 10 minutes, preferably 0.5 to 100 g / 10 minutes, more preferably 4 to 20 g / 10 minutes. is there. If the MFR is lower than the above range, the extrusion load when the resin is melt-extruded becomes high, and the film surface becomes rough during molding, which is not preferable. If the MFR exceeds the above range, the hot tack property at the time of heat sealing is lowered or the strength when used as a packaging material is lowered, which is not preferable. In addition, the measurement of MFR was performed based on JIS-K6922-2: 1997 appendix (190 degreeC, 21.18N load). In the present invention, the magnitude relationship between the MFR of the resin composition A and the MFR of the resin composition B is not important.

(A4) Swell ratio (SR) characteristic The resin composition A preferably has a swell ratio (SR) of 1.5 or more, more preferably 1.55 or more. When the SR is in the above range, the neck-in at the time of extrusion laminating is less likely to be large, and processing is easy, which is preferable. The upper limit of SR is not particularly limited, but is preferably less than 2.1. When SR exceeds 2.1, workability at high speed may deteriorate. The SR measurement conditions are as follows.
Equipment: Melt indexer nozzle manufactured by Takara Industries Co., Ltd .: L = 8 / D = 2.095 mm
Temperature: 240 ° C
Extrusion rate: 3 g / min (equivalent to 73 sec- ¹ )
Diameter measurement: The extruded strand is received in ethanol at 1 cm below the nozzle, cooled, and the diameter is measured with calipers. SR is calculated from the ratio between the measured diameter and the nozzle diameter (2.095 mm).

  In order to control the properties (A1) to (A3) of the resin composition A to fall within a predetermined range, the type, properties, blending amount, etc. of the ethylene / α-olefin copolymer as a raw material are appropriately selected. . For example, to obtain the resin composition A of the present invention, it is important to control crystallinity and its distribution. The crystallinity is generally controlled by the amount of α-olefin copolymerized, and the crystallinity distribution is generally controlled by the uniformity of the active points of the catalyst. However, it is difficult to obtain the ethylene / α-olefin copolymer of the present invention by polymerizing in a single stage with a single catalyst. A method of polymerizing by blending two or more catalysts giving different crystallinity (distribution), a method of multistage polymerization under two or more polymerization conditions (copolymerization amount, temperature, etc.) giving different crystallinity (distribution), each component The method of blending these and the method of combining these are preferred.

Next, each component which comprises the resin composition B, and its characteristic are demonstrated.
Resin composition B is a polyethylene-based resin composition comprising an ethylene / α-olefin copolymer and HPLD in the same manner as resin composition A, and has specific physical properties (B1), (B2), and (B3). In particular, the TREF characteristic defined by (B1) is an important feature of the present invention.

  The ethylene / α-olefin copolymer constituting the resin composition B is basically the same as that used in the resin composition A. If some differences are described, those with a somewhat lower density are preferred.

  The ethylene / α-olefin copolymer is preferably produced using a metallocene catalyst, but can also be produced using a so-called Ziegler catalyst containing titanium and halogen. In this case, even if it is a copolymer of ethylene and α-olefin, in the TREF characteristics to be described later, S4b (elution with an elution temperature of 80 ° C. or higher and the ethylene content is close to 100% by weight. Highly crystalline component) is easily produced as a by-product. In the case where the S4b content in the ethylene / α-olefin copolymer produced using a Ziegler catalyst deviates from a predetermined value, the S4b component may be removed by fractionation. When ethylene / α-olefin copolymers having different physical properties are used in combination, the technique may be a blend of the copolymers or multistage polymerization. A metallocene catalyst and a Ziegler catalyst can also be mixed and used. The Q value of the ethylene / α-olefin copolymer is preferably 3.0 or less, particularly 2.5 or less. The weight average molecular weight of the ethylene / α-olefin copolymer is preferably about 50,000 to 80,000, particularly about 55,000 to 75,000. When the weight average molecular weight is smaller than this, the material strength is lowered and the heat sealability is deteriorated. On the other hand, if the weight average molecular weight is larger than this, the extrusion load and high-speed processability at the time of extrusion laminating deteriorate.

  The HPLD constituting the resin composition B can be selected from those used in the resin composition A.

  Next, the characteristics (B1) to (B3) of the resin composition B will be described. Among these, (B1) relates to the TREF characteristic, and further subdivides the technical contents into (Bi) to (Biv).

(Bi) The ratio of the eluate (S1b) having an elution temperature of 40 ° C. or lower is 45 to 65% by weight.
The eluate (S1b) is a component of a low crystal region. In the present invention, it becomes a factor that affects the low temperature sealing performance. S1b is 45 to 65% by weight, preferably 50 to 65% by weight, more preferably 55 to 60% by weight, as the content in the resin composition B. When S1b is higher than the above range, stickiness occurs, slipperiness deteriorates, crystallization in the high temperature seal region is slow, and foaming is likely to occur. Moreover, when S1b is lower than the said range, the sealing performance in low temperature will be inferior. S1b is composed of a component having an ethylene content of about 80 to 60% by weight in the ethylene / α-olefin copolymer, and S1b can be changed by increasing or decreasing the component.

(Bii) The ratio of the eluate (S2b) having an elution temperature of 40 to 60 ° C. is 10 to 30% by weight.
The eluate (S2b) is a component having relatively high crystallinity compared to S1b. Due to the presence of S2b, the crystallization speed at the time of heat sealing is increased, and as a result, the appearance of the seal is clean. S2b is 10-30 weight% as content in the resin composition B, Preferably it is 15-30 weight%, More preferably, it is 20-30 weight%. However, when S2b is higher than the above range, the low-temperature sealing property is deteriorated. On the other hand, when S2b is lower than the above range, the seal is retracted, and the appearance of the packaged product is impaired, or foaming occurs at a high temperature to impair the appearance. S2b is composed of a component having an ethylene content of about 80 to 90% by weight in the ethylene / α-olefin copolymer, and S2b can be changed by increasing or decreasing the component.

(Biii) The ratio of the eluate (S3b) having an elution temperature of 60 to 80 ° C. is 10 to 35% by weight.
The eluate (S3b) is a component having higher crystallinity than S1b and S2b. In the present invention, it becomes a factor that affects the heat resistance and extrusion lamination processability. S3b is 10-35 weight% as content in the resin composition B, Preferably it is 15-30 weight%, More preferably, it is 15-25 weight%. However, when S3b is higher than the above range, the low-temperature sealing property is deteriorated, and when it is lower than the above range, neck-in at the time of extrusion lamination processing is deteriorated, and the processing becomes difficult. Since S3b has an HPLD elution temperature in this region, S3b can be changed by increasing or decreasing such components.

(Biv) The ratio of the eluate (S4b) having an elution temperature of 80 ° C. or higher is 0 to 2% by weight.
The eluate (S4b) is a component having higher crystallinity than the S3b (eluate corresponding to the high-pressure method low-density polyethylene). In the present invention, it becomes a factor that affects the heat resistance and the low temperature sealability inhibition. S4b is 0 to 2 weight% as content in the resin composition B, Preferably it is 0 to 1 weight%, More preferably, it is 0 weight%. That is, it is most preferable that S4b is not substantially present. If S4b is higher than the above range, the low temperature sealing property is deteriorated, which is not preferable. S4b is composed of a component having an ethylene content of about 95 to 100% by weight in the ethylene / α-olefin copolymer, and S4b can be changed by increasing or decreasing the component.

  An example of an elution curve obtained by TREF measurement is shown in FIG. The horizontal axis represents the elution temperature (° C.), and the vertical axis represents the relative differential mass. In FIG. 2, the solid line is the differential elution curve relating to the resin composition B obtained in Example 1, and the broken line is the integral elution curve. It has two peaks of elution amount around 32 ° C. and 66 ° C., and it is understood that the distribution of components having different solubility characteristics in the solvent is wide. In addition, the elution component is extremely small in the region where the elution temperature exceeds 80 ° C. [FIG. 2] shows a TREF elution curve of the resin composition B obtained in Example 1 described later, and by reading the integrated values at 40 ° C., 60 ° C., and 80 ° C., the ratio of each eluate can be calculated. . Here, the integrated value at 40 ° C. is 63%, the integrated value at 60 ° C. is 76.1%, and the integrated value at 80 ° C. is 99.4%. Therefore, S1b = 63%, S2b = 13.1%, S3b = 23.3%, S4b = 0.6%.

(Bv) In addition, the weight average molecular weight (Mwb1) of the S1b component is preferably 50000-
It is 70000, More preferably, it is 55000-65000. Moreover, the weight average molecular weight (Mwb2) of S2b component becomes like this. Preferably it is 60000-80000, More preferably, it is 65000-75000. The weight average molecular weight (Mwb3) of the S3b component is preferably 150,000 to 220,000, and more preferably 170000 to 210000. Further, S4b is not particularly limited with respect to its weight average molecular weight. Here, the ratio (Mw2 / Mw1) b of the weight average molecular weight (Mwb2) of S2b to the weight average molecular weight (Mwb1) of S1 is preferably 1 to 2, more preferably 1 to 1.5. If (Mw2 / Mw1) b is higher than the above range, seal retraction tends to occur during low temperature sealing, and if (Mw2 / Mw1) b is lower than the above range, foaming tends to occur during high temperature sealing. The average molecular weight was measured by gel permeation chromatography (GPC), details of which will be described later.

  Since the TREF data is generally additive, when the polyethylene resin composition of the present invention is produced by mixing several types of copolymers, the TREF data of individual copolymers and high-pressure method low-density polyethylene are used. Based on the above, it is possible to slightly increase / decrease the ratio of the mixture components after predicting the mixture ratio to be a desired TREF pattern.

(B2) Density Characteristics The density of the resin composition B (JIS-K 6922: 1997 appendix (23 ° C.)) is 0.88 to 0.94 g / cm ³ , particularly 0.88 to 0.91 g / cm ³ . It is preferable. If the density is higher than the above range, the low temperature heat sealability is poor. If the density is lower than the above range, it is not preferable because it tends to foam when sealed at a high temperature. As described above, the density of the resin composition B is preferably small in comparison with the density of the resin composition A. The density difference, preferably 0.01 g / cm ³ or more, more preferably from 0.01~0.03g / cm ^3.

(B3) Melt Flow Rate (MFR) Characteristic Resin Composition B has an MFR (JIS-K 6922: 1997 appendix (190 ° C., 21.18 N)) at 190 ° C. of 1 to 100 g / 10 minutes, preferably 2 to 50 g. / 10 minutes, more preferably 4 to 20 g / 10 minutes. If the MFR is lower than the above range, the extrusion load when the resin is melt-extruded becomes high, and the film surface becomes rough during molding, which is not preferable. If the MFR exceeds the above range, the hot tack property at the time of heat sealing is lowered or the strength when used as a packaging material is lowered, which is not preferable.

(B4) Swell ratio (SR) characteristic The resin composition B preferably has a swell ratio (SR) of 1.5 or more, more preferably 1.55 or more. If the SR is less than the above range, the neck-in at the time of extrusion laminating is difficult to increase and the processing becomes easy. The upper limit of SR is not particularly limited, but is preferably less than 2.1. When SR exceeds 2.1, workability at high speed may be deteriorated. The SR measurement conditions are the same as described above.

(Measurement of molecular weight)
The molecular weight of each component of the resin composition B was measured by a cross fractionation chromatograph (CFC). CFC consists of a temperature rising elution fractionation (TREF) part for performing crystalline fractionation and a gel permeation chromatography (GPC) part for molecular weight fractionation. The analysis using the CFC is performed as follows. First, a polymer sample was completely dissolved in orthodichlorobenzene (ODCB) containing 0.5 mg / mL BHT (3,5-di-tertiarybutyl-4-hydroxytoluene) at 140 ° C., and then this solution was added to the apparatus. The polymer sample is crystallized by pouring through a sample loop into a TREF column (column filled with inert glass bead carrier) maintained at 140 ° C. and gradually cooling to a predetermined first elution temperature. After maintaining at a predetermined temperature for 30 minutes, ODCB is passed through a TREF column, whereby the eluted components are injected into the GPC section to perform molecular weight fractionation, and a chromatogram is obtained by an infrared detector. Meanwhile, in the TREF part, the temperature is raised to the next elution temperature, and after obtaining the chromatogram of the first elution temperature, the elution component at the second elution temperature is injected into the GPC part. Thereafter, the same operation is repeated to obtain a chromatogram of the eluted components at each elution temperature. Details of the measurement conditions are as follows.
Equipment: CFC-T102L manufactured by Dia Instruments
GPC column: Showa Denko AD-806MS (3 connected in series)
Solvent: orthodichlorobenzene (ODCB)
Sample concentration: 3 mg / mL
Injection volume: 0.4mL
Crystallization rate: 1 ° C./min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stabilization time after GPC measurement: 5 minutes Elution temperature:
0,5,10,15,20,25,30,35,40,45,49,52,55,58,61,64,67,70,73,76,79,82,85,88,91, 94,97,100,102,120,140 infrared detectors: MIRAN 1A IR detector manufactured by FOXBORO Measurement wavelength: 3.42 μm

(Data analysis method)
The chromatogram of the eluted components at each elution temperature obtained by TREF measurement is processed by a data processing program attached to the apparatus, and the eluted amount (proportional to the area of the chromatogram) normalized so that the total is 100%. Desired. In addition, an integrated elution curve for the elution temperature is calculated. The integrated elution curve is differentiated with temperature to obtain a differential elution curve.
Moreover, molecular weight distribution is calculated | required by the following procedure from each chromatogram.
Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
The standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is created by injecting 0.4 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL.
The calibration curve uses a cubic equation obtained by approximation by the least square method.
For conversion to molecular weight (M), a general calibration curve is used with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Publishing). Viscosity formula [η] = K × Mα used at that time
The following numerical values are used as K and α.
K = 3.92 × 10 ⁻⁴ , α = 0.733
Note that in the chromatogram at the first elution temperature, the peak due to BHT added to the solvent may overlap with the low molecular weight side of the elution component. In this case, the baseline is drawn as shown in FIG. Define the interval for which

  Heretofore, the components constituting the resin compositions A and B of the present invention and the characteristics thereof have been described. Hereinafter, the technical matters common to the resin compositions A and B will be supplemented.

(Production method of polyethylene resin composition)
Resin compositions A and B of the present invention are both polyethylene resin compositions and are composed of the above-described ethylene / C _3-20 α-olefin copolymer and high-pressure low-density polyethylene. For the resin composition A, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is preferably 50 to 95% by weight, more preferably 40 to 90% by weight, and high pressure method low density polyethylene 5 to 50% by weight. More preferably, it can be produced by blending 10 to 40% by weight. For the resin composition B, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is preferably 60 to 95% by weight, more preferably 65 to 90% by weight, high pressure method low density polyethylene 5 to 40% by weight, More preferably, it can manufacture by mix | blending 10 to 35 weight%. Each of the resin compositions A and B is an antioxidant, a light stabilizer, an ultraviolet absorber, an antistatic agent, an antifogging agent, a crystal nucleating agent, a neutralizing agent, as long as the effects of the present invention are not significantly impaired. It may contain a metal deactivator, a colorant, a dispersant, a slip agent, a peroxide, a filler, an optical brightener and the like.

When two types of metallocene ethylene copolymers having different densities are used in combination, for resin composition A, for example, a copolymer having a density of 0.87 to 0.90 g / cm ³ is 5 to 20% by weight, copolymer 40 to 70 wt% of the density of 0.90~0.92g / cm ^3, and a copolymer 5-10 wt% of the density of 0.92~0.94g / cm ^3, this density 0.91～ A mode in which 0.93 g / cm ^{3 of} high-pressure low-density polyethylene is blended in an amount of 10 to 40% by weight is preferable. For the resin composition B, for example, a copolymer having a density of 0.86 to 0.89 g / cm ³ is 35 to 70% by weight, and a copolymer having a density of 0.89 to 0.91 g / cm ³ is 5 to 35. An embodiment in which 5% to 40% by weight of a high-pressure method low-density polyethylene having a density of 0.91 to 0.93 g / cm ³ is blended is preferable.

  Resin compositions A and B are generally obtained by melt-kneading HPLD with one or more ethylene / α-olefin copolymers obtained by polymerization. Although performance may be obtained by simple blending, it is easy to obtain stable performance by melt-kneading, and it is easy to obtain a clean appearance when processed into a film. Furthermore, when blending the above compounding agents and the like, it is easier to disperse the compounding agent by melt kneading.

  In the present invention, the density of the obtained resin composition A is preferably larger than the density of the resin composition B. When the density of both resin compositions is in this relationship, a clean appearance and good pressure strength can be obtained from low temperature to high temperature when liquid-filled packaging is performed. When the density of the resin composition A is equal or conversely smaller than the density of the resin composition B, low-temperature filling may be difficult, or foaming may easily occur at high temperatures.

  Any conventionally known method can be used for melt-kneading, but usually it can be carried out with a Banbury mixer, a kneader blender, a uniaxial or biaxial kneading extruder. Among these, it is preferable to perform mixing or melt-kneading with a uniaxial or biaxial kneading extruder. A general kneading temperature is about 150 to 220 ° C., but it is also possible to knead while performing nitrogen sealing in order to prevent thermal deterioration of the resin composition. Moreover, a kneader can also combine 2 or more types of what was mentioned above.

(Manufacture of laminated film)
A film for packaging can be obtained by laminating the polyethylene resin composition of the present invention on a substrate. Specifically, a layer made of the resin composition A of the present invention (intermediate layer) and a layer made of the resin composition B (sealant layer) are laminated in this order on one side of the substrate, and the layer made of the resin composition B Is a packaging material laminated as a heat seal layer.

  As the base material layer constituting the laminate, paper, aluminum foil, cellophane, woven fabric, non-woven fabric, polymer film, for example, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene / vinyl acetate copolymer Polymers, ethylene / acrylic acid ester copolymers, ionomers, polypropylene, poly-1-butene, poly-4-methylpentene-1, and other olefin polymers, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate, polyacrylonitrile Vinyl copolymers such as nylon 6, nylon 66, nylon 7, nylon 10, nylon 11, nylon 12, nylon 610, polyamides such as polymetaxylylene adipamide, polyethylene terephthalate, polyethylene terephthalate / isophthalate, polybutylene Polyester terephthalate, such as, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, may be mentioned a film of polycarbonate. Further, one kind of the above film may be used alone, or two or more kinds of the above films may be used in combination. Further, depending on the kind of the base material, the film may be stretched. In particular, a uniaxial or biaxially stretched polypropylene film, a stretched nylon film, a stretched polyethylene terephthalate film, a stretched polystyrene film, or the like is also used. Further, a substrate obtained by coating polyvinylidene chloride, polyvinyl alcohol or the like on the above substrate, or a substrate obtained by vapor deposition of aluminum, alumina, silica, or a mixture of alumina and silica may be used.

  The metal foil is not particularly limited, and an aluminum foil, tin foil, lead foil, galvanized thin steel plate, an ionized metal thin film formed by electrolysis, an iron foil, or the like is used. Moreover, although it does not specifically limit about a metal vapor deposition film, As a vapor deposition metal, aluminum and zinc and 0.01-0.2 micrometer are normally used preferably. The deposition method is not particularly limited, and a known method such as a vacuum deposition method, an ion plating method, or a sputtering method is used. Furthermore, in the ceramic vapor deposition film, examples of the ceramic to be vapor-deposited include, for example, silicon oxide represented by the general formula SiOx (0.5 ≦ x ≦ 2), and metals such as glass, alumina, magnesium oxide, and tin oxide. Examples thereof include metal fluorides such as oxide, fluorite, and selenium fluoride. The metal oxide may contain a trace amount of metal, other metal oxide, or metal hydroxide. Vapor deposition can also be performed by applying the various vapor deposition methods described above to at least one side of the film. The thickness of a vapor deposition film is about 12-40 micrometers normally. Moreover, there is no restriction | limiting in particular as a vapor deposition film, Transparent films, such as a stretched polyester film, a polypropylene film, a polyamide film, are mentioned.

  As a liquid or viscous packaging material, a biaxially stretched nylon film or a biaxially stretched polyethylene terephthalate film, or a material obtained by vapor-depositing silica or alumina on a base material, or a laminate of these materials is often used.

  The method for laminating the resin composition of the present invention on the surface of the substrate is not particularly limited and can be carried out according to a known method. For example, there are a dry lamination method, a wet lamination method, an extrusion method, a sandwich lamination method, a coextrusion method, and the like. A film for a heat seal layer used for dry lamination or the like can be produced by any method such as a calendar method, an air-cooled inflation method, a water-cooled inflation method, or a T-die molding method using the ethylene resin and the propylene resin. In the case of an extrusion method, an extrusion laminating method, a dry laminating method, a sandwich laminating method, a coextrusion method (including coextrusion without an adhesive layer, coextrusion with an adhesive layer, coextrusion with an adhesive resin, etc.) There are methods. A tandem extrusion laminating method is often used as a method for producing a liquid or viscous packaging material with a laminated film comprising the resin composition of the present invention. This is a method of laminating two types of resin layers in succession, such as an intermediate layer as the first layer and a sealant layer as the second layer on the substrate by extrusion laminating, which is suitable in terms of productivity and quality. It is.

  The intermediate layer and the sealant layer are formed by melt-extrusion of the polyethylene resin composition of the present invention separately or simultaneously, and the molding temperature thereof is 150 to 320 ° C. In this category, the base material and the intermediate layer, Moreover, it is also preferable from the viewpoint of adhesion between the intermediate layer and the sealant layer, processability, odor, and the like. Moreover, when melt-extrusion molding an intermediate | middle layer to a base material, it is preferable from an adhesive point to perform an anchor-coat process to the surface by which the base material is extrusion-molded, and to perform ozone treatment in the said shaping | molding temperature range. The anchor coat treatment is carried out by using a known anchor coat agent or adhesive such as polyurethane, isocyanate compound, urethane polymer, or a mixture and reaction product thereof, a mixture or reaction product of polyester or polyol and isocyanate compound, or a solution thereof. Etc. are applied to the substrate surface.

  In the laminate of the present invention, the basic (minimum) configuration is indispensable to have a total of three layers, each of the base layer, the intermediate layer made of the resin composition A, and the sealant layer made of the resin composition B. . Here, each layer of the base material layer, the intermediate layer, and the sealant layer may be a single layer, but in some cases, each of the layers may be composed of a plurality of layers. For example, a two-layer film obtained by dry laminating a polyester film and a ceramic vapor-deposited polyester film can be used as the base material layer. In the case of laminating one intermediate layer and one sealant layer on a base material layer composed of a two-layer film, a total of four layers is formed. Further, for example, when a total three-layer film in which a polyester film and an aluminum foil are dry-laminated and further a polyester film is dry-laminated on the surface of the aluminum foil is used as a base material layer, a five-layer structure is formed. The intermediate layer and the sealant layer are usually used as a single layer (only one layer).

Ozone treatment is performed by directing ozone-containing gas (air, etc.) from the nozzle or slit-shaped outlet in the air gap to the base material adhesion surface of the intermediate layer or the base material surface laminated with this. It is performed by spraying toward the crimping part. In addition, when extrusion laminating at a speed of 100 m / min or more, it is preferable to spray toward both the above-mentioned crimping portions. The concentration of ozone in the gas containing ozone is preferably 1 g / m ³ or more, and more preferably 3 g / m ³ or more. The amount of spraying is preferably 0.03 liter / min / cm or more, more preferably 0.1 liter / min / cm or more with respect to the width of the adhesive layer.

  The laminating speed is generally 100 to 150 m / min from the viewpoint of productivity. Further, the air gap of a known extrusion laminator is generally 100 to 150 mm. The laminate of the present invention is preferably subjected to an aging treatment immediately after molding from the viewpoint of adhesiveness. Aging is performed within 12 hours after molding the laminate by leaving it at a temperature of 23 to 45 ° C., preferably 35 to 45 ° C., in an atmosphere of 0 to 50% humidity for 12 to 24 hours.

  As for the laminated body obtained in this way, it is common that the thickness of a base material layer is 10-40 micrometers, the thickness of an intermediate | middle layer is 10-30 micrometers, and the thickness of a sealant layer is 5-80 micrometers.

  The thickness of the entire laminated film, the thickness of each layer, and the thickness ratio are not particularly limited and may be appropriately determined according to the contents, usage, and the like. Specifically, the thickness of the entire laminated film is 40 to 120 μm. The thickness of the material layer is preferably 10 to 40 μm, the thickness of the intermediate layer is preferably about 10 to 40 μm, and the thickness of the sealant layer is preferably about 8 to 80 μm.

(Manufacture of packaging bags)
The laminated film of the present invention thus obtained can be used as various packaging materials such as food packaging materials, medical packaging materials, and industrial material packaging materials such as engine oil. In particular, it is suitably used as a packaging material for containing a liquid such as liquid, fiber, powder, etc., a liquid containing solid insoluble matter, a fluid such as a viscous body, and the like as contents.

(Filling methods such as liquid and mucus)
The die roll type liquid and viscous continuous filling machine is roughly composed of a feeding part, a half-cut part, a vertical seal roll, a filling nozzle, a horizontal seal roll, a cooling roll, a cut part, and a discharge part. From the top to the cut part, it is aligned with the half-folded part and the vertical seal roll from the top in the vertical direction. The half-folding operation needs to be performed with the layer made of the resin composition B of the laminate inside. The filling is a liquid or viscous content, adjusted to another tank, heated as necessary, and then transferred to the filling nozzle by a pump. The temperature of the filling varies depending on the type and nature of the contents, the necessity of sterilization, etc., but is usually performed at 10 to 95 ° C. In some cases, a heater for preheating the half-folded portion at the portion from the half-cut portion to the vertical seal roll may be provided.

  The vertical seal roll consists of two rolls arranged in front and back, and generally seals one part of the film while rotating at the same speed as the filling speed, but there are two types such as ketchup and mustard. When the contents are filled, they are exchanged so that two seals can be made. The horizontal seal roll consists of two rolls arranged in front and back. Generally, there are four seal heads on one roll, and they rotate variably to fit the set horizontal seal pitch. Seal in a form that fits together. The transverse cooling roll is directly below the transverse seal roll and is not heated, but the way of movement is the same as the transverse seal roll. Both vertical rolls and horizontal rolls may have a mesh pattern or no pattern as required. The cut part is directly under the horizontal cooling roll, and the central part of the horizontal seal part is cut in half with a rotating blade. In some cases, a perforation is made without cutting. In some cases, an ironing roll or ironing guide is provided on the vertical seal roll to adjust the liquid level.

  In the filling procedure, a roll-wrapped film is unrolled, half-folded with a guide plate so that the sealing surface is aligned at the upper part of the die roll, and first, vertically sealed with a vertical seal roll to form a cylindrical film. Subsequently, horizontal sealing is performed with a horizontal sealing roll, and further, the horizontal sealing surface is cooled with a horizontal cooling roll. There is a filling nozzle for the contents directly above the horizontal seal, and the structure is structured to blow the contents downward downward continuously or intermittently. Therefore, in practice, the horizontal sealing is performed at the place where the filler is present. This is a so-called miscellaneous seal. The filling amount per bag is determined by the speed of the vertical seal, the horizontal seal pitch, and the filling speed, and the filling rate is determined by adjusting the liquid level with a ironing board or the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The ethylene / α-olefin copolymer used in the following Examples and Comparative Examples was produced by the method shown below.

  The physical properties of the ethylene / α-olefin copolymer used in Resin Composition A are shown in [Table 1 (1)], those used in Resin Composition B are shown in [Table 1 (2)], and ethylene The physical property values of HPLD used by mixing with the α-olefin copolymer are shown in [Table 1 (3)].

(1) Production of ethylene / α-olefin copolymer (1-1) Preparation of PE-A1 and PE-A3 polymerization catalyst:
To a catalyst preparation apparatus 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 tripropyl was maintained at 90 ° C. 100 g of aluminum was added dropwise over 100 minutes, and then reacted at the same temperature for 2 hours. After cooling to 40 ° C., 3200 ml of a toluene solution of methylalumoxane (concentration 2.5 mmol / ml) was added and stirred for 2 hours. Next, 2000 g of silica (Grace, # 952, surface area 300 m ² / g) preliminarily baked at 450 ° C. for 5 hours is added, stirred at room temperature for 1 hour, blown with nitrogen at 40 ° C., and dried under reduced pressure. A good solid catalyst was obtained.

(1-2) Preparation of PE-A2, PE-B1 to PE-B4 polymerization catalyst:
The catalyst was prepared by the method described in JP-T-7-508545. That is, to the complex dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) hafnium dimethyl 2.0 mmol, tripentafluorophenyl boron was added in an equimolar amount to the above complex, and diluted to 10 liters with toluene. A catalyst solution was prepared.

(1-3) Polymerization <PE-A1>
The molar ratio of 1-hexene / ethylene was 0.027, the molar ratio of hydrogen / ethylene was 7.5 × 10 ⁻⁴ , the nitrogen concentration was 30 mol%, the total pressure was 0.8 MPa, and the temperature was 75 ° C. Then, a hexane solution (0.01 mmol / ml) of triethylaluminum was supplied at 25 ml / h to a gas-phase continuous polymerization apparatus (internal volume 100 L, fluidized bed diameter 10 cm, fluidized bed seed polymer (dispersant) 1.5 kg). While maintaining the gas composition and temperature constant, polymerization was carried out by intermittently supplying a solid catalyst so that the production amount per hour was about 300 g. The activity was 410 g / (g catalyst · MPa · h), and the physical properties of the obtained ethylene / 1-hexene copolymer (PE-A1) were measured. As a result, the 1-hexene content was 11% by weight, and the MFR was 15 g / 10. Min, density 0.911 g / cm ³ , TREF elution curve has 3 peaks (60 ° C., 65 ° C., 86 ° C.), maximum peak temperature (Tp) is 65 ° C., Q value is 2.2. It was.

<PE-A2>
A stirring autoclave type continuous reactor having an internal volume of 1.5 liters was maintained at a pressure of 130 MPa, and a mixture of ethylene and 1-hexene was 40 kg / hour so that the composition of 1-hexene was 73% by weight. Continuously. Further, the catalyst supply amount was adjusted so that the polymerization temperature was maintained at 127 ° C. The polymer production per hour was about 2.1 kg. After completion of the reaction, the physical properties of the obtained ethylene / 1-hexene copolymer (PE-A2) were measured. As a result, the 1-hexene content was 24% by weight, the MFR was 3.5 g / 10 minutes, and the density was 0.880 g / cm ^3. The temperature (Tp) of the highest peak of the TREF elution curve was 32 ° C. and the Q value was 2.0.

<PE-A3>
The molar ratio of 1-hexene / ethylene was 0.009, the hydrogen / ethylene molar ratio was 3.5 × 10 ⁻⁴ , the nitrogen concentration was 30 mol%, the total pressure was 0.8 MPa, and the temperature was 80 ° C. Then, a hexane solution (0.01 mmol / ml) of triethylaluminum was supplied at 25 ml / h to a gas-phase continuous polymerization apparatus (internal volume 100 L, fluidized bed diameter 10 cm, fluidized bed seed polymer (dispersant) 1.5 kg). While maintaining the gas composition and temperature constant, polymerization was carried out by intermittently supplying a solid catalyst so that the production amount per hour was about 300 g. The activity was 270 g / (g catalyst · MPa · h), and the physical properties of the obtained ethylene / 1-hexene copolymer (PE-A3) were measured. As a result, the 1-hexene content was 2% by weight, MFR 4 g / 10. Min, density 0.935 g / cm ³ , the temperature (Tp) of the highest peak of the TREF elution curve was 90 ° C., and the Q value was 2.0.

<PE-B1>
The mixture of ethylene and 1-hexene was the same as PE-A1, except that the composition of 1-hexene was 74% by weight and the catalyst supply was adjusted so that the polymerization temperature was maintained at 137 ° C. Carried out. The polymer production per hour was about 3.4 kg. When the physical properties of the obtained ethylene / 1-hexene copolymer (PE-B1) were measured, the content of 1-hexene was 25% by weight, the MFR was 10 g / 10 min, the density was 0.880 g / cm ³ , and the TREF elution curve was the highest. The peak temperature (Tp) was 32 ° C. and the Q value was 2.3.

<PE-B2>
Similar to PE-1, except that the mixture of ethylene and 1-hexene was adjusted so that the composition of 1-hexene was 60% by weight and the catalyst supply was adjusted so that the polymerization temperature was maintained at 147 ° C. Carried out. The polymer production per hour was about 2.4 kg. The obtained ethylene / 1-hexene copolymer (PE-B2) had a 1-hexene content of 14% by weight, an MFR of 4 g / 10 min, a density of 0.900 g / cm ³ , and the temperature of the highest peak of the TREF elution curve (Tp ) Was 59 ° C. and Q value was 2.3.

<PE-B3>
Similar to PE-1, except that the mixture of ethylene and 1-hexene was adjusted so that the composition of 1-hexene was 64% by weight and the catalyst supply was adjusted so that the polymerization temperature was maintained at 160 ° C. Carried out. The polymer production per hour was about 3.6 kg. The obtained ethylene / 1-hexene copolymer (PE-B3) had a 1-hexene content of 15% by weight, an MFR of 17 g / 10 min, a density of 0.900 g / cm ³ , and the temperature of the highest peak of the TREF elution curve (Tp ) Was 47 ° C. and Q value was 2.3.

<PE-B4>
A commercially available ethylene / 1-hexene copolymer (Harmolex NC585A manufactured by Nippon Polyethylene Co., Ltd., using a metallocene catalyst) was used. PE-4 had a 1-hexene content of 5.2% by weight, an MFR of 6 g / 10 min, a density of 0.930 g / cm ³ , and a Q value of 2.6. The TREF elution curve of PE-4 was in the form of two peaks with a main peak at 83 ° C. and a sub-peak at 90 ° C.

<PE-B5>
A commercially available ethylene / 1-octene copolymer (DuPond Dow Elastomer Engage EG8200, using a metallocene catalyst) was used. PE-B5 had a 1-octene content of 24.8% by weight, an MFR of 5 g / 10 min, a density of 0.870 g / cm ³ , and a Q value of 2.4. The TREF elution curve of PE-B5 had a relatively sharp shape with a single peak at 28 ° C.

(2) Procurement of HPLD Commercial products shown in [Table 1 (3)] were used.

The film evaluation methods in the following examples and comparative examples are as follows.
(1) Production of packaging film by extrusion laminating process Using an extrusion laminating apparatus set so that the temperature of the resin extruded from a T-die mounted on an extruder having a diameter of 90 mmφ is 300 ° C, the surface temperature of the cooling roll is 25 ° C, When the die width was 600 mm, the die lip opening was 0.7 mm, and the take-up processing speed was 100 m / min, the extrusion amount was adjusted so that the coating thickness was 25 μm, and melt extrusion was performed. On the other hand, a biaxially stretched nylon film (Unitika Ltd., Emblem ONM) having a width of 500 mm and a thickness of 15 μm is used as a base layer, and an isocyanate anchor coating agent (Nihon Soda Co., Ltd., Titabond T120 solution) is used as a bow roll. The resin composition A according to the present invention was taken out as an intermediate layer material while being sprayed with ozone in the laminating portion, and extruded and laminated at a coating speed of 100 m / min and a coating thickness of 25 μm. Further, the same extrusion laminating apparatus is used on this intermediate layer, and the resin composition B according to the present invention is extruded and laminated as a sealant layer at an extrusion resin temperature of 280 ° C., a take-off speed of 100 m / min, and a coating thickness of 25 μm. It was. The laminated film after processing was aged for 24 hours in an oven at 45 ° C., and then slit to a width of 130 mm to obtain a packaging film for evaluation.

(2) Extrusion laminating workability evaluation At the time of the above extrusion laminating process, the difference between the width of the die and the width of the obtained product was used as a neck-in, and was used as a measure of workability. The smaller the neck-in, the better the workability.

(3) Evaluation of liquid filling suitability Using a liquid automatic filling and packaging machine (manufactured by Nippon Seiki Co., Ltd., Dangan TYPE-III), the liquid was filled under the following conditions, and the filling speed, bag pressure resistance, and appearance were evaluated.
[Filling conditions]
Sealing temperature: (vertical roll) 185 ° C, (horizontal) 145-185 ° C
Seal pressure: (Vertical roll) Left 140 kPa, Right 70 kPa, (Horizontal roll) Left 430 kPa, Right 380 kPa
Packaging form: Three-sided seal bag Dimensions: Width 75mm x Length 100mm Pitch Filling: Water 30 ° C
Filling amount: about 30cc
Filling speed: 20 m / min [judgment criteria for filling suitability]
Filling was performed at various temperatures, and the appearance of the sealing surface of the obtained pouch was visually observed. Depending on the degree, the seal part was removed, retracted, or foamed, and evaluated in three stages. Appearance should be ○ from low to high. Moreover, a pressure test was performed for 3 minutes by applying a load of 100 kg to the bag after filling with a pressure tester (manufactured by Komatsu Ltd.), and the presence or absence of bag breakage or leakage was evaluated. In the pressure resistance test, 50 bags were evaluated, and among 50 pieces, the case where there was no broken bag or leakage was marked as ◯, the case where one piece was leaked, and the case where two pieces or more were leaked as x. It is desirable that the pressure resistance evaluation is ○ from the low temperature region as much as possible.

[Example 1]
As an ethylene / α-olefin random copolymer, as shown in Table 1 (1), PE-A1 is 50% by weight, PE-A2 is 10% by weight, PE-A3 is 10% by weight, and high pressure method low density polyethylene. , HPLD-1 was blended well in a blender using 30% by weight, and melt-extruded into pellets to obtain a resin composition A. In addition, 65% by weight of PE-B1, 10% by weight of PE-B2, 1% by weight of PE-B4, and 24% by weight of HPLD-1 described in Table 1 (2) were used. With respect to 100 parts of these resins, 0.05 part of an aliphatic amide slip agent was thoroughly blended with a blender and melt-extruded into pellets to obtain a resin composition B. Table 2 shows the physical properties of the obtained resin compositions A and B. Next, a packaging film for evaluation was obtained by extrusion laminating and subsequent post-treatment, and neck-in during extrusion laminating was evaluated. Furthermore, filling evaluation with a liquid filling apparatus was performed, and the appearance and pressure strength of the seal part were evaluated. These results are shown in Table 4.

[Example 2]
Resin composition B was obtained using 45 wt% of PE-B1, 30 wt% of PE-B2, 25 wt% of HPLD-1 and 0.05 part of an aliphatic amide slip agent. Other than that, it evaluated similarly to Example 1. FIG. Table 2 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Example 3]
60% by weight of PE-B1, 30% by weight of PE-B2, 10% by weight of HPLD-1, and 0.05 part of an aliphatic amide slip agent were used to obtain a resin composition B. Other than that, it evaluated similarly to Example 1. FIG. Table 2 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Example 4]
A resin composition A was obtained using 60% by weight of PE-A1, 5% by weight of PE-A2, 5% by weight of PE-A3, and 30% by weight of HPLD-1. Further, PE-5 was used in place of PE-B1, and the others were evaluated in the same manner as in Example 2. Table 2 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Example 5]
A resin composition B was obtained using 57% by weight of PE-B1, 28% by weight of PE-B2, 15% by weight of HPLD-1, and 0.05 part of an aliphatic amide slip agent. Otherwise, the evaluation was performed in the same manner as in Example 4. Table 2 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Comparative Example 1]
Resin composition A was obtained using 70 wt% PE-A1 and 30 wt% HPLD-1. Other than that, it evaluated similarly to Example 1. FIG. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Comparative Example 2]
Resin composition A was obtained using 70 wt% PE-A1 and 30 wt% HPLD-1. Otherwise, the evaluation was performed in the same manner as in Example 2. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Comparative Example 3]
Resin composition A was obtained using 10 wt% PE-A1, 30 wt% PE-A2, 30 wt% PE-A3, and 30 wt% HPLD-1. Also, a resin composition B was obtained using 50 wt% of PE-B1, 25 wt% of PE-B2, 5 wt% of PE-B4, and 20 wt% of HPLD-1. Other than that, it evaluated similarly to Example 1. FIG. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Comparative Example 4]
Resin composition A was obtained using 10 wt% PE-A1, 30 wt% PE-A2, 30 wt% PE-A3, and 30 wt% HPLD-1. Also, a resin composition B was obtained by using 70% by weight of PE-B1, 20% by weight of PE-B3, 5% by weight of PE-B4, and 5% by weight of HPLD-1. Other than that, it evaluated similarly to Example 1. FIG. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results. FIG. 11 is an elution curve relating to the resin composition B obtained in Comparative Example 4. In addition to having a very large elution volume peak at around 31 ° C, it has a small elution volume peak at around 46 ° C and 66 ° C, and there are considerable elution components in the region where the elution temperature exceeds 80 ° C. It is.

[Comparative Example 5]
Resin composition A was obtained using 10 wt% PE-A1, 30 wt% PE-A2, 30 wt% PE-A3, and 30 wt% HPLD-1. Moreover, 60% by weight of PE-B1 and 40% by weight of HPLD-1 were used to obtain a resin composition B. Other than that, it evaluated similarly to Example 1. FIG. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Comparative Example 6]
Resin composition A was obtained using 10 wt% PE-A1, 30 wt% PE-A2, 30 wt% PE-A3, and 30 wt% HPLD-1. Also, a resin composition B was obtained using 30 wt% of PE-B1, 40 wt% of PE-B2, and 30 wt% of HPLD-1. Other than that, it evaluated similarly to Example 1. FIG. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Comparative Example 7]
Instead of using any of PE-B1 to PE-B5 as the resin composition B, instead, Moatec 0818D (made by Idemitsu Petrochemical, Ziegler LLDPE, density 0. 908 g / cm ³ , MFR 8 g / 10 min) was used alone. Other than that, it evaluated similarly to Example 1. FIG. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Comparative Example 8]
Instead of using any of PE-B1 to PE-B5 as resin composition B, instead of affinity PT1450 (manufactured by Dow Chemical, metallocene LLDPE, density 0. 905 g / cm ³ , MFR 8 g / 10 min) was used alone. Other than that, it evaluated similarly to Example 1. FIG. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

[Comparative Example 9]
Evaluation was conducted in the same manner as in Example 1 except that 30% by weight of Moteck 0818D was used instead of 30% by weight of PE-B2 to obtain the resin composition B. Table 3 shows the physical properties of the resin compositions A and B, and Table 4 shows the evaluation results.

It is an elution curve of the resin composition A (Examples 1-3, Comparative Examples 7 and 8). It is an elution curve of resin composition B (Example 1, comparative example 1). It is an elution curve of resin composition B (Example 2, comparative example 2). It is an elution curve of the resin composition B (Example 3). It is an elution curve of the resin composition A (Example 4, comparative example 9). It is an elution curve of resin composition B (Example 4). It is an elution curve of the resin composition B (Example 5). It is an elution curve of the resin composition A (comparative example 1). It is an elution curve of the resin composition A (comparative example 3). It is an elution curve of resin composition B (comparative example 3). It is an elution curve of resin composition B (comparative example 4). It is an elution curve of resin composition B (comparative example 5). It is an elution curve of resin composition B (comparative example 6). It is an elution curve of resin composition B (comparative example 7). It is an elution curve of resin composition B (comparative example 8). It is an elution curve of resin composition B (comparative example 9). It is a baseline figure of a cross fraction chromatograph (CFC).

Claims (7)

A layered product comprising a layer made of a resin composition A and a layer made of a resin composition B laminated in this order on a substrate, and the resin compositions A and B each satisfy the following physical properties.
Resin composition A: ethylene, a copolymer of 50 to 95 wt% of the α- olefin having 3 to 20 carbon atoms, in the high-pressure low-density polyethylene (HPLD) polyethylene resin composition Do that from 5 to 50 wt% And the copolymer of this ethylene and C3-C20 alpha olefin is a polyethylene resin composition comprised from a some copolymer, and satisfying following (A1)-(A3).
(A1) In the elution curve obtained by temperature-temperature elution fractionation (TREF) using orthodichlorobenzene as a solvent, the following (Ai) to (Aiv) are satisfied.
(Ai) Number of peaks is 3 or more (Aii) Maximum peak temperature (Tha) is 85 to 100 ° C.
(Aiii) The minimum peak temperature (Tla) is 30 to 65 ° C.
(Aiv) The total amount of the eluate amount (Sla) having an elution temperature of 0 to (Tla + 6) ° C. and the eluate amount (Sha) having an elution temperature of (Tha-6) to 120 ° C. is 15 to 15% of the total eluate amount (Sta). 40% by weight
(A2) Density is 0.90 to 0.93 g / cm ³
(A3) Melt flow rate (MFR) 0.1 to 1000 g / 10 min Resin composition B: 60 to 95% by weight of a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, HPLD 5 to 40 a polyethylene resin composition that Do from the weight%, a copolymer of the ethylene and the number 3 to 20 carbon α- olefin is composed of a plurality of copolymer, and the following (B1) ~ (B3 Polyethylene resin composition satisfying
(B1) In an elution curve obtained by TREF using orthodichlorobenzene as a solvent, the following (Bi) to (Biv) are satisfied.
(Bi) The proportion of eluate (S1b) having an elution temperature of 40 ° C. or lower is 45 to 65% by weight.
(Bii) The ratio of the eluate (S2b) having an elution temperature of 40 to 60 ° C. is 10 to 30% by weight.
(Biii) The ratio of the eluate (S3b) having an elution temperature of 60 to 80 ° C. is 10 to 35% by weight.
(Biv) The ratio of eluate (S4b) having an elution temperature of 80 ° C. or higher is 0 to 2% by weight (B2) The density is 0.88 to 0.92 g / cm ³
(B3) Melt flow rate (MFR) is 1 to 100 g / 10 min In the resin composition A, the copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is 5 to 20% by weight of a copolymer having a density of 0.87 to 0.90 g / cm ³ and a density exceeding 0.90. -0.92 g / cm ³ copolymer 40-70 wt%, density 0.92-0.94 copolymer 5-10 wt%, and HPLD, density 0.91-0.93 g / cm The laminate according to claim 1, comprising ³ to 10% by weight of the ^three . In the resin composition B, as a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, a copolymer having a density of 0.86 to 0.89 g / cm ³ is 35 to 70% by weight, and the density is more than 0.89. copolymer 5-35 weight% of ~0.91g / cm ^3, and as HPLD, claim 1, characterized in that it consists of 10 to 40 wt% that of density 0.915~0.925g / cm ³ or 2. The laminate according to 2.   The density of the resin composition A is larger than the density of the resin composition B, The laminated body of any one of Claims 1-3 characterized by the above-mentioned.   A packaging bag formed by folding the layered product according to any one of claims 1 to 4 with a layer made of the resin composition B inside, and heat-sealing the layer.   A bag comprising the packaging bag according to claim 5 filled with a liquid or a viscous content. A bag in which a packaging bag according to claim 5 is filled with a liquid having a temperature of 10 to 95 ° C or a viscous content using a die roll type automatic liquid filling and packaging machine.