JPH0994931A - Laminate, bag composed thereof, chuck bag and compression housing bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain at least a three-layered structure excellent in transparency, impact resistance, gas barrier properties, low temp. heat-sealability and moldability. SOLUTION: A laminate contains a first layer consisting of an ethylene/α- olefin copolymer (A) with density of 0.86-0.94g/cm<3> and an ethylene/α-olefin copolymer (A') having specific Mw/Mn or Cb and density of 0.86-0.94g/cm<3> or an ethylene polymer (B) by a high pressure radical polymerization method, a second layer based on high density polyethylene (C) with density of 0.94g/cm<3> or more and a third layer based on an ethylene/α-olefin copolymer (A') and the second layer thereof is set to an intermediate layer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminate having at least a three-layer structure, which is excellent in transparency, impact resistance, gas barrier property, low-temperature heat-sealing property, and moldability, a bag made of the laminate, and a zipper bag. It relates to a compression storage bag. The laminate is widely used as a packaging material for foods, newspapers, magazines, machinery, etc., and these bags and bags with a zipper have excellent transparency and airtightness, and foods, pharmaceuticals, industrial products, clothing, and miscellaneous goods. Widely used as a resealable packaging bag for etc. The thermoplastic resin zipper with airtightness is a packaging bag for long-term storage of food, a packaging bag for fluid food, and a compression storage bag for deaeration and compression storage of clothing, futon, etc. Widely used for etc.

[0002]

2. Description of the Related Art Conventionally, high-pressure low density polyethylene, linear low density polyethylene, high density polyethylene film and the like have been used as packaging materials. However, high-pressure low-density polyethylene is inferior in impact resistance, gas barrier property and stiffness, and high-density polyethylene is inferior in transparency and impact resistance. On the other hand, linear low-density polyethylene is excellent in transparency and impact resistance, but is inferior in gas barrier property, rigidity and moldability. For this reason, in a single layer film, transparency, impact resistance,
There is no resin that can comprehensively satisfy the rigidity, gas barrier property, moldability, etc., and in order to satisfy these, laminated films made of various polyethylene resins have been proposed.

For example, in JP-A-59-112252, a laminated film in which a layer in which high density polyethylene and linear low density polyethylene are mixed is used as an intermediate layer and linear low density polyethylene is used as both outer layers is disclosed. 58-59080
In the publication, a laminated film using high-density polyethylene for the intermediate layer, linear low-density polyethylene for the outer layer, high-pressure low-density polyethylene or an ethylene-based copolymer for the other outer layer, and more specifically, high-density polyethylene for the intermediate layer And an ethylene-based copolymer, a linear low-density polyethylene for the outer layer, and a laminated film using a high-pressure low-density polyethylene or an ethylene-based copolymer for the other outer layer. In JP-A-59-38059, the intermediate layer has a high density. Polyethylene, a laminate using linear low-density polyethylene for both outer layers, a high-density polyethylene and a linear low-density polyethylene for the intermediate layer, and a laminate using linear low-density polyethylene for both outer layers are disclosed. .

The above-mentioned laminated film is excellent in impact resistance, waist strength, gas barrier property, etc., but is inferior in transparency and moldability. The laminated film of is excellent in impact resistance and waist strength. Excellent in gas barrier property and moldability, but inferior in transparency. Although the lamination resistance is excellent in impact resistance, waist strength, gas barrier property, etc., there is a problem that transparency and moldability are inferior. In recent years, when a bag is made and used as a bag, improvement in low-temperature heat sealability, adhesive strength of a seal portion, and the like is strongly desired as the bag is made faster. However, in the conventional laminated film as described above, the heat sealing temperature of the inner layer is high during bag making, and the productivity during bag making is not improved.

As the bag and the zipper bag, those using a general polyethylene resin are widely used in various fields (for example, Japanese Patent Publication No. 59-29500, Japanese Patent Publication No. 60-50663, and Japanese Patent Publication No. 60-50663). Kaisho 58-17134
No. 7, JP-A No. 61-203854, etc.). These zipper bags are generally composed of a single layer film,
Polyethylene resins such as low density polyethylene (referred to as LDPE), linear low density polyethylene (referred to as LLDPE), and high density polyethylene (referred to as HDPE) are used. However, although LDPE is excellent in transparency, it has a drawback that it is inferior in gas barrier property and impact resistance, and its rigidity is weak. Further, LLDPE is insufficient in gas barrier property, stiffness of the waist, and moldability. In addition, HDPE
Although it has properties such as gas barrier property, impact resistance, and waist strength, it has a problem of poor transparency.

Further, as the zipper bag, there is a laminated bag mainly used for food. The polyolefin single-layer zipper bag is highly productive and inexpensive because the zipper and bag can be integrally molded, but as described above, transparency, impact resistance, waist strength, gas barrier property, and moldability are provided. There is nothing that can satisfy the above. On the other hand, the laminated bag has polyamide (PA), polyvinylidene chloride coated biaxially oriented polypropylene (KOP), biaxially oriented polypropylene (OPP), ethylene-vinyl alcohol copolymer (EVOH), polyester (PET) as a gas barrier layer. , Aluminum deposition film is used. Therefore, the gas barrier property is very high, but there is a problem that the manufacturing cost is high and the cost is high. Therefore, even in the field of foods, etc., the gas barrier property is higher, and the transparency, impact resistance, elasticity of the waist, and moldability are excellent.
There is a need for a zipper bag, which is cheaper than a zipper bag.

Similarly, a compression storage bag for storing clothing, futon, etc. is required to have the same performance as described above. Further, when the laminated body is heat-sealed to form a laminated bag and the zipper tape is heat-sealed to the opening to form the zipper bag, the low temperature heat-sealing property of the inner layer of the laminated bag is required. When the heat-sealing temperature is high, the heat-sealing portion does not become smooth and the appearance is poor, or the two zipper tapes are often fused and do not form a bag. Further, it is required to lower the heat sealing temperature in order to increase the productivity of the zipper bag.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate excellent in transparency, impact resistance, stiffness, gas barrier property, low temperature heat sealability, moldability and the like. . Also, a bag using such a laminated body, a zipper bag,
To provide a compression storage bag and a compression storage bag with a zipper.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors achieved the above objects by using a laminate of a specific resin and reached the present invention. Further, by using such a laminate of the specific resin, it is possible to provide the bag, the compression storage bag, and the compression storage bag with the chuck of the present invention, which are excellent in various physical properties such as transparency, heat sealability, and gas barrier property. Became.

That is, the first invention of the present application satisfies (A) an ethylene / α-olefin copolymer having a density of 0.86 to 0.94 g / cm ³ , and (A ') the following (A) to (D): Density of 0.86 to 0.94 g / cm ³ ethylene / α-
An I-layer comprising at least one ethylene-based (co) polymer selected from an olefin copolymer and (B) an ethylene polymer obtained by a high-pressure radical polymerization method; and (C) a density of 0.
High-density polyethylene (C) 100 with 94 g / cm ³ or more
To 50% by weight and at least one ethylene-based (co) selected from the above (A) ethylene-α-olefin copolymer, (A ′) ethylene-α-olefin copolymer and (B) ethylene polymer. A second layer consisting of resin up to 50% by weight of polymer, said (A ') density of 0.86 to 0.94
No. II composed of an ethylene-based (co) polymer containing g / cm ^{3 of} an ethylene / α-olefin copolymer as a main component
And a layer I as an intermediate layer.

[A-D] (A) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (B) Composition distribution parameter Cb is 1.08 to 2.00 (C) Orthodichlorobenzene ( ODC
B) The amount X (wt%) of the soluble content and the density d and MFR satisfy the following a) or b) relationship: a) The values of the density d and MFR are d-0.008logM.
In the case of FR ≧ 0.93 X <2.0 b) The value of the density d and MFR is d−0.008logM
When FR <0.93 X <9.8 × 10 ³ (0.9300-d + 0.008l)
ogMFR) ² +2.0 (d) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF)

A second invention of the present application provides a bag body made of the laminated body according to the first invention.

A third invention of the present application is characterized in that a thermoplastic resin chuck having a male claw and a female claw is formed in an opening of the bag body made of the laminated body according to the first invention. It provides a zipper bag.

A fourth invention of the present application provides a compression storage bag comprising the laminate of the first invention.

[0015]

The laminated body of the present invention has (A) a density of 0.86-0.
94 g / cm ³ ethylene / α-olefin copolymer,
(A ') The density satisfying the following (a) to (d) is 0.86.
~ 0.94 g / cm ³ ethylene / α-olefin copolymer and (B) at least one ethylene-based (co) polymer selected from ethylene polymers obtained by the high-pressure radical polymerization method; (C) Density 0.94 g / cm ³
100 to 50% by weight of the above high-density polyethylene (C) and the above-mentioned (A) ethylene-α-olefin copolymer,
A second layer comprising a resin of up to 50% by weight of at least one ethylene-based (co) polymer selected from (A ′) ethylene-α-olefin copolymer and (B) ethylene polymer;

The density (A ') is 0.86 to 0.94 g.
III composed of an ethylene-based (co) polymer whose main component is an ethylene / α-olefin copolymer of 1 / cm ³
It is predicted that a resin mainly composed of high-density polyethylene having a density of 0.94 g / cm ³ or more is used as the intermediate layer by forming a laminate including the layer and the II layer as the intermediate layer. It has a transparency that is unachievable, retains gas barrier properties, impact resistance, waist strength, etc., and is a laminate with excellent low temperature heat sealability, shortening the heat seal cycle during bag making. , Productivity is greatly improved.

[A-D] (A) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (B) Composition distribution parameter Cb is 1.08 to 2.00 (C) Orthodichlorobenzene ( ODC
B) The amount X (wt%) of the soluble content and the density d and MFR satisfy the following a) or b) relationship: a) The values of the density d and MFR are d-0.008logM.
In the case of FR ≧ 0.93 X <2.0 b) The value of the density d and MFR is d−0.008logM
When FR <0.93 X <9.8 × 10 ³ (0.9300-d + 0.008l)
ogMFR) ² +2.0 (d) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF)

A bag, a zipper bag, and a compression storage bag using such a laminated body are excellent in high-speed bag-making property and high in productivity such as chuck formation, and these bags are excellent in transparency and It also has gas barrier properties, impact resistance, and waist strength.

The present invention will be described in more detail below with reference to the drawings. FIG. 3 shows a sectional view of an embodiment of the laminated body of the present invention. In FIG. 3, the laminate 1 of the present invention is
(A) an ethylene / α-olefin copolymer having a density of 0.86 to 0.94 g / cm ³ , (A ′) below (a) to
The density satisfying (d) is 0.86 to 0.94 g / cm ^3.
An ethylene / α-olefin copolymer, (B) an I-layer 2 comprising at least one ethylene-based (co) polymer selected from high-pressure radical polymerization ethylene polymers,
(C) High density polyethylene having a density of 0.94 g / cm ³ or more (C) 100 to 50% by weight and the above (A) ethylene-α
An olefin copolymer, (A ′) an ethylene-α-olefin copolymer, and (B) an ethylene polymer, and at least one ethylene-based (co) polymer, which is up to 50% by weight of a resin. , The (A ') density is 0.86 to 0.9
No. I composed of an ethylene-based (co) polymer containing 4 g / cm ^{3 of} an ethylene / α-olefin copolymer as a main component
A layered body including the II layer 4 and the II layer 3 as an intermediate layer.

[A-D] (A) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (B) Composition distribution parameter Cb is 1.08 to 2.00 (C) Orthodichlorobenzene ( ODC
B) The amount X (wt%) of the soluble content and the density d and MFR satisfy the following a) or b) relationship: a) The values of the density d and MFR are d-0.008logM.
In the case of FR ≧ 0.93 X <2.0 b) The value of the density d and MFR is d−0.008logM
When FR <0.93 X <9.8 × 10 ³ (0.9300-d + 0.008l)
0gMFR) ² +2.0 (d) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation (TREF)

In FIG. 3, the I-layer 2 of the present invention has a role of maintaining the impact resistance, transparency, molding processability and the like of the laminate 1, and the (A) ethylene-α-olefin copolymer The polymer may be composed of any one of the polymer, (A ′) ethylene-α-olefin copolymer, and (B) ethylene polymer, but the best balance of molding processability, impact resistance, etc. Considering this, a mixed composition of the component (A) and / or the component (A ′) and the component (B) is preferable.

The mixing ratio of the mixed composition of the component (A) and / or the component (A ') and the component (B), which is a preferable combination of the I-th layer 2, is such that the component (A) and / or the component (A') is mixed. The total of the components is 60 to 95% by weight, (B) component 4
0 to 5% by weight, preferably 70 to 90% by weight of the former, 30 to 10% by weight of the latter, and more preferably 75 to 9 of the former.
The range is 0% by weight and the latter 25 to 10% by weight. When the blending amount of the component (B) exceeds 40% by weight, there is a possibility that the balance between molding processability and impact resistance cannot be maintained. Further, in order to improve the moldability of the above-mentioned layer I, it is desirable to add a lubricant such as a higher fatty acid or a metal salt thereof or an amide.

The above (A) density is 0.86 to 0.94 g /
The ethylene · alpha-olefin copolymer cm ^3, density using the catalyst (referred to as Ziegler-type catalysts for short below), such as a Ziegler catalyst or Phillips catalyst of 0.91~0.94g / cm ³ A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms (hereinafter referred to as LLDPE) by a high / medium / low pressure method and other known methods, having a density of 0.86 to 0.94 g / cm 3. ³ ultra low density polyethylene (hereinafter referred to as VLDPE), density 0.86
˜0.91 g / cm ³ of ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber.

The above-mentioned LLDPE produced by the Ziegler type catalyst means ethylene.α-having a density in the range of 0.91 to 0.94 g / cm ³ , preferably 0.91 to 0.93 g / cm ^3.
It is an olefin copolymer and has an MFR of 0.05 to 30 g.
/ 10 minutes, preferably 0.1 to 20 g / 10 minutes. The molecular weight distribution (Mw / Mn) is not particularly limited, but it is generally in the range of 3.0 to 13, preferably 3.5 to 8.

The α-olefin of LLDPE is an α-olefin having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms, and specifically, propylene and 1- Butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like can be mentioned.
If the MFR is less than 0.05 g / 10 minutes, the moldability will be deteriorated, and if it exceeds 30 g / 10 minutes, impact resistance, heat seal strength and the like may be deteriorated.

The ultra-low density polyethylene (VLDPE) using the above Ziegler type catalyst has a density of 0.86 to
0.91 g / cm ³ , preferably 0.88 to 0.905
It is an ethylene-α-olefin copolymer in the range of g / cm ³ , and the MFR is selected in the range of 0.01 to 20 g / 10 minutes, preferably 0.1 to 10 g / 10 minutes. The VL
DPE is linear low density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EPD).
M) is a polyethylene showing an intermediate property, and has a maximum peak temperature (Tm) of 6 by differential scanning calorimetry (DSC).
It is a specific ethylene / α-olefin copolymer having a property of 0 ° C. or higher, preferably 100 ° C. or higher, and boiling n-hexane insoluble content of 10% by weight or higher, and a high crystal part and ethylene / α-shown by LLDPE. It is a resin that also has an amorphous part shown by olefin copolymer rubber, and the former characteristics such as impact resistance and heat resistance are well balanced with the latter characteristics such as rubber elasticity and low temperature impact resistance. Coexist.

The ethylene / α-olefin copolymer rubber is an ethylene / propylene copolymer rubber or an ethylene / propylene / diene copolymer rubber having a density of 0.86 to less than 0.91 g / cm ^3. Examples of the ethylene / propylene rubber include a random copolymer (EPM) containing ethylene and propylene as main components, and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as a third component. The random copolymer (EPDM) used as a component is mentioned.

The ethylene / α-olefin copolymer having a density of 0.86 to 0.94 g / cm ³ satisfying the following (A) to (A) of the present invention is ethylene and 3 carbon atoms. ~
It is a copolymer with one or more selected from 20 α-olefins. The α-olefin having 3 to 20 carbon atoms is preferably one having 3 to 12 carbon atoms, specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene. , 1-decene, 1-dodecene, and the like. Further, it is desirable that the total content of these α-olefins is selected in the range of usually 30 mol% or less, preferably 20 mol%.

[A-D] (A) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (B) Composition distribution parameter Cb is 1.08 to 2.00 (C) Orthodichlorobenzene ( ODC
B) The amount X (wt%) of the soluble content and the density d and MFR satisfy the following a) or b) relationship: a) The values of the density d and MFR are d-0.008logM.
In the case of FR ≧ 0.93 X <2.0 b) The value of the density d and MFR is d−0.008logM
When FR <0.93 X <9.8 × 10 ³ (0.9300-d + 0.008l)
ogMFR) ² +2.0 (d) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF)

The ethylene / α-olefin copolymer (A ') of the present invention has a density of 0.86 to 0.94 g / cm ³ , preferably 0.88 to 0.94 g / cm ³ , and more preferably 0. It is in the range of 89 to 0.94 g / cm ³ . When the density is less than 0.90 g / cm ³ , the heat resistance is lowered, the blocking property of the film is deteriorated, and the low crystalline components are leached into the contents. On the other hand, those exceeding 0.94 g / cm ³ have poor transparency and lose flexibility.

The melt flolate (MFR) of the ethylene / α-olefin copolymer (A ') is 0.01-10.
0 g / min, preferably 0.1 to 50 g / min, more preferably 0.5 to 40 g / 10 min. If the MFR is less than 0.01 g / 10 minutes, the moldability is poor, and 100
If g / 10 minutes or more, the strength decreases.

The (A) Mw / Mn of the ethylene / α-olefin copolymer (A ') of the present invention is 1.5 to 4.5, preferably 1.8 to 4.0, and more preferably 2. ．
It is preferably in the range of 0 to 3.0. If the Mw / Mn is less than 1.5, the moldability is poor, and if it exceeds 4.5, the impact resistance is poor. The above-mentioned method of calculating the molecular weight distribution (Mw / Mn) is to obtain the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and obtain the ratio Mw / Mn.

The method for measuring the composition distribution parameter Cb of the ethylene / α-olefin copolymer is as follows. That is, ortho-dichlorobenzene (O
DCB) 135 so that the sample concentration becomes 0.2% by weight
Dissolve by heating at ℃. This solution was added to diatomaceous earth (Celite 5
45) is transferred to a column packed and cooled to 25 ° C. at a rate of 0.1 ° C./min to deposit a sample on the surface of Celite. Next, while flowing ODCB through the column at a constant flow rate, the temperature of the column is increased stepwise to 120 ° C. in steps of 5 ° C. to elute and separate the sample. Methanol is mixed with the eluate, the sample is reprecipitated, filtered and dried to obtain a fraction sample at each elution temperature. The weight fraction of the eluted sample at each temperature and the degree of branching (the number of branches per 1000 carbon atoms) are measured by 13 C-NMR.

For the fraction from 30 ° C. to 90 ° C., the branching degree is corrected as follows. That is, the measured branching degree is plotted against the elution temperature, and the correlation is approximated to a straight line by the method of least squares to create a calibration curve. The correlation coefficient of this approximation is large enough. The value obtained from this calibration curve is defined as the degree of branching of each fraction. The elution temperature is 95 ° C
For these components, a linear relationship is not always established between the elution temperature and the degree of branching, so this correction is not performed and measured values are used.

Next, the weight fraction w of each fraction
The i, the amount of change in the degree of branching _{b i} per the elution temperature 5 ° C. _{(b i}
-Bi _-1 ) to obtain the relative concentration c _i , and plot the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided with a constant width, and the composition distribution parameter Cb is calculated from the following equation.

[0036]

[Equation 1]

Here, c _j and b _j are the relative density and branching degree of the j-th section, respectively. Composition distribution parameter Cb
Is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Many proposals have been made for the method of describing the composition distribution of the ethylene / α-olefin copolymer. For example, in JP-A-60-88016, numerical processing is performed assuming that the cumulative weight fraction has a specific distribution (lognormal distribution) with respect to the number of branches of each fractionated sample obtained by solvent fractionation of the sample. , Weight average branching degree (Cw) and number average branching degree (C
n) is calculated. This approximation calculation becomes less accurate when the number of branches of the sample and the cumulative weight fraction deviate from the lognormal distribution, and the correlation coefficient R is obtained when measurement is performed on commercially available LLDPE.
² is quite low and the accuracy of the value is not sufficient. Also, this C
The method of measuring w / Cn and the method of numerical processing are different from those of Cb of the present invention, but if the values are compared, Cw /
The value of Cn is considerably larger than that of Cb.

The composition distribution parameter Cb of the (A ') ethylene / α-olefin copolymer of the present invention is 1.08 to
It is 2.00, preferably 1.10 to 1.80, and more preferably 1.12 to 1.70. If it is larger than 2.00, blocking is easy,
The heat-sealing property also becomes poor, and a low molecular weight or high-branching component oozes out on the surface of the resin to cause a sanitary problem.

The amount of the ODCB-soluble component at 25 ° C. (c) of the ethylene / α-olefin copolymer (A ′) of the present invention is measured by the following method. 0.5 g of sample is 20 m
Heat at 135 ° C. for 2 hours with 1 ODCB to completely dissolve the sample and cool to 25 ° C. Put this solution at 25 ° C
After overnight standing, filter through a Teflon filter and collect the filtrate. The absorption peak area near the wave number 2925 cm ⁻¹ of the asymmetric stretching vibration of methylene of this filtrate is obtained, and the sample concentration is calculated from the calibration curve prepared in advance. From this value, the ODCB-soluble matter at 25 ° C. is determined.

According to the present invention, (c) the relationship between the amount (c) X wt% of the ODCB-soluble component at 25 ° C. and the density d and MFR, the values of d and MFR satisfy d-0.008logMFR ≧ 0.93. In the case of, X is less than 2% by weight, preferably less than 1% by weight. In the case of d-0.008logMFR <0.93, X <9.8 × 10 ³ (0.9300-d + 0.008l).
ogMFR) ² +2.0, preferably X <7.4 × 10 ³ × (0.9300−d + 0.008)
logMFR) ² +1.0 More preferably, X <5.6 × 10 ³ × (0.9300−d + 0.008)
It is necessary to satisfy the relation of (logMFR) ² +0.5.

The ODCB-soluble component at 25 ° C. is a highly branched component and a low molecular weight component contained in the ethylene / α-olefin copolymer, which causes problems of hygiene and blocking of the inner surface of the molded product. It is desirable that the content is small. The amount of ODCB solubles is affected by the comonomer content and molecular weight. Therefore, the fact that the density and the amounts of MFR and ODCB-soluble component, which are indicators, satisfy the above relationship indicates that the uneven distribution of α-olefin contained in the whole copolymer is small.

The (A ') ethylene / α-olefin copolymer of the present invention may have a plurality of peaks in the elution temperature-elution amount curve (d) determined by the continuous temperature rising elution fractionation method (TREF). is necessary. Further, it is particularly preferable that a peak exists between 85 ° C and 100 ° C. The presence of this peak improves the heat resistance of the molded body. FIG. 1 shows the elution temperature-elution amount curve of the copolymer of the present invention, and FIG. 2 shows the difference from the so-called metallocene-catalyzed copolymer.

The method of measuring TREF according to the present invention is as follows. The sample is heated and dissolved at 135 ° C. in ODCB containing an antioxidant so that the sample concentration becomes 0.05% by weight. 5 ml of this sample solution is injected into a column filled with glass beads and cooled to 25 ° C. at a cooling rate of 0.1 ° C./min to deposit the sample on the surface of the glass beads. next,
The sample is sequentially eluted while the column temperature is raised at a constant rate of 50 ° C./hr while flowing ODCB at a constant flow rate through this column. At this time, the concentration of the sample eluted in the solvent was 2925 cm ⁻¹ of wave number of asymmetric stretching vibration of methylene.
The infrared absorption is continuously detected by an infrared detector. From this value, the concentration of the ethylene / α-olefin copolymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. Since the TREF analysis can analyze the change of the elution rate with respect to the temperature change continuously with a very small amount of sample, it is possible to detect relatively fine peaks that cannot be detected by the fractionation method.

The production of the specific (A ') ethylene / α-olefin copolymer of the present invention is preferably carried out by the following D1 to D
Polymerization with a catalyst consisting of 5 is desirable. That is,
D1: General formula Me ¹ R ¹ _p (OR ² ) _q X ¹ _4-p-q.
(Wherein Me ¹ represents zirconium, titanium, and hafnium, and R ¹ and R ² each have 1 carbon atom).
To 24 hydrocarbon groups, X ¹ represents a halogen atom, p and q are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4), D2: general formula Me ² R ³ _m. (O
R ⁴ ) _n X ² _z-m-n A compound (in the formula, Me ²
Is a Group I to III element of the periodic table, R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom (provided that when X ² is a hydrogen atom, Me ² is (Limited to the case of Group III element of the periodic table), and Z is M
represents the valence of e ² , and m and n are 0 ≦ m ≦ z and 0 ≦, respectively.
An integer satisfying the range of n ≦ z, and 0 ≦ m + n ≦
z), D3: an organic cyclic compound having a conjugated double bond, and D4: a modified organoaluminum compound containing an Al—O—Al bond obtained by the reaction of an organoaluminum compound with water, D5: an inorganic carrier and / or Alternatively, it is a catalyst obtained by bringing the particulate polymer carriers into contact with each other.

The above catalyst component D1 has the general formula Me ¹ R
¹ _p wherein Me ¹ of _{^{(OR 2) q X 1 4}} -p-q compounds represented by represents zirconium, titanium, hafnium.
The type of these transition metals is not limited, and a plurality of transition metals can be used. However, it is particularly preferable that zirconium having excellent weather resistance of the copolymer is contained. R ¹ and R ² are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and specifically, methyl group, ethyl group, propyl group, isopropyl group. , Alkyl groups such as butyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group, styryl group Group, benzhydryl group, phenylbutyl group, aralkyl group such as neophyl group, and the like. These may have branches. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p and q satisfy the ranges of 0 ≦ p <4, 0 ≦ q <4, 0 ≦ p + q ≦ 4, and preferably 0 ≦ p + q ≦ The range is 4.

Examples of the compound represented by the above general formula of the catalyst component D1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetrabutoxyzirconium, tetrabutoxytitanium, tetrabutoxyhafnium. Examples thereof include Zr (OR) ₄ compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium, and two or more kinds of these may be mixed and used.

The catalyst component D2 has the general formula Me ² R
^In the formula of the compound represented by ³ _m (OR ⁴ ) _n X ² _z-mn , Me ² represents a Group I to III element of the periodic table, and lithium, sodium, potassium, magnesium, calcium, zinc, boron. , Aluminum, etc. R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. An alkyl group such as a group; an alkenyl group such as a vinyl group and an allyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, an indenyl group and a naphthyl group; a benzyl group, a trityl group, a phenethyl group, a styryl group, Examples thereof include aralkyl groups such as a benzhydryl group, a phenylbutyl group and a neophyl group. These may have branches. X ² represents a halogen atom such as fluorine, iodine, chlorine and bromine, 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 exemplified by boron, aluminum and the like. Further, z represents the valence of Me ² , m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z.

Examples of the compound represented by the general formula of the catalyst component D2 include organic lithium compounds such as methyllithium and ethyllithium; organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; dimethyl. Organozinc compounds such as zinc and diethylzinc; Organoboron compounds such as trimethylboron and triethylboron; Trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesqui Organic aldehydes such as chloride, diethyl aluminum ethoxide, and diethyl aluminum hydride Derivatives such as iodonium compounds.

The above-mentioned organic cyclic compound having a conjugated double bond of the catalyst component D3 is a ring having two or more conjugated double bonds, preferably 2 to 4 and more preferably 2 to 3 conjugated double bonds. Or a cyclic hydrocarbon compound having 2 or more and having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially 1 to 6 hydrocarbon residues (typically, A cyclic hydrocarbon compound substituted with an alkyl group having 1 to 12 carbon atoms or an aralkyl group); 2 or more, preferably 2 to 4, and more preferably 2 to 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 24 to 24, preferably 4 to 12; wherein the cyclic hydrocarbon group is partially a hydrocarbon residue of 1 to 6 or an alkali metal salt (sodium or lithium salt). Included are substituted organosilicon compounds. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

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

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

Specific examples of the organic cyclic hydrocarbon compound of the above component D3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-. Cyclopolyene or substituted cyclopolyene having 5 to 24 carbon atoms such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene and methylfluorene, monocyclopentadienylsilane, biscyclopentadiene Phenylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane,
Examples include trisindenylsilane and the like.

The modified organoaluminum compound containing an Al--O--Al bond obtained by reacting the organoaluminum compound of catalyst component D4 with water is usually called an aluminoxane by reacting an alkylaluminum compound with water. A modified organoaluminum is obtained, which is usually 1 to 100, preferably 1 to 50 Al- in the molecule.
It contains an O-Al bond. The modified organoaluminum compound may be linear or cyclic.

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

Examples of the inorganic carrier and / or the particulate polymer carrier of the catalyst component D5 include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, or thermoplastic resins, thermosetting resins and the like. Can be mentioned. Suitable metals that can be used for the inorganic carrier include:
Examples include iron, aluminum, and nickel. Specifically, SiO 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 , S
_{iO 2 -V 2 O 5, SiO} 2 -MgO, SiO 2 -Cr
₂ O _{3 and the} like. Among these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

As the organic compound, either a thermoplastic resin or a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, Examples thereof include polystyrene, polynorbornene, various natural polymers, and mixtures thereof. The inorganic carrier and / or the particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are subjected to contact treatment with an organoaluminum compound or a modified organoaluminum compound containing an Al-O-Al bond. After the ingredient C
It can also be used as 5.

The production method of the ethylene / α-olefin copolymer (A ') of the present invention is produced by a gas phase method, a slurry method, a solution method or the like, and is particularly limited to a one-step polymerization method, a multi-step polymerization method or the like. is not.

The ethylene polymer by the high pressure radical polymerization method (B) of the present invention means an ethylene homopolymer (low density polyethylene) having a density of 0.91 to 0.94 g / cm ³ by the high pressure radical polymerization method, ethylene vinyl. Examples thereof include an ester copolymer and a copolymer of ethylene and an α, β-unsaturated carboxylic acid or its derivative.

The low density polyethylene (referred to as LDPE) is selected in the range of MFR of 0.05 to 30 g / 10 minutes, preferably 0.1 to 20 g / 10 minutes. Within this range, the melt tension of the composition is in an appropriate range, and film formation and the like are easy. The density of the LDPE is 0.91
To 0.94 g / cm ³ , preferably 0.912 to 0.9
35 g / cm ³ , more preferably 0.912 to 0.9
It is selected in the range of 30 g / cm ³ . The molecular weight distribution (Mw / Mn) is 3.0 to 12, preferably 4.0.
8.0. The LDPE is produced by a known high-pressure radical polymerization method, and may be any of a tubular method and an autoclave method.

The above ethylene / vinyl ester copolymer is produced by a high-pressure radical polymerization method and contains ethylene as a main component and contains vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearic acid. It is a copolymer with vinyl ester monomers such as vinyl and trifluorovinyl acetate. Among them, particularly preferred is vinyl acetate. Ethylene 50 to 99.5% by weight, vinyl ester 0.5 to 50% by weight, other copolymerizable unsaturated monomer 0
A copolymer consisting of 49.5% by weight is preferred. Further, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight. The MFR of these copolymers is 0.1 to 20 g / 10 minutes, preferably 0.1.
It is selected in the range of 3 to 10 g / min.

Further, as a typical copolymer of the above ethylene and α, β-unsaturated carboxylic acid or its derivative, ethylene / (meth) acrylic acid or its alkyl ester copolymer can be mentioned. As these comonomers, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid-n- Butyl, methacrylic acid-n-
Butyl, 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 in the range of 3 to 20% by weight, preferably 5 to 15% by weight. The MFR of these copolymers is 0.1
-30 g / 10 min, preferably 0.2-20 g / min.

Among the specific preferable combinations of the resins forming the I layer 2 of the present invention, the mixed composition of (A) LLDPE and (B) LDPE is the most preferable in terms of transparency, moldability and impact resistance. preferable. It is also possible to use (A ′) ethylene-α-olefin copolymer instead of (A) LLDPE. Further, a mixed composition in which (A) + (A ′) and (B) are mixed may be used.

In FIG. 3, the intermediate layer II 3 of the present invention.
Is composed of a resin containing (C) a high-density polyethylene (referred to as HDPE) having a density of 0.94 g / cm ³ or more as a main component in order to maintain the rigidity of the laminate 1 and various physical properties such as gas barrier properties. To be done. The intermediate second layer 3 may be HDPE alone, but preferably the above HDPE, the above-mentioned (A) ethylene-α-olefin copolymer, and (A ′) ethylene-α.
A mixed composition with at least one ethylene (co) polymer selected from the olefin copolymer and the ethylene polymer (B) is desirable because it satisfies the above physical properties in a well-balanced manner.

The mixing composition ratio of the resin forming the second layer 3 of the present invention is 5 to 40% by weight of the ethylene (co) polymer, preferably HD to 95 to 60% by weight of HDPE.
90 to 70% by weight of PE and 1 of ethylene-based (co) polymer
It is desirable to select in the range of 0 to 30% by weight. If the blending amount of the ethylene (co) polymer exceeds 40% by weight, performances such as stiffness and gas barrier property may deteriorate.

A specific preferable combination of the layer II of the present invention has a density of 0.95 to ◯. HDP of 97 g / cm ³
E, LLDPE, VLDPE, ethylene / α-olefin copolymer rubber, (A ′) density 0.86 to 0.94 g
/ Cm ³ ethylene / α-olefin copolymer and the like, but the transparency, impact resistance, waist strength of the laminate 1,
HDPE from the viewpoint of satisfying various physical properties such as molding stability
And (A ') ethylene / α-olefin copolymer having a density of 0.86 to 0.94 g / cm ³ , or VLDPE is most preferable.

The above (C) HDPE has a density of 0.94.
˜0.97 g / cm ³ , preferably 0.95 g / cm ³
In the above HDPE, an ethylene homopolymer or ethylene and an α-olefin having 3 to 12 carbon atoms produced by a known process such as a slurry method, a solution method or a gas phase method using a known Ziegler type catalyst. And copolymers thereof, and specific α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecene and the like. it can. Among these α-olefins, α-olefins having 3 to 8 carbon atoms are particularly preferable.

The layer III of the present invention plays a role of maintaining the transparency, heat sealing property, moldability, impact resistance and the like of the laminate 1. The third layer 4 is required to have high heat-sealing strength at low temperatures and an effect of improving transparency in order to maintain high-speed productivity during bag making. The resin forming the third layer 4 is
The specific (A ′) density 0.86 to 0.94 g / cm ³
It is composed of an ethylene-based (co) polymer whose main component is the ethylene / α-olefin copolymer. The (A ') copolymer preferably has a heat sealing temperature of 1
The temperature is 20 ° C or lower, preferably 115 ° C or lower, and more preferably 110 ° C or lower. The resin forming the third layer 4 may be (A ′) ethylene-α-olefin copolymer alone, but retains transparency, heat seal characteristics, and impact resistance,
In order to further improve molding processability and the like, the above-mentioned (A) ethylene-α-olefin copolymer and / or (B)
It is desirable to incorporate a small amount of at least one ethylene-based (co) polymer selected from ethylene polymers. The blending amount of these ethylene-based (co) polymers is 5 to 40% by weight.
The range is selected. If the blending amount exceeds 40% by weight, the transparency, heat seal characteristics, impact resistance, etc. may be impaired.

The heat-sealing temperature of the present invention means the single-layer film (80) of the resin used for the heat-sealing layer of the laminate.
μm), heat seal width 15 mm, length 80
mm test piece is prepared, and the heat sealing time is 1.0
Seconds, heat seal under the condition of heat seal pressure of 1.5 kgf / cm ² , and then a tensile test is performed at a tensile speed of 300 mm / min, and heat seal strength (gf / 15 mm width)
Ask for. Heat sealing is performed by changing the sealing temperature at several points, and the heat sealing strength is obtained by a tensile test as described above. Create a graph of seal temperature and heat seal strength,
The seal temperature at which the heat seal strength was 500 g / 15 mm width was defined as the heat seal temperature in the present invention.

The laminate of the present invention is a laminate having at least a three-layer structure, and if necessary, another thermoplastic resin layer of the same kind or different kind may be provided between the I layer 2 and the III layer 4 in the figure. It can be installed. The layer ratio of each layer is not particularly limited, and generally 0.5 / 9 / 0.5 to
It may be appropriately determined within the range of 3/4/3. Furthermore, a polyamide layer having excellent gas barrier properties, an ethylene / vinyl alcohol copolymer layer, a polyester layer, or an adhesive layer made of an adhesive resin such as an acid-modified polyolefin may be added to the present laminate. Further, in the laminated body of the present invention, when both layers on the surface require heat sealability, both layers may be formed by the layer III.

A specific example of the laminate of the present invention is A / C / A 'as the I layer / intermediate II layer / III layer,
A / B / C / A ', A / C / B / A', A + B / C /
A ', A + B / C + A / A', A + B / C + A / A '+
B, A / C / M / A ', A / M / C / A', A '/ C /
A ', A' + B / C + A / A '+ B, A / C + A' /
A'and the like. (However, A: LLDPE with Ziegler type catalyst, B: LDP with high pressure radical
E, etc., C: HDPE with Ziegler type catalyst, A ':
The copolymer (A ') of the present invention, M: another resin)

As the method for producing the laminate of the present invention, various known methods such as a coextrusion method, an extrusion lamination method, a sandwich lamination method, a dry lamination method and a combination thereof can be adopted.
Specifically, the coextrusion inflation method or the coextrusion T-die method in which the I layer 2, the III layer 4, and the intermediate II layer 3 in FIG. 3 are extruded by separate extruders and fed to a die having a multilayer structure. The I layer 2 is molded in advance, and the intermediate II layer 3 is melt extruded to form the I layer 2.
Extrusion lamination method of performing extrusion lamination of the intermediate second layer 3 and further melt-extruding the third layer 4, preforming the first layer 2 and the third layer 4,
A sandwich lamination method in which an intermediate II-layer 3 is melt-extruded between both layers, or the I-layer 2, III-layer are previously prepared.
A dry lamination method or the like in which the layer 4 and the intermediate second layer 3 are separately molded and laminated using an adhesive or the like can be used. Layer I 2, intermediate layer II 3, layer II
If the I-layer 4 is preformed, these layers may be uniaxially or biaxially stretched or rolled.

In the present invention, an antioxidant, an antiblocking agent, a lubricant, an antistatic agent, an antifogging agent, an ultraviolet absorber, an organic or inorganic filler, an organic or inorganic pigment, and Known additives such as a nucleating agent and a cross-linking agent can be added within a range that does not essentially impair the characteristics of the present invention.

The second invention of the present application is a bag made of the above-mentioned laminated body, and the zipper bag of the third invention will be described as a representative. The zipper bag of the present invention relates to a zipper bag in which a thermoplastic resin zipper having male and female claws is formed in the opening of the bag body made of the above laminated body. Conventionally, a zipper bag using a polyethylene resin is also well known. For example, Japanese Patent Publication No. 59-29500, Japanese Patent Publication No. 6
0-50663, JP-A-58-171347, JP-A-61-203354, and the like.
These zipper bags are generally made of a single layer film and made of polyethylene resin such as LDPE, LLDPE and HDPE. However, although LDPE is excellent in transparency, it has a drawback that it is inferior in gas barrier property and impact resistance, and its rigidity is weak. Further, LLDPE has insufficient gas barrier properties, impact resistance, and waist strength. Further, although HDPE has characteristics such as gas barrier property, impact resistance, and waist strength, it has a problem of poor transparency, and all of them have poor low-temperature heat-sealing properties and are not suitable for bag making. A resin having high-speed productivity is desired.

The present invention improves the high-speed productivity such as shortening the heat-sealing cycle at the time of bag making and fusing of the zipper tape by using the above-mentioned specific laminate. That is, the third invention provides a zipper bag, which is characterized in that a thermoplastic resin chuck having male and female claws is formed in an opening of a bag body made of the laminated body of the first invention. To do.

The present invention will be described in more detail below with reference to the drawings. FIG. 4 is a plan view of a zipper bag as an example of the present invention. As shown in FIG. 4, the zipper bag of the present invention is
In the vicinity of the opening 6 of the bag 5, one to a plurality of rows of thermoplastic resin chucks 7 having male and female claws are provided. 4, the bag body 5 of the present invention becomes the laminated film 1 having the same structure as that of FIG. 1 when cut along the AA cutting line of FIG.

FIG. 5 is a sectional view showing an example of a thermoplastic resin zipper tape having male and female claws used in the present invention. The thermoplastic resin zipper tape 8 is formed by integrally forming a thermoplastic resin zipper having at least one pair of hook-shaped male claw 9 and female claw 10 as a set, and as shown in FIG. In order to further improve the performance, the zipper may be formed in upper and lower rows in one or more rows in the bag opening, and in the case of a plurality of rows, male nails and female nails are arranged in parallel in the same direction, or male nails are arranged. It is also possible that 9 and female claws 10 are alternately arranged in opposite positions.
By forming the thermoplastic resin zipper at the opening of the bag in this way, the contents inside the bag can be packaged and stored, and when necessary, only the required amount of the contents can be taken out and the rest can be saved. Can be given.

FIG. 6 is a cross-sectional view of the sealing material applied to the thermoplastic resin chuck. The two sets of male pawls (9, 9) and female pawls (1) of the chuck tape 8 shown in FIG.
0, 10) are alternately arranged at the opposite positions and are engaged with each other, and a plurality of ridges 11 are provided on the inner wall of the female claw 10 as a sealing material. By providing a plurality of sealing members for the protrusions 11 in this manner, it is possible to maintain a higher airtightness. The sealing material is made of a soft substance such as silicon or soft urethane, thermoplastic rubber, etc., and by providing a plurality of convex strips 11, the tip of the male pawl is formed into a convex strip 11 when the male pawl is fitted with the female pawl. The state of close contact is achieved, and the degree of tightness is extremely good even for gas or liquid contents.

As a method of adhering the thermoplastic resin chuck to the opening 6 of the bag body 5 in FIG. 4, the male nail 9 and the female nail 10 which are manufactured in advance in the opening portion 6 of the bag body 5 are respectively attached with an adhesive. A method of bonding, a method of fusion-bonding the male nail 9 and the female nail 10 extruded from the die in a molten state to the opening 6 of the bag body 5, and forming the male nail 9 and the female nail 10 in advance as shown in FIG. The thermoplastic resin chuck tape 8 is manufactured, and the tape 8 is fused to the opening 6 of the bag body 5.

In the present invention, a thermoplastic resin zipper tape, in which male and female claws are formed in advance in order to apply a chuck to the laminated body, is manufactured, and this tape is fused to the opening 6 of the bag body 5. The method of wearing is most preferred. The thermoplastic resin used for the thermoplastic resin chuck is not particularly limited, but it is preferable to use the same kind of resin as the inner and outer layers of the laminate.

Specifically, high-medium / low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene.
Examples thereof include homopolymers such as vinyl monoacetate copolymer and ethylene / ethyl acrylate copolymer, and mixtures thereof. Further, the male nail and the female nail may be combined with two or more kinds of hard and soft resins.

When the thermoplastic resin zipper tape is fused to the bag body, corona discharge treatment, ultraviolet ray treatment, and ozone are preliminarily applied to the non-fused portion of the surface of the tape on which the male and female claws are formed. By applying a surface treatment such as a treatment, an acid treatment, or a crosslinking treatment, the effect that the zipper tapes are not fused to each other is imparted, and the conventionally used release paper or the like can be omitted. The surface treatment has a surface tension of 4
It is preferably 2 dyn / cm or more. Of these surface treatments, corona discharge treatment is most preferable.

A fourth invention of the present application is a compression storage bag using a bag body comprising the laminated body of the first invention, and is preferably made of a thermoplastic resin having male and female claws at the opening of the bag. A compression storage bag having a zipper structure, having transparency, and having gas barrier properties, impact resistance, waist strength, airtightness, and the like. The compression storage bag is a bag or the like in which an object to be packaged such as a futon or a costume is stored, and then the inside of the bag is evacuated and decompressed to prevent mold, antibacterial, etc.
This bag is used for mites and long-term storage. Further, it has a feature that space saving of the storage place can be achieved.

Conventionally, a compression bag such as a wrapping bag for storing a futon or a garment bag which is required to have high airtightness, gas barrier property, impact resistance, and waist strength is well known. For example, JP-A-53-2
1689, JP-A-56-13362, JP-A-58-193269, JP-A-1-139346.
Japanese Patent Laid-Open No. 1-254554, Japanese Patent Laid-Open No. 3-9
8856, JP-A-4-114867, JP-A-4-142255, JP-A-4-154556, JP-A-6-24455 and the like. These airtight compression storage bags and the like are generally made of a resin having a high gas barrier property such as polyamide, polyester, and saponified ethylene / vinyl acetate as an intermediate layer, and at least the inner layer thereof is heat-sealed with a polyethylene resin or the like. Laminated bags with layers are used. However, since the high gas barrier resin and the polyethylene resin are not generally adhered to each other, the adhesive resin is interposed between the high gas barrier resin and the polyethylene resin, and the coextrusion molding method and the extrusion lamination method are used. It is necessary to stack by the sandwich lamination method, the dry lamination method, etc., and there are problems of economical efficiency such as soaring of equipment cost and raw material cost and complexity of process.

The compression storage bag of the present invention has an intermediate layer mainly composed of high-density polyethylene having an appropriate gas barrier property, and an outer layer preferably having relatively good moldability.
Highly impact-resistant linear low-density polyethylene laminated ethylene-based (co) polymer as a main component, with good low-temperature heat sealability and high heat seal strength as the inner layer By stacking a heat-sealing layer made of coalesced material, it is possible to dramatically improve the transparency as compared with the case of a single layer of high-density polyethylene, and further, moldability, gas barrier property, impact resistance, waist strength, etc. Will be excellent. In addition, since it is composed only of the same kind of cheap polyethylene resin, there is no need for an adhesive resin as in the past, and there is a problem of economic efficiency such as soaring equipment cost and raw material cost and complexity of process. Will be resolved.

Another advantage is that the compression storage bag of the present invention has a short heat-sealing cycle and a good productivity when the opening is heat-sealed with the zipper tape.
Further, by applying a sealing material to the inner wall of the chuck, reopening and closing is easy, and high airtightness is maintained.

Further details will be described below with reference to the drawings. 7A is a plan view of an example of a conventional futon compression storage bag, and FIG. 7B is a cross-sectional view of the laminated film 15 taken along the line BB of FIG. 7A, and FIG. (C) shows a pair of rims 18 and a sealing aid for the bar 19 for sealing the futon compression storage bag. 7 (a), (b),
In (c), the compression storage bag 20 is for sealing polyethylene resin or the like with an intermediate layer 13 made of a high gas barrier resin such as polyamide resin and adhesive resin layers 14 such as acid-modified polyolefin resin on both sides thereof. It has a resin film 12 and a laminated film 15 and has an opening 16 and a ventilation pipe 17 having a check valve provided at the bottom of the bag. 8 (a) and 8 (b) are enlarged sectional views of the ventilation pipe 17, and FIG. 8 (a) shows the ventilation pipe 17a equipped with a check valve 21a in the form of a film. (B) is
It shows a ventilation pipe 17b equipped with a check valve 21b in the form of a valve plate (arrows indicate the flow direction of exhaust gas).

The method of using the compression storage bag is as follows. After the futon is put in from the opening 16 of the compression storage bag 20, the opening 16 is assisted in sealing the pair of rim 18 and bar 19 shown in FIG. 7C. It is to be pinched and sealed with a tool, and the air inside the bag is sucked from the ventilation pipe 17 with a suction device such as a vacuum cleaner to be deaerated, and the contents are stored under a deaerated state.

FIG. 9 is a plan view of an embodiment of the compression storage bag of the present invention. In FIG. 9, a chuck 28 is fused near the opening 26 of the compression storage bag 25, and a ventilation pipe 27 having a check valve for deaeration is provided at the bottom of the bag.
The ventilation pipe 27 is not limited to the bottom portion, and may be provided at the opening portion, the side portion, the opening side end, or the like. By providing such a ventilation pipe 27, the air inside the bag can be sucked by a suction device such as an electric vacuum cleaner, the bag can be efficiently deaerated and compressed, and the contents can be stored in a deaerated state. it can. Also,
The storage bag storing the contents can prevent the inflow of air by the check valve.

Further, the compression storage bag 25 of the present invention can be easily opened and closed again and can be kept airtight by providing a plurality of rows of chucks 28 in the vicinity of the opening 26. In particular, by providing the sealing material in the chuck, higher airtightness can be obtained, and a pair of rims 18 for sealing the opening in FIG. 7 (c) used in the conventional futon compression storage bag. The auxiliary tool of the bar 19 is unnecessary.

The zipper bag and compression storage bag of the present invention are
Since it is a bag with excellent impact resistance and strong rigidity, the thermoplastic resin chuck will not easily come off due to the weight of the contents and the force of distorting the bag due to tipping or compression. It is possible to secure good airtightness.
In addition, by providing a sealant inside the chuck, it is possible to maintain high airtightness, and because it has gas barrier properties, it is suitable for long-term storage packaging of foods, packaging containers for fluid foods and chemicals, and air. It can be widely used for packaging of metals that rust when touched, packaging of clothing and the like for the purpose of insect repellent and mildew proofing, and a compression storage bag for deaeration and compression storage of clothing and bedding.

[0092]

BEST MODE FOR CARRYING OUT THE INVENTION

[0093]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The resin components used in Examples and Comparative Examples are shown below.

Resin (A ') ethylene used in the present invention
The α-olefin copolymer was polymerized by the following method. (Preparation of Solid Catalyst) Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen, and then dipropoxydichlorozirconium (Zr (OPr) ₂ C was added.
28 g of 1 ₂ ) and 48 g of methylcyclopentadiene were added, and 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the addition, the reaction system was maintained at 50 ° C. and stirred for 16 hours. This solution is designated as solution A. Next, purified toluene was added to another catalyst preparation device with a stirrer (No. 2) under nitrogen, and the above solution A and then a 6.4 mol solution of methylaluminoxane in toluene were added and reacted.
This is designated as solution B.

Next, under nitrogen, a preparer with a stirrer (No.
Purified toluene was added to 1) and then 400 ° C in advance.
After adding 1400 g of silica (manufactured by Fuji Devison Co., Ltd., grade # 952, surface area 300 m ² / g), which was calcined for a predetermined time, the whole amount of the solution B was added and stirred at room temperature. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst C.

(Polymerization of Sample) Using a continuous fluidized bed gas phase polymerization apparatus, the polymerization temperature was 70 ° C. and the total pressure was 20 kgf / cm ^2.
G copolymerized ethylene with 1-butene or 1-hexene. Polymerization is carried out by continuously supplying the catalyst C, and in order to keep the gas composition in the system constant, polymerization is carried out while continuously supplying each gas, and (A′1) and (A′2) are Obtained.

Component (A) A1: Linear low density polyethylene (L
LDPE) Density = 0.922 g / cm ³ , MFR = 0.9 g / 10
Minute comonomer: 1-butene Molecular weight distribution (Mw / Mn) = 3.8 Composition distribution parameter Cb = 1.5 ODCB Soluble content (%) = 3.1> Calculated value (2.6) A2: Super by Ziegler catalyst Low density polyethylene (VL
DPE) Density = 0.900 g / cm ³ , MFR = 0.5 g / 10
Component Comonomer: 1-butene Molecular weight distribution (Mw / Mn) = 4.1 Composition distribution parameter Cb = 1.52 ODCB soluble component (%) = 24> Calculated value (9.5) (B) component B1: High pressure radical Method Low Density Polyethylene (LDPE) Density = 0.924 g / cm ³ , MFR = 2.0 g / 10
Component (C) Component C: High-density polyethylene (HDP with Ziegler catalyst)
E) Density = 0.950 g / cm ³ , MFR = 0.9 g / 10
Component (A ′): Copolymer of the present invention A′1: Comonomer; 1-butene Density = 0.912 g / cm ³ , MFR = 1.0 g / 10
Minute (a) Molecular weight distribution (Mw / Mn) = 2.8 (b) Composition distribution parameter Cb = 1.15 (c) ODCB soluble content (%) = 3.2 <calculated value (5.
2) (d) TREF peak temperature: plural A'2: comonomer; 1-hexene density = 0.915 g / cm ³ , MFR = 1.0 g / 10
Minute (a) Molecular weight distribution (Mw / Mn) = 2.7 (b) Composition distribution parameter Cb = 1.18 (c) ODCB soluble content (%) = 2.6 <calculated value (4.
2) (d) TREF peak temperature: multiple

[Physical property test method] Haze: ASTM D1003 compliant Clarity: Murakami Color Research Laboratory Clarity meter “TM-1D type” transmitted light amount Tensile elastic modulus: JIS K6758 compliant Dart impact strength: ASTM D1709 compliant Oxygen permeable Rate: MODERN CONTROLS INC
Oxygen permeability is measured using a company-made measurement transmittance measuring device (OX-TRAIN TWIN) (MOCON method) Measurement conditions: 25 ° C., 65% RH ASTM D3985-81, JIS K7126 B method compliant Heat seal temperature: The heat seal strength is determined according to JIS Z1707, and the heat seal strength is 0.5 kg.
f / 15mm width temperature

[Example 1] Density = 0.950 g / c
m ³ and MFR = 0.9 g / 10 min (C) high density polyethylene (HDPE) as an intermediate layer II resin, density = 0.922 g / cm ³ , MFR = 0.9 g / 10 min,
Comonomer: 1-butene (A1) 90% by weight of linear low density polyethylene (LLDPE) and density = 0.924
g / cm ³ , MFR = 2.0 g / 10 min (B1) High-pressure process low density polyethylene (LDPE) 10 wt% blend in the I layer, density = 0.912 g / cm ³ , MFR
= 1.0 g / 10 min, so that (A'1) which is a comonomer: 1-butene is used as the third layer, a three-kind three-layer coextrusion inflation film molding machine (screw diameter 60 m
A film was formed under the conditions of an extrusion temperature of 200 ° C. and a blow-up ratio of 2.0 using m, L / D = 30 single screw extruder). The thickness of the laminated film is 40 μm for the intermediate layer,
The outer layer and the heat seal layer each had a thickness of 20 μm. The physical properties of the obtained laminated film were measured, and the results are shown in Table 1.

[Examples 2 to 6] and [Comparative Examples 1 to 4] Laminated films having the configurations shown in Tables 1 and 2 were molded under the same conditions as in Example 1 and the physical properties were measured. 1 and Table 2.

As a result, in all of Examples 1 to 6 of the present invention, the heat sealing temperature was 120 ° C. or less and the low temperature heat sealing property was excellent, and the optical characteristics, the tensile elastic modulus (the rigidity of the film), and the dart impact strength were obtained. , Shows a balanced performance in oxygen permeability. On the other hand, in Comparative Example 1, since the HDPE single layer is used, the heat sealing temperature is high, the optical characteristics and the dart impact strength are insufficient, and the film is too stiff. In Comparative Example 2, since the film is an LLDPE single layer, the film has a weak stiffness and oxygen permeability is insufficient. Comparative Example 3 is the third
Since the ethylene / α-olefin copolymer which does not satisfy the requirements of the present invention is used for the layer, the heat sealing temperature and the dart impact strength are insufficient. Comparative Example 4 is HDPE of the intermediate layer
Is less than 50% by weight, the film has a weak rigidity and oxygen permeability is insufficient.

Example 7 The laminated body of Example 1 was used,
Then, a zipper bag was prepared by fusing the zipper tape having airtightness in which three convex ridges made of soft urethane were provided on the inner wall of the female claw of the thermoplastic resin chuck to the opening, and the results were evaluated. The result was similar to that of 1.

[Embodiment 8] 1 of the bag obtained in Embodiment 1
An aeration pipe equipped with a check valve was formed in the part to manufacture a compression storage bag capable of compressing and storing the contents in a deaerated state. I used the compressed storage bag to store the futon and stored it for 8 months.
Almost kept the original compressed state.

[0104]

The laminate of the present invention has a (C) density of 0.94.
(A) Density of 0.86 to 0.94 g / cm in the middle II-layer mainly composed of high-density polyethylene of g / cm ³ or more.
³ , ethylene / α-olefin copolymer, (A ′) density satisfying the following (a) to (d): 0.86 to 0.94 g /
cm ³ of ethylene / α-olefin copolymer, (B) at least one ethylene-based (co) polymer selected from ethylene polymers prepared by the high pressure radical polymerization method, and the following layer (a). ~ Density 0.86 to satisfy (d)
By forming a laminate having an ethylene-based (co) polymer mainly composed of 0.94 g / cm ³ of the ethylene / α-olefin copolymer (A ′) as the third layer, the density of the layer is 0.3.
Despite having an intermediate layer of resin mainly composed of high-density polyethylene of 94 g / cm ³ or more, it has unpredictable transparency and has gas barrier properties, impact resistance, waist strength, etc. And a low temperature heat-sealing property was obtained. Further, a bag, a zipper bag, and a compression storage bag using such a laminated body are excellent in high-speed bag-making property and have high productivity in forming a chuck, and these bags are transparent, and have a gas barrier property, It also has impact resistance and waist strength.

[A-D] (A) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (B) Composition distribution parameter Cb is 1.08 to 2.00 (C) Orthodichlorobenzene ( ODC
B) The amount X (wt%) of the soluble component and the density d and the melt flow rate (MFR) satisfy the following relationships a) or b): a) The values of the density d and MFR are d-0.008logM.
In the case of FR ≧ 0.93 X <2.0 b) The value of the density d and MFR is d−0.008logM
When FR <0.93 X <9.8 × 10 ³ (0.9300-d + 0.008l)
ogMFR) ² +2.0 (d) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF)

[Brief description of drawings]

FIG. 1 is a copolymer TREF curve of the present invention.

FIG. 2 TREF curve of metallocene copolymer

FIG. 3 shows a cross-sectional view of one embodiment of the laminated body of the present invention.

FIG. 4 is a plan view of a zipper bag according to an example of the present invention.

FIG. 5 shows a cross-sectional view of a thermoplastic resin zipper tape having male and female claws.

FIG. 6 shows a cross-sectional view of a fitting chuck in which a sealing material is applied to an inner wall of a female claw.

7A is a plan view of an example of a conventional futon compression storage bag, FIG. 7B is a cross-sectional view of the laminated film taken along the line BB of FIG. 7A, and FIG. 7C is a perspective view of a sealing aid. The figure is shown.

8A is an enlarged sectional view of the ventilation pipe 13, and FIG. 8B is an enlarged sectional view of the ventilation pipe 13.

FIG. 9 is a plan view of the futon compression storage bag of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Laminated body 2 Outer layer 3 Intermediate layer 4 Heat seal layer 5 Bag body 6 Opening 7 Chuck 8 Chuck tape 9 Male claw 10 Female claw 11 Convex sealant 12 Outer layer 13 Intermediate layer 14 Adhesive layer 15 Laminated body 16 Opening 17, a, b ventilation pipe 18 rim 19 bar 20 compression storage bag 21a, b check valve 25 laminated body 26 opening 27 ventilation pipe 28 chuck

[Table 1]

[Table 2]

Claims (5)

[Claims] 1. (A) Density 0.86 to 0.94 g / cm
³ , ethylene / α-olefin copolymer, (A ′) having a density satisfying the following (a) to (d): 0.86 to 0.94 g
/ Cm ³ ethylene / α-olefin copolymer and (B) at least one ethylene-based (co) polymer selected from ethylene polymers by high-pressure radical polymerization, and (C) density From 100 to 50% by weight of high-density polyethylene of 0.94 g / cm ³ or more and the (A) ethylene-α-olefin copolymer, (A ′) ethylene-α-olefin copolymer and (B) ethylene polymer A second layer II comprising at least one selected ethylene-based (co) polymer resin up to 50% by weight; and (A ') an ethylene-based (co) predominant ethylene-α-olefin copolymer II composed of polymers
A layered product comprising an I layer and an II layer as an intermediate layer. [A to D] (A) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (B) Composition distribution parameter Cb is 1.08 to 2.00 (C) Orthodichlorobenzene (ODC) at 25 ° C
B) The amount X (wt%) of the soluble component and the density d and the melt flow rate (MFR) satisfy the following relationships a) or b): a) The values of the density d and MFR are d-0.008logM.
In the case of FR ≧ 0.93 X <2.0 b) The value of the density d and MFR is d−0.008logM
When FR <0.93 X <9.8 × 10 ³ (0.9300-d + 0.008l)
ogMFR) ² +2.0 (d) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF) 2. A bag body comprising the laminated body according to claim 1. 3. A zipper bag, wherein a zipper made of a thermoplastic resin having male and female claws is formed in the opening of the bag made of the laminated body according to claim 1. 4. A compression storage bag made of the laminate according to claim 1. 5. A compression storage bag, characterized in that a thermoplastic resin chuck having male and female claws is formed in the opening of the compression storage bag according to claim 3.