JP2002052668A - Pouch - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pouch excellent in rigidity, low temperature heat sealability, steam barrier properties, aroma retention, sanitariness and heat resistance and having high seal sealing strength and thrust strength. SOLUTION: The pouch is obtained by molding the following laminate consisting of a first layer I and a second layer II into a bag shape so that the second layer II becomes inside. The laminate is formed by laminating the first layer I which comprises a polyolefinic resin (i) with an elastic modulus in bending of 2,500 kgf/cm2 or more and the second layer II which comprises a resin material (ii) based on linear low density polyethylene (A) having (a) a density of 0.86-0.94 g/cm3, (b) MFR of 0.01-50 g/10 min and (c) Mw/Mn of 1.5-4.5 and satisfying (D) the relation of T75-T25<=-670×d+644 between the difference T75-T25 between temperature T25 eluting 25% of the whole and temperature T75 eluting 75% of the whole calculated from an integrated elution curve of an elution temperature-elution quantity curve due to TREF, and density (d).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pouch used for detergents, cosmetics, foodstuffs, etc., which is excellent in rigidity, low-temperature heat sealability, water vapor barrier property, fragrance retention, hygiene, high heat seal strength, and puncture. The present invention relates to a pouch having strength and particularly suitable for a standing pouch, a retort pouch, and the like.

[0002]

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

[0003] Such a pouch includes a single-layer film made of high-density polyethylene, linear low-density polyethylene, low-density polyethylene, or a laminated film of high-density polyethylene and low-density polyethylene, or a linear low-density polyethylene. Is used. These pouches are required to be easily heat-sealed, have a high heat-sealing strength, and be easily formed into a bag shape. In recent years, pouches obtained from such single-layer films, laminated films, and the like are required to have higher performance and lower cost. Excellent; hygienic so that taste and quality do not change due to transfer of low molecular weight components from the pouch, and odor does not transfer to the contents from the pouch; pinholes are not generated by vibration during product transportation Therefore, it is required to have a sufficient piercing strength. Further, the standing pouch is further required to have sufficient rigidity (waist) required for self-support. Furthermore, recently, from the viewpoint of resource saving and environmental protection, containers and packaging materials have been required to be easily recyclable and easily collected. It has been demanded.

[0004]

However, a pouch made of a laminated film of these high-density polyethylene and linear low-density polyethylene or low-density polyethylene,
It is inferior in low-temperature heat-sealing properties and needs to be heat-sealed at high temperatures to obtain sufficient sealing strength. Therefore, the high-speed filling property and the high-speed moldability are inferior, and the odor and the like are easily generated in the pouch, which is a cause of deteriorating the quality of the contents, and does not simultaneously satisfy the above required performance.

Accordingly, it is an object of the present invention to provide a pouch having excellent rigidity, low-temperature heat sealability, water vapor barrier property, fragrance retention, hygiene, heat resistance, pinhole resistance and high heat seal strength. Another object of the present invention is to provide a pouch excellent in recyclability because it is made of the same type of resin material.

[0006]

The pouch of the present invention comprises a first layer (I) made of a polyolefin resin material (i) having a flexural modulus of not less than 2500 kgf / cm ² , and
(A) A laminate laminated with a second layer made of a resin material (ii) mainly composed of linear low-density polyethylene which satisfies the requirement of (d) is packaged such that the second layer is on the inside. It is characterized by being formed into a shape. (A) a density of 0.86 to 0.94 g / cm ³ , (b) a melt flow rate of 0.01 to 50 g / 10 min, (c)
Molecular weight distribution (Mw / Mn) of 1.5 to 4.5, (d) Temperature at which 25% of the whole is eluted from the integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) Difference T ₇₅ between T ₂₅ and temperature T _{75 at} which 75% of the whole elutes
−T ₂₅ and density d satisfy the relationship of the following (formula 1) (formula 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644

The flexural modulus is 2500 kgf /
cm ² or more polyolefin resin material (i)
It is desirable to use a medium / high density polyethylene and / or polypropylene resin as a main component having a density of 0.93 g / cm ³ or more. In the pouch of the present invention, the heat sealing pressure of the ^second layer is 1 kg / cm ² , and the heat sealing time is 1 hour.
The heat sealing temperature is such that the heat sealing strength when heat sealing under the condition of 2 seconds is 3 kg / 15 mm,
It is desirable to be in the range of 85 to 125 ° C.

The thickness of the laminate is 10 μm to 0.5 m.
m, and the thickness of each of the first and second layers is 3
Desirably, the range is from μm to 0.4 mm. Also,
The first layer or the second layer is made of a blended resin of the resin material (i) and the resin material (ii) obtained by recycling the pouch, or a recycled resin layer (IV) made of the blended resin Is desirably further provided on the laminate.

It is desirable that the (A) linear low-density polyethylene is (A1) a linear low-density polyethylene that further satisfies the following requirements (e) and (f). (E) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by weight), the density d and the melt flow rate (MFR) satisfy the relationship of the following (Formula 2) and (Formula 3) (Formula 2) d−0.008 log MFR ≧ 0.93 X <2.0 (Equation 3) d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008)
(logMFR) ² +2.0 (f) Presence of multiple peaks in elution temperature-elution amount curve by continuous heating elution fractionation method (TREF)

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

The (A) linear low-density polyethylene is produced in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. It is desirable. Further, it is desirable that the additive compounded in the resin material (ii) is an additive that does not substantially migrate to the contacted object, or that no additive is compounded in the resin material (ii). The halogen concentration of the resin material (ii) is desirably 10 ppm or less.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The resin material (i) forming the first layer has a flexural modulus of 25.
00kgf / cm^Two Polyolefin resin material
Need to be a fee. The flexural modulus is preferably
Is 3500kgf / cm^Two Above, more preferably 450
0kgf / cm ^Two It is desirable that this is the case. The bending bullet
2500 kgf / cm^Two Less than the pouch rigidity
(Waist) is reduced, independence is lost, and automatic filling performance is low.
Will be down. Here, the bending elasticity of the resin material (i)
The ratio is measured according to JIS K7203.

The flexural modulus for forming the first layer is 2500 kg.
The f / cm ² or more polyolefin resin material (i), density is mainly composed of 0.93 g / cm ³ or more of high-density polyethylene and / or polypropylene-based resin, other polyethylene optionally It contains resin. Various types of medium-density polyethylene and high-density polyethylene can be used as long as the density is 0.93 g / cm ³ or more. In particular,
Homopolymers composed of ethylene only, copolymers composed of ethylene and other monomers (for example, α-olefins such as propylene, 1-butene and 1-hexene), or multi-component copolymers composed of ethylene and two or more monomers And the like.

The density of medium / high density polyethylene is 0.93
If it is less than g / cm ³ , the resulting pouch will have poor waist strength (rigidity), water vapor barrier properties, fragrance retention, moisture resistance, heat resistance, and the like. In addition, MFR of medium and high density polyethylene
(190 ° C.) is preferably 0.01 to 50 g / 10 minutes,
It is more preferably in the range of 0.05 to 30 g / min, and still more preferably in the range of 0.1 to 10 g / min. MFR (190
(° C) is less than 0.01 g / 10 minutes, there is a problem in workability, and if it exceeds 50 g / 10 minutes, the strength of the pouch tends to decrease.

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

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

Other polyethylene resins that can be blended with the resin material (i) include, for example, a linear low-density polyethylene obtained by a Ziegler-type catalyst, a metallocene-based catalyst, etc., a high-pressure radical process ethylene-based polymer, and a specific ethylene polymer described below. (A) Linear low density polyethylene and the like.

The melt flow rate (hereinafter referred to as MFR) of the linear low-density polyethylene obtained by the Ziegler-type catalyst is generally 0.01 to 50 g / 10 min, preferably 0.5 to 30 g / 10 min. Preferably 0.
5 to 10 g / min. When the MFR is less than 0.01 g / 10 minutes, the fluidity (the moldability of the laminate by inflation) is reduced, and when it exceeds 50 g / 10 minutes, the strength and the like are reduced.

High-pressure radical polymerization ethylene polymers include low-density polyethylene (LDPE), ethylene-vinyl ester copolymer, and copolymers of ethylene with α, β-unsaturated carboxylic acids or derivatives thereof by high-pressure radical polymerization. Polymers.

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

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

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

The resin material (ii) containing (A) a linear low-density polyethylene as a main component of the second layer is defined as a specific (A) linear resin satisfying the following requirements (a) to (d). It is composed of low-density polyethylene as a main component and other polyethylene-based resins as necessary.

(A) The linear low-density polyethylene is an ethylene copolymer obtained by copolymerizing ethylene and an α-olefin.
0, preferably a copolymer with an α-olefin having 3 to 12 carbon atoms. As the α-olefin having 3 to 20 carbon atoms, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-octene and the like are used. (A) The constituent unit derived from the α-olefin having 3 to 20 carbon atoms in the linear low-density polyethylene is 1 to 7 mol%, preferably 1 to 5 mol%, more preferably 2 to 3 mol%. . When the constituent unit derived from an α-olefin having 3 to 20 carbon atoms exceeds 7 mol%,
Impact resistance, creep resistance, and heat seal strength are reduced, and if less than 1 mol%, transparency is reduced.

The (A) density of the linear low density polyethylene (A) in the present invention is 0.86 to 0.94 g / cm ³ ,
Preferably, it is in the range of 0.89 to 0.94 g / cm ³ , more preferably 0.90 to 0.93 g / cm ³ .
If the density is less than 0.86 g / cm ³ , rigidity (lumbar strength) and heat resistance may be reduced. If the density exceeds 0.94 g / cm ³ , the pinhole resistance, tear strength, impact resistance, and the like may be insufficient.

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

The (c) molecular weight distribution (Mw / Mn) of (A) the linear low-density polyethylene in the present invention is 1.5 to 1.5.
The range is 4.5, preferably 2.0 to 4.0, and more preferably 2.5 to 3.0. If Mw / Mn is less than 1.5, moldability is poor, and if Mw / Mn exceeds 4.5, pinhole resistance, tear strength, impact resistance, and the like are poor. Here, the molecular weight distribution of the linear low-density polyethylene (Mw / M
n) is gel permeation chromatography (G
PC), the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined, and the ratio (Mw / Mn) is calculated.

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

The method of measuring TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) has been added so that the sample concentration becomes 0.05% by weight, and heated and dissolved at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, while flowing ODCB through this column at a constant flow rate, the column temperature was raised to 50 ° C.
The sample is sequentially eluted while heating at a constant rate of / hr. At this time, the concentration of the sample eluted in the solvent is continuously detected by measuring the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm ^-1 with an infrared detector.
From this value, the concentration of the ethylene copolymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. According to the TREF analysis, a change in the elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, so that a relatively fine peak which cannot be detected by the fractionation method can be detected.

The (A) linear low-density polyethylene according to the present invention further comprises (A1) a linear low-density polyethylene satisfying the requirements of (e) and (f) described below, or (g) and ( Preferably, it is any one of (A2) linear low-density polyethylene satisfying the requirement of h).

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

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

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

The (A1) linear low-density polyethylene according to the present invention can be obtained by (f) continuous heating elution fractionation (TRE).
In the elution temperature-elution amount curve obtained by F), a plurality of peaks are present. It is particularly preferred that the plurality of peak temperatures be between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.

Here, as shown in FIG. 2, (A1) linear low-density polyethylene was subjected to a continuous heating elution fractionation method (TR).
The peak is substantially a specific linear low-density polyethylene (ethylene / α-olefin copolymer) having a plurality of peaks in the elution temperature-elution amount curve obtained by EF). on the other hand,
The ethylene copolymer shown in FIG.
EF) is a linear low-density polyethylene having substantially one peak in an elution temperature-elution amount curve obtained by EF), and is a conventional typical metallocene-based catalyst.
An α-olefin copolymer corresponds to this.

As shown in FIG. 1, (A2) the linear low-density polyethylene of the present invention has one peak of an elution temperature-elution amount curve obtained by (g) continuous heating elution fractionation (TREF), In addition, T ₇₅ -T ₂₅ and the density d satisfy the relationship of the following (Equation 4). When the equation _{(4) T 75 -T 25 ≧ -300} × d + 285 T 75 -T 25 and density d do not satisfy the relation of the equation (4) will heat seal strength and heat resistance are poor. The (A2) linear low-density polyethylene of the present invention has (h) one or two melting point peaks, and the highest melting point T _ml and the density d among them satisfy the relationship of the following (formula 5). Things. (Formula 5) _Tml ≧ 150 × d−17 If the melting point Tm1 and the density d do not satisfy the relationship of the above (Formula 5), the heat resistance will be poor.

Further, among (A2) linear low-density polyethylenes, linear low-density polyethylenes which further satisfy the following requirement (i) are preferable. (I) The melt tension (MT) and the melt flow rate (MFR) satisfy the relationship of the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR + 0.3 By satisfying the relationship (2), the formability of the laminate and the like becomes good.

As shown in FIG. 1, the (A2) linear low-density polyethylene has one TREF peak, but the conventional typical metallocene-based ethylene copolymer has the above-mentioned formula (Formula 1). 4) is not satisfied, and is distinguished from a conventional typical metallocene-based catalyst-based ethylene copolymer.

The linear low-density polyethylene (A) in the present invention is not particularly limited to a catalyst, a production method and the like as long as it satisfies the above parameters, but is preferably an organic cyclic compound having at least a conjugated double bond. And Periodic Table No.
A linear ethylene (co) polymer obtained by (co) polymerizing ethylene and an α-olefin in the presence of a catalyst containing a Group IV transition metal compound is preferred. Such a linear ethylene (co) polymer has a narrow molecular weight distribution and a narrow composition distribution, and thus has excellent mechanical properties, excellent heat sealing properties, excellent heat blocking properties, and the like, and has good heat resistance. .

In the production of (A) the linear low-density polyethylene in the present invention, it is particularly desirable to polymerize with a catalyst obtained by mixing the following compounds a1 to a4. a1: Compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr (where Me ¹ represents zirconium, titanium, or hafnium, and R ¹ and R ³ each represent a carbon number) 1 to
24 hydrocarbon groups, R ² is a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand,
A benzoylacetonate ligand or a derivative thereof, X ¹ represents a halogen atom, p, q and r each represent 0 ≦ p
≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4) a2: a compound represented by the general formula Me ² R ⁴ _m (OR ⁵ ) _n X ² _zmn (In the formula, Me ² is an element in Groups I to III of the periodic table, R ⁴
And R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, X
² represents a halogen atom or a hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a Group III element of the periodic table), z represents a valence of Me ² , and m and n represent A is an integer satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z. A3: Organic cyclic compound having a conjugated double bond a4: Al—O—Al bond Containing modified organoaluminum oxy compound and / or boron compound

The details will be described below. The above-mentioned catalyst component a1
In the formula of the compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr , Me ¹ represents zirconium, titanium or hafnium, and the types of these transition metals are limited. It is not limited to this, and a plurality of them can be used, but it is particularly preferable that the copolymer contains zirconium having excellent weather resistance. R ¹ and R ³ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group;
Alkenyl groups such as vinyl group and allyl group; phenyl group,
Aryl groups such as tolyl, xylyl, mesityl, indenyl and naphthyl; benzyl, trityl,
And aralkyl groups such as phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofuyl group. These may have branches. R ² is 2,
It shows a 4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine. p and q are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q
An integer satisfying the range of + r ≦ 4 is an integer.

Examples of the compounds represented by the general formula of the above-mentioned catalyst component a1 include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodiconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrabutoxy titanium , Tetrabutoxy hafnium and the like, and especially Z such as tetrapropoxy zirconium and tetrabutoxy zirconium.
r (OR) ₄ compounds are preferred, and two or more of these may be used in combination. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonato ligand or derivative thereof include tetra (2,4-pentanedionato) zirconium. , Tri (2,4-pentanedionato)
Zirconium chloride, di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride zirconium, di (2,4-pentanedionato) diethoxide zirconium, di (2,4- Pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n
-Butoxide zirconium, di (2,4-pentanedionato) dibenzyl zirconium, di (2,4-pentanedionato) dineofylzirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) die Zirconium toxide, zirconium di (dibenzoylmethanato) di-n-propoxide, zirconium di (dibenzoylmethanato), zirconium di-n-butoxide, zirconium diethoxide zirconium, di (benzoylacetonate) ) Di-n-propoxide zirconium, di (benzoylacetonate)
And di-n-butoxide zirconium.

The general formula Me ² R ⁴ _m (O
R ⁵ ) _n X ^{2 In} the formula of the compound represented by _zmn , Me ² represents a group I-III element of the periodic table, and lithium, sodium,
Potassium, magnesium, calcium, zinc, boron,
Aluminum and the like. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 1 to 8, specifically alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, Aryl groups such as a xylyl group, a mesityl group, an indenyl group, and a naphthyl group; and aralkyl groups such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofuyl group. These may have branches. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.

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

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

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

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

Specific examples of the organic cyclic hydrocarbon compound of the component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-
Indene, 4,7-dimethylindene, butylcycloheptadiene, 1-methyl-3-propylcyclopentadiene and indene, 1-methyl-3-butylcyclopentadiene and indene, propylcyclopentadiene, 1-
Methyl-3-ethylcyclopentadiene, 1,2,4-
Trimethylcyclopentadiene cycloheptatriene,
C5-C24 cyclopolyene or substituted cyclopolyene such as methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadiene Examples include enylsilane, monoindenylsilane, bisindenylsilane, trisindenylsilane, and methylcyclopentadientinemethylsilane.

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

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

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

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

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

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

The linear low-density polyethylene (A) in the present invention is produced by using a catalyst which does not contain halogen such as chlorine in the above-mentioned catalyst components, so that the halogen concentration is at most 10 ppm or less, preferably at most 10 ppm. Is 5 ppm
Hereinafter, it is more preferably substantially free of (ND: 2p
pm or less). By using such a halogen-free linear low-density polyethylene such as chlorine, it is not necessary to use an acid neutralizer as in the past, and the chemical stability and hygiene are excellent, and especially, food packaging materials and the like. Can be provided.

The mixing ratio of (A) the linear low-density polyethylene in the resin material (ii) for forming the second layer is from 50 to 1
00% by weight, preferably 70 to 100% by weight. When the ratio of the linear low-density polyethylene is less than 50% by weight, the heat resistance, puncture resistance, low-temperature heat sealability, heat seal strength, and mechanical strength of the laminate are reduced.

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

High, medium and
An ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms by a low pressure method or another known method has a density of 0.94 to 0.97 g / cm.
³ , high density polyethylene, density 0.91-0.94g
/ Cm ³ linear low density polyethylene (LLDPE), density 0.86-0.91 g / cm ³ very low density polyethylene (VLDPE), density 0.86-0.91 g / c
m ³ of ethylene-propylene copolymer rubber, ethylene-
Ethylene / α-olefin copolymer rubber such as propylene / diene copolymer rubber can be mentioned.

The LLDPE using the Ziegler type catalyst is defined as ethylene • α-density having a density of 0.91 to 0.94 g / cm ³ , preferably 0.91 to 0.93 g / cm ^3.
An olefin copolymer, wherein the α-olefin has 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and specifically includes propylene, 1-butene, and 4-methyl-
1-pentene, 1-hexene, 1-octene and the like can be mentioned.

The ultra low density polyethylene (VLDPE) using the Ziegler type catalyst has a density of 0.86 to
0.91 g / cm ³ , preferably 0.88 to 0.905
It is an ethylene / α-olefin copolymer in the range of g / cm ³ and is a polyethylene having properties intermediate between LLDPE and ethylene / α-olefin copolymer rubber (EPR, EPDM).

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

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

In the present invention, an antioxidant, an antiblocking agent, a lubricant, an antistatic agent, an antifogging agent, an ultraviolet absorber, an organic or inorganic pigment, a nucleating agent, Even if a known additive such as a crosslinking agent is not blended, or even if the additive is blended with the resin material (ii), the blended additive substantially migrates to the contacted object such as the contents. It is desirable that the additive is not used.
In the present invention, an additive that elutes to the outside, for example, when the content is a liquid, an additive that is eluted in the liquid, an additive to which odor is transferred,
Alternatively, an additive that is unevenly distributed on the film surface with time is not included in the resin material (ii),
It is possible to provide a sanitary, clean laminate and container with little odor.

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

The laminate of the present invention comprises a first layer made of the polyolefin resin material (i) and a second layer made of the resin material (A) containing (A) the linear low-density polyethylene as a main component. It has.

In the laminate of the present invention, when the pouch is formed into a pouch, the layer corresponding to the innermost layer of the pouch is formed by the second layer, and the properties of each layer (the first layer: rigidity, water vapor barrier property, It is important to take advantage of the fragrance retention and the second layer: low-temperature heat sealability, heat seal strength, piercing strength, hygiene). Other layers may be interposed between the I-th layer and the II-th layer. Other layers include an adhesive resin layer for more firmly bonding the I-th layer and the II-th layer.

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

Here, the 120 ° C. heat seal strength is specifically measured as follows. Using a heat seal tester (seal bar width 1 mm), the pouches of the second layer were sealed at a seal temperature of 120 ° C. and a seal pressure of 1 kg / cm.
² for 1 second, room temperature 23 ° C and humidity 50%
After adjusting the condition for 24 hours, the heat-sealed part was cut out into a strip shape with a width of 15 mm, and the tensile strength was measured at 300 mm / min with a tensile tester.
Then, the heat-sealed portion is peeled off, and the maximum load is measured.

The heat-sealing temperature of the laminate of the present invention is such that the heat-sealing strength is 3 kg / 15 mm when the second layers are heat-sealed under the conditions of a heat-sealing pressure of 1 kg / cm ² and a heat-sealing time of 1 second. (Hereinafter referred to as 3 kg load heat sealing temperature) is 85 to 1
It is desirable to be in the range of 25 ° C. When the heat-sealing temperature under a 3 kg load is less than 85 ° C., the heat resistance is poor, and when it exceeds 125 ° C., the high-speed filling property is poor.

Here, the 3 kg load heat sealing temperature is:
Specifically, it is measured as follows. Using a heat seal tester (seal bar width 1 mm), the pouches of the second layer were heat-sealed at a heat seal temperature of 80 ° C. and a heat seal pressure of 1 kg / cm ² for 1 second, and were sealed at room temperature 23 ° C. and 50% humidity for 24 hours. After adjusting the time condition, the heat-sealed part was cut out into a strip shape with a width of 15 mm, and 300
The heat seal portion is peeled off at a rate of mm / min, and the maximum load (heat seal strength) is measured. The above measurement was repeated while increasing the heat seal temperature by 5 ° C., and 85,
90, 95, 100, 105, 110, 115, 12
The heat seal strength at 0, 125 and 130 ° C. is measured. A heat seal temperature-heat seal strength curve was created by plotting the heat seal strength against the heat seal temperature. From this curve, the heat seal strength was 3 kg / heat seal strength.
Read the heat seal temperature at 15 mm.

The thickness of the laminate in the present invention varies depending on the purpose and application, but is generally from 10 μm to 0.5 mm.
It is preferably selected in the range of 30 μm to 0.3 mm, more preferably in the range of 50 μm to 0.2 mm. Further, the first layer and the first layer of the laminate of the present invention
The thickness of each layer of the II layer is from 3 μm to 0.4 mm, preferably from 10 μm to 0.2 mm / 10 μm, respectively.
Preferably, it is selected in the range of 02 mm. The thickness ratio of each layer (the first layer: the second layer) is 1:10 to 10: 1.
It is preferred that

The laminate of the present invention may have a barrier layer (III) bonded to the first layer. Barrier layer (II
By providing I), the water vapor barrier property and the fragrance retention property are further improved. Further, the barrier layer (III) can also play a role as a reinforcement of the pouch, a protective layer, a printing layer, a light-shielding layer, and a role as a heat-resistant layer for maintaining the shape of the pouch at the time of heat sealing. I am carrying it.

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

Further, any one of the layers I and II constituting the laminate may be formed of a blend resin of the resin material (i) and the resin material (ii) obtained by recycling. Good. The laminate constituting the pouch of the present invention may further have a recycled resin layer (IV) made of the blend resin. Here, the blended resin obtained by recycling the laminate is a defective resin of the laminate, a recovered product of the pouch composed of the laminate, a mixed resin obtained by pulverizing burrs and the like generated in a finishing stage after processing into the pouch and the like. That is. Thus, the pouch of the present invention can use a recycled blended resin,
In addition, since the same type of resin material is used, recyclability is good.

Examples of the above laminate include I / II / and I / II /
III / II, III / I / II, I / Adhesive / IV / Adhesive / II
And the like. More specifically, HD / SL
L, HD + LL / SLL, HD / SLL + LD, HD +
LL / SLL + LD, RC / SLL, RC / HD / SL
L, RC + HD / SLL, HD / LL, barrier layer (EV
OH, PA, PEs, OPP, etc.) / Adhesive / HD / S
LL and the like (here, HD: high-density polyethylene, LD: low-density polyethylene by high-pressure radical polymerization method,
LL: linear low density polyethylene, SLL: specific (A)
Linear low-density polyethylene, RC: recycled blend resin, EVOH: saponified ethylene-vinyl acetate copolymer, PA: polyamide resin, PEs: polyester resin, OPP: oriented polypropylene resin, adhesive: acid-modified polyethylene resin Is shown).

The laminate according to the present invention is excellent in rigidity (lumpy), and thus can be suitably used for a standing pouch requiring self-sustainability. Further, since the laminate in the present invention can exhibit sufficient heat sealing strength even at a relatively low heat sealing temperature, a pouch or the like can be manufactured by low-temperature heat sealing, and the manufactured pouch or the like can be used. There is little generation of odor and the like, and the quality of the contents is not deteriorated.

The laminate according to the present invention can be produced by various methods, but is preferably produced by molding the first and second layers by a co-extrusion method. As a molding method, for example, it can be manufactured with high productivity by a multilayer inflation molding method, a multilayer cast molding method, or the like. Among them, a multilayer inflation molding method is suitably used in terms of economy, moldability, and the like.

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

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

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

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

The pouch of the present invention is obtained by heat-sealing the above-mentioned laminated body so that the second layer is on the inside, so as to form a bag. Examples of the type of pouch include a self-standing standing pouch, a retort pouch for a retort food having a barrier layer made of aluminum foil, a pouch with a spout for drinking and drinking, and more specifically, a flexible spout pouch, a dual chamber pouch, Dispenser pouches and the like. Examples of the shape of the pouch include a gusset bag, a four-sided seal bag, a three-sided seal bag attached to a palm, a bag in which the upper and lower sides of a tubular film are sealed by an inflation method, and the like.

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

The pouch of the present invention, in particular, the standing pouch, is very excellent in self-sustainability, and can be made thinner and lighter, because the above-mentioned laminate has excellent rigidity (lumpy). In addition, the pouch of the present invention can be manufactured by low-temperature heat sealing, since the laminate can exhibit sufficient heat sealing strength even at a relatively low heat sealing temperature, and the generation of odor and the like is small, It does not degrade the quality of the contents.

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

[0086]

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

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

[Measurement of T _ml by DSC] Thickness: 0.2 m
m was formed by hot pressing, and about 5 mg of a sample was punched from the sheet. This sample was kept at 230 ° C. for 10 minutes and then cooled to 0 ° C. at 2 ° C./min. Then again 10
The temperature was raised to 170 ° C. at a rate of ° C./min, and the temperature at the top of the highest temperature peak that appeared was defined as the highest peak temperature Tml. [TREF] With the column maintained at 140 ° C., a sample was injected into the column, the temperature was lowered to 25 ° C. at 0.1 ° C./min, and the polymer was deposited on glass beads. The concentration of the polymer eluted at each temperature after the temperature was raised was detected by an infrared detector. (Solvent: ODCB, flow rate: 1 ml /
Min, heating rate: 50 ° C./hr, detector: infrared spectrometer (wavelength: 2925 cm ⁻¹ ), column: 0.8 cmφ × 12 cm
L (filled with glass beads), sample concentration: 0.05% by weight)

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

<Evaluation of Laminate> [Heat Seal Strength] Heat seal tester manufactured by Tester Sangyo Co., Ltd. (seal bar width 1 mm, seal pressure 1 kg / c)
m ² ), the ^second layer of the laminate is sealed at a heat sealing temperature of 120 ° C. for 1 second, and a room temperature of 23 ° C. and a humidity of 5
After adjusting the state at 0% for 24 hours, the seal portion was cut out in a strip shape with a width of 15 mm, the seal portion was peeled off at 300 mm / min with a tensile tester, and the maximum load was measured. [3 kg load heat seal temperature] Using a heat seal tester manufactured by Tester Sangyo Co., Ltd. (seal bar width 1 mm, seal pressure 1 kg / cm ² ), the ^second layers of the laminate were heat sealed at a heat seal temperature of 80 ° C. Pressure 1kg / cm
² for 1 second, room temperature 23 ° C and humidity 50%
After adjusting the condition for 24 hours, the heat-sealed part was cut out into a strip shape with a width of 15 mm, and the tensile strength was measured at 300 mm / min with a tensile tester.
The maximum load (heat seal strength) was measured by repeating the above measurement while increasing the heat seal temperature by 5 ° C. at 85, 90, 95, 100, 105, 11
The heat seal strength at 0, 115, 120, 125 and 130 ° C. was measured. A heat seal temperature-heat seal strength curve was created by plotting the heat seal strength against the heat seal temperature, and the heat seal temperature at a heat seal strength of 3 kg / 15 mm was read from this curve.

[Pinhole Resistance] A test piece having a width of 200 mm and a length of 300 mm was cut from the laminate in the flow direction during molding. The test piece was attached to a gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd., and after loading 3,000 strokes at room temperature, the number of pinholes in the test piece was measured. The same test was repeated three times, and the average value of the number of pinholes was obtained. [Water vapor transmission rate] Based on JIS K7129. [Haze] Based on ASTM D1003. [Tensile modulus] MD (extrusion direction) was measured in accordance with ASTM D882. [Tensile impact strength] According to ASTM D1822, MD
(Extrusion direction) was measured.

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

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

The various components used in the examples and comparative examples are as follows. [(A) Linear low density polyethylene] 1) (A1) The specific linear low density polyethylene was polymerized by the following method. (Preparation of solid catalyst) To a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ) and 74 g of indene were added. 100 g of aluminum is dropped over 100 minutes,
Thereafter, the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration: 2.5 m
(mol / ml) and stirred for 2 hours.
Next, silica (manufactured by Grace, # 952, surface area 300 m ² / g) 2 previously calcined at 450 ° C. for 5 hours 2
After stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst having good fluidity.

(Gas phase polymerization) Continuous type fluidized bed gas phase polymerization apparatus
At a polymerization temperature of 80 ° C. and a total pressure of 20 kgf / cm ^Two In G
Copolymerization of ethylene and 1-hexene was performed. The solid touch
The medium is fed continuously, ethylene, 1-hexene and water
The polymerization is carried out by supplying the element so as to maintain a predetermined molar ratio, and the
A tylene copolymer (LLDPE-1) was obtained. Also, LL
The same ethylene copolymer as DPE-1 and an additive
Was not used as LLDPE-3. These physical properties
Are shown in Table 1.

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

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

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

[0099]

[Table 1]

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

Examples 1-6, Comparative Examples 1-3 Antioxidants (Irganox 1076 = 0.1% by weight, Irgafos 168 = 0.1% by weight) and calcium stearate (neutralizing agent = 0.1%) % By weight) of HDPE, HP-LDPE, LLDPE (provided that LL
No antioxidant is added to DPE-3) and a two-layer inflation molding machine (40 mmφ) manufactured by Tommy Machine Industry Co., Ltd.
Using two extruders, molding was performed under the conditions of a molding lip gap of 3 mm and a molding temperature of 200 ° C. to produce a laminate having a width of 300 mm and a layer thickness configuration shown in Tables 2 to 4. Then, O-nylon (thickness: 15 μm, manufactured by Unitika Ltd.) was bonded by a dry lamination method using an adhesive (anchor coating agent: Toyo Morton TM-329).

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

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

[Table 4]

As is clear from the results shown in Tables 2 and 3, the laminates of the examples are excellent in heat sealability, pinhole resistance, water vapor barrier properties, transparency and mechanical strength. Further, the pouches of the examples had sufficient heat resistance and drop strength. In particular, LLDPE-1 containing almost no halogen is used as the inner layer (Layer II).
The pouch used in Example 1 had little odor and was excellent in hygiene.

On the other hand, as is clear from the results in Table 4, the laminate and pouch of Comparative Example 1 had the specific (A)
Since MDPE was used without using linear low-density polyethylene, heat seal strength, pinhole resistance, tensile impact strength, and drop strength were poor. Since the laminate and the pouch of Comparative Example 2 used HP-LDPE without using (A) linear low-density polyethylene for the second layer, the heat seal strength,
It was inferior in pinhole resistance, tensile impact strength and drop strength, and had a strong odor and poor hygiene. The laminate and pouch of Comparative Example 3 also used (A) Z-LLDPE instead of (A) linear low-density polyethylene for the second layer, so that heat seal strength, pinhole resistance, tensile impact strength, and drop strength were reduced. It was inferior, had an odor, and had poor hygiene. Since the laminate and the pouch of Comparative Example 4 used LDPE for the I-th layer, they were inferior in heat resistance, drop strength, and independence.

[0108]

As described above, the pouch of the present invention is
Has a flexural modulus of 2500 kgf / cm ^Two That's all
A first layer made of a polyolefin resin material (i);
(A) The linear low-density polymer satisfying the requirements (a) to (d)
Part II consisting of a resin material (ii) containing ethylene as a main component
The layered body is laminated so that the second layer is on the inside.
Because it is formed into a bag, it has rigidity and low-temperature heat
Sealing property, water vapor barrier property, fragrance retention, hygiene, heat resistance
Excellent, high heat seal strength and piercing strength.

Further, if the heat sealing temperature at which the heat sealing strength when the second layers are heat-sealed to each other is 3 kg / 15 mm is in the range of 85 to 125 ° C., the heat resistance and the high-speed filling property are further improved. I do. Further, the thickness of the laminate is 10 μm to 0.5 mm, and the I-th layer and the
When the thickness of each of the II layers is in the range of 3 μm to 0.4 mm, the pouch is easy to use and the characteristics of each layer are sufficiently exhibited. In addition, when the laminate further has the barrier layer (III), the water vapor barrier property and the fragrance retention of the pouch are further improved. Further, any one of the layer I and the layer II is
Resin material (i) obtained by recycling the laminate
If a recycled resin layer (IV) formed of a blended resin of the resin material (ii) or the blended resin is further provided, it is possible to use the recycled blended resin. The property becomes good.

If the (A) linear low-density polyethylene is (A1) a linear low-density polyethylene that further satisfies the requirements (e) and (f), the heat resistance and sanitary properties of the pouch The rigidity is further improved. Further, (A) the linear low-density polyethylene further comprises (g)
If (A2) the linear low-density polyethylene that satisfies the requirements of (h), the heat resistance and heat seal strength of the pouch are further improved. If the (A2) linear low-density polyethylene further satisfies the above requirement (i),
Formability is further improved.

The (A) linear low-density polyethylene is obtained by converting ethylene and an α-olefin in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. A linear ethylene copolymer obtained by copolymerization further improves the mechanical properties, heat sealability, heat blocking property and heat resistance of the pouch. Further, if the additive blended in the resin material (ii) is an additive that does not substantially migrate to the contacted object, or if the additive is not blended in the resin material (ii), the odor is small, A pouch having hygiene properties can be obtained. Further, when the halogen concentration of the resin material (ii) is 10
When it is at most ppm, it is possible to provide a pouch which is excellent in chemical stability and hygiene and is suitably used particularly in the field of food packaging materials and the like.

[Brief description of the drawings]

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

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

FIG. 3 is a graph showing an elution temperature-elution amount curve of an ethylene copolymer with a metallocene catalyst.

Continued on the front page F-term (reference) 3E064 AA05 AA08 AA11 AB23 BA01 BA07 BA09 BA17 BA18 BA27 BA28 BA29 BA30 BA36 BA38 BA54 BA60 BB03 BC01 BC08 BC18 EA04 EA17 EA30 FA01 FA04 FA05 FA06 HN05 HN65 4F100 AH02A05A07KAKA AK03 AK03 AK63B AK63K AL05A AL05C BA02 BA03 BA06 BA10A BA10C BA15 CA06 CA24 CB00 GB16 GB23 JA04B JA06B JA07B JA13A JA13B JA13C JA20B JD01A JD01C JD04 JJ03 JK01 JK04A JK04C JK06 JK00 YK00 YK00Y

Claims (12)

[Claims] 1. A polyolefin resin material (i) having a flexural modulus of not less than 2500 kgf / cm ² .
A laminate obtained by laminating a layer and a second layer made of a resin material (ii) containing (A) a linear low-density polyethylene as a main component satisfying the following requirements (a) to (d) is referred to as a second layer. A pouch characterized by being formed into a bag shape such that a layer is inside. (A) a density of 0.86 to 0.94 g / cm ³ , (b) a melt flow rate of 0.01 to 50 g / 10 min, (c)
Molecular weight distribution (Mw / Mn) of 1.5 to 4.5, (d) Temperature at which 25% of the whole is eluted from the integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) Difference T ₇₅ between T ₂₅ and temperature T _{75 at} which 75% of the whole elutes
−T ₂₅ and density d satisfy the relationship of the following (formula 1) (formula 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644 2. The flexural modulus is 2500 kgf / cm.
^2. The pouch according to claim 1, wherein the polyolefin resin material (i) having a density of ² or more contains a medium / high density polyethylene and / or polypropylene resin having a density of 0.93 g / cm ³ or more as a main component. 3. A heat sealing pressure of 1 k between the second layers.
^2. A heat sealing temperature in a range of 85 to 125 [deg.] C. such that a heat sealing strength when heat sealing under a condition of g / cm < ² > and a heat sealing time of 1 second is 3 kg / 15 mm. Or the pouch according to claim 2. 4. The laminate has a thickness of 10 μm to 0.5 mm, and each of the first and second layers has a thickness of 3 μm.
The pouch according to any one of claims 1 to 3, wherein the distance is in a range of 0.4 mm to 0.4 mm. 5. A barrier material (iii) adhered to the layer I
The pouch according to any one of claims 1 to 4, further comprising a barrier layer (III) comprising: 6. The resin material (i) or resin material (i) obtained by recycling the pouch, wherein the layer I or the layer II is
The recycled resin layer (IV) formed of a blended resin of i) and a barrier material (iii) or made of the blended resin is further provided on the laminate. 5. The pouch according to any one of 5. 7. The (A) linear low-density polyethylene,
Further, the following requirements (e) and (f) are satisfied (A
1) The pouch according to any one of claims 1 to 6, wherein the pouch is linear low-density polyethylene. (E) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by weight), the density d and the melt flow rate (MFR) satisfy the relationship of the following (Formula 2) and (Formula 3) (Formula 2) d−0.008 log MFR ≧ 0.93 X <2.0 (Equation 3) d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008)
(logMFR) ² +2.0 (f) Presence of multiple peaks in elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) 8. The (A) linear low-density polyethylene,
Further, the following requirements (g) and (h) are satisfied (A
2) The pouch according to any one of claims 1 to 6, wherein the pouch is a linear low-density polyethylene. (G) elution temperature by continuous Atsushi Nobori elution fractionation (TREF) - it is one peak of elution curve and the T ₇₅ -T ₂₅ and density d is, satisfy the relation of the following (Equation 4) ( (H) T ₇₅ −T ₂₅ ≧ −300 × d + 285 (h) One or two melting point peaks, and the highest melting point T _ml and density d satisfy the relationship of the following (Formula 5) ( Formula 5) T _ml ≧ 150 × d−17 9. The pouch according to claim 8, wherein the (A2) linear low-density polyethylene further satisfies the following requirement (i). (I) Melt tension (MT) and melt flow rate (MFR) satisfy the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR + 0.3 10. The (A) linear low-density polyethylene produced in the presence of a catalyst containing at least an organic cyclic compound having at least a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. 10. The method according to claim 1, wherein:
A pouch according to any one of the preceding claims. 11. An additive compounded in the resin material (ii) is an additive that does not substantially migrate to a contacted object, or no additive is compounded in the resin material (ii). The pouch according to any one of claims 1 to 10, wherein 12. The pouch according to claim 1, wherein the resin material (ii) has a halogen concentration of 10 ppm or less.