JP4199551B2 - Polyethylene resin composition - Google Patents

Polyethylene resin composition Download PDF

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JP4199551B2
JP4199551B2 JP2003023555A JP2003023555A JP4199551B2 JP 4199551 B2 JP4199551 B2 JP 4199551B2 JP 2003023555 A JP2003023555 A JP 2003023555A JP 2003023555 A JP2003023555 A JP 2003023555A JP 4199551 B2 JP4199551 B2 JP 4199551B2
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polyethylene resin
density polyethylene
film
high
resin composition
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JP2004231844A (en
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雄一 折笠
俊昭 江頭
圭 高橋
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日本ポリオレフィン株式会社
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[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyethylene resin composition having high transparency, high rigidity, and high strength and a molded article thereof, and the polyethylene resin composition is a film that satisfies all of high transparency, high rigidity, high strength, and moldability. It is suitable as a raw material for molding.
[0002]
[Prior art]
Polyethylene resin is widely used in our lives. For example, film products represented by supermarket plastic bags, laminated products represented by milk paper packs, small containers such as edible oils, detergents, cosmetics, Large industrial products such as gasoline tanks for automobiles, plastic drums, gas pipes and water pipes are listed. Gross domestic demand reaches 2.6 million tons. Polyethylene resins have been devised such as molecular design and additive blending according to their use, and the above product groups satisfy different required characteristics. In recent years, there has been an increasing demand for film products that exhibit high strength even if the thickness is reduced from the viewpoint of economy, and if the rigidity and impact resistance of a conventional polyethylene resin having high transparency can be improved, It is expected to be able to greatly contribute to and contribute to resource saving and plastic waste reduction, and at the same time, it can be used for new usage development.
Regarding the film field using this polyethylene resin, in order to obtain a film having high transparency, high-pressure radical method low-density polyethylene and linear low-density polyethylene are used, but the drawback is that the film has low rigidity. There is. In addition, high-density polyethylene is used to obtain a film exhibiting high rigidity, but has a drawback of low transparency.
Films that have both high transparency and high rigidity are in great demand as various packaging materials. In order to obtain films that exhibit these characteristics, they have already been put into practical use using polypropylene resin or polyethylene terephthalate (PET) resin. ing. However, since these are inferior in terms of molding processability, heat sealability, and impact strength compared to polyethylene resin products, the advent of a polyethylene resin having both high transparency and high rigidity has been awaited.
In addition, high-density polyethylene-based films are widely used in our lives because they are inexpensive because they are made of ethylene and have high rigidity.
A typical application is a packaging film, which is used, for example, for wrapping and packaging a plurality of (for example, five) tissue paper packs by automatic packaging. This is because a high-density polyethylene film has high rigidity and is stiff and has little slack, so that it can be easily put on an automatic packaging machine (suitable for automatic packaging machines).
This packaging film is rarely required to have decorativeness and design properties such as printing itself. For example, even in the case of pack packaging of the tissue paper storage box, the storage box surface decoration, design (print mark, etc.), etc. The film itself is required to be transparent so that the details can be visually recognized through the film. Since it is visible from the outside as described above, the barcode on the surface of the storage box can be read mechanically from above the film, which is convenient.
Conventionally, polyethylene makers and film makers have already supplied high-rigidity and transparent high-density polyethylene packaging films to the market.
However, there is no exception to recent cost reductions such as cost reductions, and there is an increasing demand for thinner packaging films.
By the way, the thinning of the film reduces the strength of the film itself. Therefore, it is difficult to reduce the thickness of the film unless mechanical strength such as rigidity is further improved.
For such conventional films, a method using a polyethylene resin having a narrow molecular weight distribution (see, for example, Patent Document 1) or a method using a resin composition comprising a high density polyethylene resin having a narrow molecular weight distribution and a high pressure radical method low density polyethylene. (For example, refer to Patent Document 2), or methods for obtaining a polyethylene film having both high rigidity and high transparency by devising an inflation film forming method (for example, refer to Patent Document 3). The film proposed in the publication is still insufficient.
In addition, there is one that discloses a method for producing a polyethylene film using a multistage cooling ring using a composition of high-density polyethylene, low-density polyethylene, and linear low-density polyethylene (see, for example, Patent Document 4). Only a low film is obtained.
[0003]
[Patent Document 1]
JP-A-54-87778
[Patent Document 2]
JP 63-218740 A
[Patent Document 3]
JP-A-1-196326
[Patent Document 4]
JP-A-5-293886
[0004]
The inventors of the present invention have made a new attempt to improve the rigidity while maintaining transparency based on a high-density polyethylene resin to further increase the rigidity.
That is, although the high-density polyethylene resin itself is highly rigid, the transparency and processability are not always sufficient. For example, in terms of transparency, high-density polyethylene produced by multi-stage polymerization or the like has a wide molecular weight distribution, and such high-density polyethylene hardly exhibits sufficient transparency.
In addition, it can be said that the narrow molecular weight distribution is more transparent, but it is not simply that the molecular weight distribution is narrow. Also, high-density polyethylene with many long-chain branches represented by chromium-based high-density polyethylene produced by a commercially available calcined chromium oxide catalyst is similarly difficult to obtain sufficient transparency.
In terms of rigidity, the high-density polyethylene has high rigidity, but further improvement is desired to reduce the thickness as described above.
Therefore, in order to obtain high rigidity, it is conceivable to try blending linear low-density polyethylene, but if the rigidity is improved while maintaining transparency, the processability of the resulting resin is inferior, and the film molding itself is inferior. The problem of becoming difficult can be considered. Of course, it is preferable to further improve the transparency rather than simply maintaining it.
[0005]
[Problems to be solved by the invention]
The present invention provides a polyethylene resin composition having both high transparency, high rigidity, and high strength and excellent molding processability, particularly a polyethylene resin composition suitable as a resin composition for a film and a molded product thereof. Objective.
The resulting film is highly transparent, has high rigidity and high strength, and therefore can be thinned. For example, a film having a thickness of 5 to 30 μm can be obtained with practical strength. Since the thickness can be reduced in this way, the transparency is further improved as the film becomes thinner.
Moreover, since it shape | molds from a resin material with favorable workability, film shaping | molding of an inflation film etc. can be performed easily.
[0006]
[Means for Solving the Problems]
In the first aspect of the present invention, the melt flow rate is 0.1 to 10 g / 10 min, and the density is 0.940 to 0.965 g / cm.3High-density polyethylene resin (A) in the range of 60 to 90% by mass, high-pressure radical ethylene (co) polymer resin (B) in the range of 0.1 to 10 g / 10 min, and 1 to 39% by mass. , And a melt flow rate of 0.1 to 10 g / 10 min, and a density of 0.900 to 0.935 g / cm.3It is related with the polyethylene resin composition which consists of 1-39 mass% (here, the total amount of A, B, and C is 100 mass%) in the range of linear low density polyethylene resin (C).
According to a second aspect of the present invention, in the first aspect of the present invention, the high-density polyethylene resin (A) has a viscosity curve index (FCI) and a melt flow rate (MFR) of −0.063 × log (MFR) +1. The present invention relates to a polyethylene resin composition that is a high-density polyethylene resin that satisfies a relationship of 10 ≧ FCI ≧ −0.046 × log (MFR) +1.06.
According to a third aspect of the present invention, in the first or second aspect of the present invention, the linear low density polyethylene resin (C) satisfies a molecular weight distribution (Mw / Mn) in the range of 1.5 to 3.5. The present invention relates to a polyethylene resin composition which is a linear low density polyethylene resin.
According to a fourth aspect of the present invention, in any one of the first to third aspects of the present invention, the linear low-density polyethylene resin (C) satisfies the following requirements (a) to (b): To a polyethylene resin composition.
(B) A temperature T at which there are substantially a plurality of elution temperature-elution amount curve peaks by continuous temperature rising elution fractionation method (TREF) and (b) 25% of the total elution amount is eluted.25And the temperature T at which 75% of the total elution occurs75T which is the difference between75-T25However, in relation to the density d, −300 × d + 285 ≦ T75-T25≦ −670 × d + 644 is satisfied.
According to a fifth aspect of the present invention, in the first or second aspect of the present invention, the linear low-density polyethylene resin (C) comprises an organic cyclic compound having at least a conjugated double bond and a transition metal of Group IV of the periodic table. The present invention relates to a polyethylene resin composition that is a linear low-density polyethylene resin obtained by copolymerizing ethylene and an α-olefin using a single-site catalyst containing a compound.
6th of this invention is related with the molded object which consists of a polyethylene resin composition in any one of the said 1st to 5th of the said invention, Especially the film obtained by shape | molding easily from the resin composition of this invention is The film is highly rigid as a thin film, and is so transparent that details of decorations, designs, etc. of the package can be visually recognized from the outside. Therefore, it can be supplied at low cost and is suitable as a packaging film.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The polyethylene resin composition according to the present invention is basically composed of a high-density polyethylene resin (A), a high-pressure radical process ethylene (co) polymer resin (B), and a linear low-density polyethylene resin (C). ing. Next, each of these components and the resin composition will be described in detail.
[0008]
(A) High density polyethylene resin
The high-density polyethylene resin (A) that can be used in the present invention has a melt flow rate (hereinafter referred to as MFR) measured at 190 ° C. under a 2.16 kg load in accordance with JIS K6922-2 of 0.1 to 10 g / 10 min, preferably 0.13 to 5 g / 10 min, more preferably 0.15 to 3 g / 10 min, and the density measured according to JIS K6922-2 is 0.940 to 0.965 g / cm.3, Preferably 0.945 to 0.960 g / cm3More preferably, 0.949-0.958 g / cm3It is in the range.
When the MFR of the high-density polyethylene resin (A) is less than 0.1 g / 10 min, an overload is applied to the motor of the processing machine when processing the film molded body using the target polyethylene resin composition. Significantly reduce production efficiency. Moreover, when MFR of a high-density polyethylene resin (A) is larger than 10 g / 10min, the intensity | strength of the film molded object obtained using the target polyethylene resin composition will fall remarkably.
The density of the high density polyethylene resin (A) is 0.940 g / cm.3If it is less than 1, the rigidity of the film molded product obtained by using the target polyethylene resin composition is significantly reduced. The density of the high density polyethylene resin (A) is 0.965 g / cm.3If it is higher, the strength of the film molded product obtained using the intended polyethylene resin composition will be significantly reduced.
[0009]
In the high-density polyethylene resin (A) according to the present invention, it is particularly desirable that the relationship between the viscosity curve index (hereinafter referred to as FCI) and MFR (g / 10 min) satisfies the range of the following formula.
−0.063 × log (MFR) + 1.10 ≧ FCI ≧ −0.046 × log (MFR) +1.06
When the FCI does not satisfy the range of the above formula, there is a possibility that the balance between transparency and rigidity of the molded film obtained by using the target polyethylene resin composition remains at the level of the prior art.
[0010]
The viscosity curve index (FCI) of the high-density polyethylene resin (A) of the present invention is a complex viscosity η obtained at 190 ° C. at a measurement frequency of 0.1 rad / s obtained using a rotary rheometer.* 0 . 1And the complex viscosity η at a measurement frequency of 10 rad / s at 190 ° C.* 10Defined by the ratio of the logarithm of
FCI = log (η* 0 . 1) / Log (η* 10)
It is represented by
In general, FCI has a correlation with the molecular weight distribution of the polyethylene resin. When the molecular weight distribution is wide, FCI shows a large value, and when the molecular weight distribution is narrowed, FCI tends to show a small value.
[0011]
The high-density polyethylene resin (A) of the present invention can be produced by the method described in Kazuo Matsuura and Naotaka Mikami, “Polyethylene Technology Reader”, published by Industrial Research Association, 2001, p.123-160. . That is, it can be produced by various polymerization apparatuses, polymerization conditions and catalysts in each of the polymerization methods of slurry method, solution method and gas phase method. In order to produce the high-density polyethylene resin of the present invention by the above-described method, it is preferable to use a specific Ziegler catalyst as described in, for example, Japanese Patent Publication No. 55-14084. In addition, when a so-called general Philips catalyst is used, the above-mentioned FCI greatly exceeds −0.063 × log (MFR) +1.10, and a film molded body actually obtained by using such a polyethylene resin composition. May not exhibit sufficient transparency.
[0012]
(B) High-pressure radical ethylene ( Both ) Polymer resin
The high-pressure radical method ethylene (co) polymer resin (B) of the present invention comprises an ethylene homopolymer or an ethylene / α-olefin copolymer (hereinafter referred to as low density polyethylene), an ethylene / vinyl ester copolymer, ethylene And a copolymer of α, β-unsaturated carboxylic acid or a derivative thereof.
The high-pressure radical method ethylene (co) polymer resin (B) of the present invention has a melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg according to JIS K6922-2 of 0.1 to 10 g / The range is 10 min, preferably 0.15 to 5 g / 10 min, more preferably 0.17 to 3 g / 10 min.
In the present invention, among the low-density polyethylene, the ethylene / vinyl ester copolymer, and the copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof, the low-density polyethylene is economical and has an odor point. It is desirable to use
[0013]
When the MFR of the high-pressure radical ethylene (co) polymer resin (B) is less than 0.1 g / 10 min, when processing into a film molded body using the target polyethylene resin composition, Solubility deteriorates and causes gel and fish eyes, which may remarkably deteriorate the appearance of the molded film. On the other hand, if the MFR of the high-pressure radical ethylene (co) polymer resin (B) is larger than 10 g / 10 min, the thickness distribution of the film molded product obtained using the target polyethylene resin composition is remarkably impaired.
[0014]
Low density polyethylene
The low density polyethylene (LDPE) includes an ethylene homopolymer and a copolymer of ethylene and an α-olefin.
The α-olefin is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene. , 1-decene. Two or more of them may be used in combination.
According to JIS K6922-2 of the above low density polyethylene, the MFR measured at 190 ° C. under a 2.16 kg load is 0.1 to 10 g / 10 min, preferably 0.15 to 5 g / 10 min, more preferably 0.17. ~ 3g / 10min.
The density measured in accordance with JIS K6922-2 of low density polyethylene is 0.915 to 0.930 g / cm.3, Preferably 0.917 to 0.926 g / cm3More preferably, 0.918 to 0.925 g / cm3Those in the range of are desirable.
The density of the low density polyethylene is 0.915 g / cm3If it is less than this, there is a possibility that the rigidity of the film molded product obtained by using the target polyethylene resin composition is significantly lowered. The density is 0.930 g / cm.3If it is higher, the transparency of the film molded product obtained using the intended polyethylene resin composition may be significantly reduced.
[0015]
Ethylene / vinyl ester copolymer
The ethylene-vinyl ester copolymer is ethylene propyleneate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, which are mainly produced by high-pressure radical polymerization. And a copolymer with a vinyl ester monomer. Among these, vinyl acetate is particularly preferable.
[0016]
Ethylene and α , Copolymer with β-unsaturated carboxylic acid or derivative thereof
Examples of the copolymer of ethylene and α, β-unsaturated carboxylic acid or a derivative thereof include ethylene / (meth) acrylic acid or an alkyl ester copolymer thereof, and these comonomers include acrylic acid and methacrylic acid. , Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, methacryl Examples include cyclohexyl acid, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and the like. Among these, alkyl esters such as methyl and ethyl of (meth) acrylic acid are particularly preferable.
Specifically, ethylene / (meth) acrylic acid copolymer, ethylene / maleic anhydride; ethylene / (meth) methyl acrylate copolymer, ethylene / (meth) ethyl acrylate copolymer, ethylene / (meth) Glycidyl acrylate copolymers, ethylene / maleic anhydride / vinyl acetate copolymers, ethylene / (meth) alkyl acrylate copolymers such as ethylene / maleic anhydride / ethyl acrylate copolymers, ethylene / (meth) Examples thereof include acrylic acid copolymer metal salts (ionomers).
[0017]
The high-pressure radical ethylene (co) polymer resin (B) of the present invention is a method described in Kazuo Matsuura and Naotaka Mikami, “Polyethylene Technology Reader”, published by the Industrial Research Society, 2001, p. Can be manufactured.
That is, the pressure is 50 to 350 MPa · Gauge (500 to 3500 Kg / cm2G), polymerization temperature is in the range of 100 to 400 ° C., radical polymerization using oxygen or organic peroxide as a polymerization initiator, and can be produced in an autoclave type or tubular type reactor. Regardless of whether the reactor for producing the high-pressure radical process ethylene (co) polymer resin of the present invention is an autoclave type or a tubular type, a film molded body obtained by using the target polyethylene resin composition Has little effect on transparency, rigidity and impact resistance.
[0018]
(C) Linear low density polyethylene resin
The linear low density polyethylene resin (C) of the present invention refers to a copolymer of ethylene and an α-olefin. The α-olefin is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene. , 1-decene and the like. Two or more of them may be used in combination. Among these copolymers, an ethylene / 1-hexene copolymer, an ethylene / 4-methyl-1-pentene copolymer, and an ethylene / 1-octene copolymer are preferable from the viewpoints of strength and economy.
[0019]
The linear low density polyethylene resin (C) that can be used in the present invention has an MFR measured under 190.degree. C. and 2.16 kg load in accordance with JIS K6922-2, 0.1 to 10 g / 10 min, preferably 0. 0.3 to 5.0 g / 10 min, and more preferably 0.5 to 3.0 g / 10 min. Further, the density measured in accordance with JIS K6922-2 is 0.900 to 0.935 g / cm.3, Preferably 0.903 to 0.930 g / cm3More preferably, 0.904-928 g / cm3It is in the range.
When the MFR of the linear low-density polyethylene resin (C) is less than 0.1 g / 10 min, compatibility with other components is deteriorated when processing into a film molded body using the target polyethylene resin composition. As a result, gel and fish eyes may be caused, and the appearance of the film molded product may be remarkably impaired.
Moreover, when MFR of linear low density polyethylene resin (C) is larger than 10 g / 10min, there exists a possibility that the intensity | strength of the film molded object obtained using the target polyethylene resin composition may fall remarkably.
The density of the linear low density polyethylene resin (C) is 0.900 g / cm.3If it is less than 1, the rigidity of the film molded product obtained by using the target polyethylene resin composition may be significantly reduced. The density of the linear low density polyethylene resin (C) is 0.935 g / cm.3If it is higher, the strength of the film molded product obtained using the intended polyethylene resin composition may be significantly reduced.
[0020]
Among the linear low-density polyethylene resins (C), those having a molecular weight distribution (Mw / Mn) in the range of 1.5 to 3.5 are preferable. In particular, (a) continuous temperature rising elution fractionation (TREF) ) The temperature T at which there are substantially a plurality of peaks in the elution temperature-elution amount curve and25And the temperature T at which 75% of the total elution occurs.75T which is the difference between75-T25However, the relationship with the density d is −300 × d + 285 ≦ T75-T25A linear low density polyethylene satisfying ≦ −670 × d + 644 is preferable.
[0021]
The molecular weight distribution (Mw / Mn) of the linear low density polyethylene resin (C) is preferably in the range of 1.5 to 3.5, more preferably 2.0 to 3.3, more preferably 2. It is desirable to be in the range of 3 to 3.2.
When Mw / Mn is less than 1.5, when processing into a film molded body using the target polyethylene resin composition, there is a possibility that the production efficiency is remarkably reduced because the motor of the processing machine is overloaded. Arise. Moreover, when Mw / Mn exceeds 3.5, there exists a possibility that the intensity | strength of the film molded object obtained using the target polyethylene resin composition may fall significantly.
Generally, Mw / Mn of a polyethylene resin is obtained by calculating a weight average molecular weight (Mw) and a number average molecular weight (Mn) by gel permeation chromatography (hereinafter referred to as GPC) and calculating a ratio (Mw / Mn) thereof. .
[0022]
Furthermore, the requirements for the linear low density polyethylene resin (C) (a) The fact that there are substantially a plurality of elution temperature-elution amount curve peaks by the continuous temperature rising elution fractionation method (TREF) is shown in FIG. In this elution temperature-elution amount curve obtained by TREF, a specific copolymer of ethylene and α-olefin in which a plurality of peaks substantially appear, and the peak on the high temperature side of the plurality of peaks is from 85 ° C. to 100 ° C. It is particularly desirable to be between 0C.
This is substantially equivalent to a peak in the elution temperature-elution amount curve obtained by TREF like the copolymer of ethylene and α-olefin obtained in the presence of a typical metallocene catalyst as shown in FIG. A distinction is made from copolymers of ethylene and α-olefins, which show only one.
By satisfying such requirement (A), the heat resistance, hot tackiness, etc. of the film can be improved.
[0023]
Moreover, the temperature T at which 25% of the total elution is obtained in the integral value of the requirement (b) elution amount of the linear low density polyethylene resin (C)25And the temperature T at which 75% of the total elution occurs.75T which is the difference between75-T25Is -300 × d + 285 ≦ T75-T25≦ −670 × d + 644 satisfies the relationship: elution temperature of linear low density polyethylene resin (C) by TREF with the horizontal axis shown in FIG. 3 as the elution temperature and the vertical axis as the relative elution amount − In the elution volume curve, the temperature at which 25% of the total elution volume is eluted from the low temperature side is obtained from the elution curve.twenty five(° C), and the temperature at which 75% is eluted is T75(℃) and T75-T25(C) is the density d (g / cm3) And the above relationship.
When the above relationship is satisfied, the strength of the film molded body obtained by using the target polyethylene resin composition can be sufficiently improved.
[0024]
The linear low-density polyethylene resin (C) of the present invention is not limited to a catalyst, a production method, and the like. A polymerization catalyst such as a Ziegler catalyst or a metallocene catalyst is used to form a gas phase polymerization method, a solution. It can be produced by a production process such as a polymerization method, a slurry polymerization method or a high pressure ion polymerization method.
That is, it can be produced by the method described in Kazuo Matsuura and edited by Naotaka Mikami, “Polyethylene Technology Reader”, Kogyo Kenkyukai, 2001, p. 179-195.
[0025]
In addition, as a method for easily producing a linear low density polyethylene resin that can satisfy the molecular weight distribution of a specific range of the linear low density polyethylene resin (C) of the present invention and the requirements (a) and (b) of TREF. Copolymerize ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a single-site 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 particularly desirable to produce using a catalyst obtained by mixing the following compounds a1 to a4.
a1: General formula Me1R1 pR2 q(OR3)rX1 4-pqr
A compound represented by the formula:1Represents zirconium, titanium, hafnium, R1And R3Are each a hydrocarbon group having 1 to 24 carbon atoms, R2Is a 2,4-pentandionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof, X1Represents a halogen atom, and p, q, and r are integers indicating ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4, respectively.
a2: General formula Me2R4 m(OR5)nX2 z-mn
A compound represented by the formula:2Is the Group I-III element of the periodic table, R4And R5Are each a hydrocarbon group having 1 to 24 carbon atoms, X2Is a halogen atom or a hydrogen atom (however, X2Me is a hydrogen atom2Is only for Group III elements of the Periodic Table), z is Me2And m and n are integers indicating ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z.)
a3: an organic cyclic compound having a conjugated double bond
a4: Modified organoaluminum oxy compound and / or boron compound containing Al—O—Al bond
[0026]
Further details will be described below. General formula Me of the catalyst component a11R1 pR2 q(OR3)rX1 4-pqrIn the formula of the compound represented by1Represents zirconium, titanium, and hafnium, but the type of these transition metals is not limited to any one, and a plurality of them can be used. R1And R3Are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. 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, xylyl group, mesityl group, indenyl group and naphthyl group Aryl groups such as benzyl groups, trityl groups, phenethyl groups, styryl groups, benzhydryl groups, phenylbutyl groups, neophyll groups, and the like. These may be branched. R2Represents a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof. X1Represents a halogen atom such as fluorine, iodine, chlorine and bromine. p, q, and r are integers that satisfy ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ P + q + r ≦ 4, respectively.
Examples of the compound represented by the general formula of the catalyst component a1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrabutoxytitanium, tetrabutoxyhafnium, and the like. Zr (OR) such as tetrapropoxyzirconium and tetrabutoxyzirconium4Compounds are preferred, and two or more of these may be used in combination.
[0027]
Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonate ligand or derivative thereof include tetra (2,4-pentandionato) zirconium. , Tri (2,4-pentanedionato) chloride zirconium, di (2,4-pentandionato) dichloride zirconium, (2,4-pentandionato) trichloride zirconium, di (2,4-pentandionato) Diethoxide zirconium, di (2,4-pentandionato) di-n-propoxide zirconium, di (2,4-pentandionato) di-n-butoxide zirconium, di (2,4-pentane) Dionato) dibenzylzirconium, di (2,4-pentanedionato) dineophilylzirconium, tetra (dibenzoylme) Thanato) zirconium, di (dibenzoylmethanato) diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (dibenzoylmethanato) di-n-butoxidezirconium, di (dibenzoylacetonato) ) Dietoxide zirconium, di (dibenzoylacetonato) di-n-propoxide zirconium, di (dibenzoylacetonato) di-n-butoxide zirconium and the like.
[0028]
General formula Me of the catalyst component a22R4 m(OR5)nX2 z-mnIn the formula of the compound represented by2Represents a group I-III element of the periodic table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. R4And R5Are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8, specifically alkyl such as methyl group, ethyl group, propyl group, isopropyl group and butyl group. Group: alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenyl Examples include aralkyl groups such as butyl group and neophyll group. These may be branched. X2Represents a halogen atom or hydrogen atom such as fluorine, iodine, chlorine and bromine. However, X2Me is a hydrogen atom2Is limited to the group III elements of the periodic table exemplified by boron, aluminum and the like. Z is Me2M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.
[0029]
The organic cyclic compound having a conjugated double bond of the catalyst component a3 is cyclic and has one or two rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. A cyclic hydrocarbon compound having at least 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms; the cyclic hydrocarbon compound is partially a hydrocarbon residue having 1 to 6 carbon atoms (typically having 1 carbon atom) A cyclic hydrocarbon compound substituted with ˜12 alkyl groups or aralkyl groups; one or more rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds An organosilicon compound having a cyclic hydrocarbon group having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially composed of 1 to 6 hydrocarbon residues or alkali metal salts ( Sodium salt or lithium salt) Organosilicon compounds substituted are included. Particularly preferred are those having a cyclopentadiene structure in any of the molecules.
[0030]
Suitable examples of the compound include cyclopentadiene, indene, azulene, or alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Moreover, the compound which these compounds couple | bonded (bridge | crosslinked) via the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.
[0031]
The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.
ALSiR4-L
Here, A represents the cyclic hydrocarbon 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, an isopropyl group, An alkyl group such as a butyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group; 1 to 24, preferably 1 to 12 hydrocarbon residues or hydrogen, L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.
[0032]
Specific examples of the organic cyclic hydrocarbon compound of component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, Cyclopolyene having 5 to 24 carbon atoms such as cycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadienyl Examples thereof include silane, monoindenyl silane, bisindenyl silane, and trisindenyl silane.
The modified organoaluminum oxy compound containing an Al—O—Al bond of the catalyst component a4 is obtained by reacting an alkylaluminum compound with water to obtain a modified organoaluminum oxy compound usually referred to as an aluminoxane. Usually, it contains 1 to 100, preferably 1 to 50 Al—O—Al bonds. The modified organoaluminum oxy compound may be linear or cyclic.
The reaction between 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 preferable. 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.
[0033]
Examples of boron compounds include triethylaluminum triethylammonium tetra (pentafluorophenyl) borate tetra (pentafluorophenyl) borate, dimethylanilinium dimethylanilinium tetra (pentafluorophenyl) borate tetra (pentafluorophenyl) borate, butylammonium tetra (Pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (3,5-difluorophenyl) borate and the like.
[0034]
The catalyst may be used by mixing and contacting a1 to a4, but preferably it is used by supporting it on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or particulate polymer carrier (a5) include carbon materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, thermoplastic resins, thermosetting resins, and the like.
Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Specifically, SiO2, Al2O3, MgO, ZrO2TiO2, B2O3, CaO, ZnO, BaO, ThO2Etc. or a mixture thereof, SiO 22-Al2O3, SiO2-V2O5, SiO2-TiO2, SiO2-MgO, SiO2-Cr2O3Etc. Among these, SiO2And Al2O3The main component is at least one component selected from the group consisting of: 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 methacrylate, polystyrene, polynorbornene, Examples include various natural polymers and mixtures thereof.
The inorganic carrier and / or the particulate polymer carrier can be used as they are, but preferably these carriers are brought into contact with an organoaluminum compound or a modified organoaluminum oxy compound containing an Al—O—Al bond as a pretreatment. After that, it can also be used as component a5.
[0035]
A preferred production method of the linear low density polyethylene resin (C) is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, etc. substantially free of a solvent in the presence of the catalyst, and substantially oxygen. Examples are aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Produced in the presence or absence of an inert hydrocarbon solvent. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C., preferably 20 to 200 ° C., more preferably 50 to 110 ° C., and the polymerization pressure is usually normal pressure to 7 MPa · Gauge (low to medium pressure method). 70 kg / cm2G), preferably normal pressure to 2 MPa · Gauge (20 kg / cm2G), and in the case of the high pressure method, usually 150 MPa · Gauge (1500 kg / cm2G) The following is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from about 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 one-stage polymerization method, but also a two-stage or more multi-stage polymerization method in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other. A particularly preferable production method includes the method described in JP-A-5-132518.
[0036]
Polyethylene resin composition
The mixing ratio of each component constituting the polyethylene resin composition of the present invention is as follows: high-density polyethylene resin (A) 60 to 90% by mass, high-pressure radical ethylene (co) polymer resin (B) 1 to 39% by mass, The chain low density polyethylene resin (C) is 1 to 39% by mass. In particular, when used for film forming, the high-density polyethylene resin (A) is preferably 70 to 87% by mass, more preferably 75 to 85% by mass, and the high-pressure radical ethylene (co) polymer resin (B) is preferable. By selecting from 3 to 21% by mass, more preferably 4 to 16% by mass, and the linear low density polyethylene resin (C) is preferably 9 to 35% by mass, more preferably 14 to 25% by mass. A molded product having high transparency and high rigidity and excellent strength can be obtained (however, the total amount of the three components is 100% by mass).
[0037]
In this polyethylene resin composition, other resins and various additives can be appropriately blended without departing from the object of the present invention. Examples of the additive include an antioxidant, a lubricant, an antiblocking agent, an antistatic agent, a pigment, a weathering stabilizer, a nucleating agent, a flame retardant, a crosslinking agent, a foaming agent, and a filler.
[0038]
Production of polyethylene resin composition
The polyethylene resin composition of the present invention, after using a Henschel mixer, a tumbler blender, etc., and dry blending each component constituting the polyethylene resin composition at a predetermined mixing ratio, usually a single screw extruder, a twin screw extruder, By adding melt-kneading using a kneader, Banbury mixer, mixing roll or the like, a polyethylene resin composition adjusted to a uniform composition can be produced.
[0039]
Compact
As a molded object which consists of a polyethylene resin composition of this invention, the molded object obtained from extrusion molding, injection molding, blow molding, rotational molding, etc. is included. For example, film products represented by supermarket shopping bags, laminated products represented by milk paper packs, small containers such as cooking oil, detergents, cosmetics, large industrial products such as automobile gasoline tanks, plastic drums, gas pipes and waterworks A pipe etc. are mentioned, Especially preferably, a film or a processed product using the film is mentioned. Although there is no restriction | limiting of thickness as a film, it has a remarkable effect especially about a film molded object below 50 micrometers, Preferably it is 30 micrometers or less.
In order to obtain a film molding comprising the polyethylene resin composition of the present invention, the composition obtained as described above can be molded into a film by an inflation molding method or a cast film method by a conventional method. Since the resin composition of the present invention has good processability, it can be easily formed into a film by any known method.
If necessary, the melt-kneading operation can be omitted. That is, a film molded body can be obtained by dry blending each component constituting the polyethylene resin composition at a predetermined mixing ratio and then directly feeding it into a film molding machine.
[0040]
Use of film
The film obtained by molding as described above can be used in the form of the film or further processed into an appropriate form such as a bag.
In use, it is possible to perform appropriate printing for decoration, design, etc., but in order to make use of transparency, a certain transparent portion is held for use.
A typical use of the film according to the present invention is a packaging film, which is a packaging film for automatically packaging a tissue paper storage foil pack as described above. Here, the packaging film includes a film in a container form for storing and packaging appropriate contents.
The film according to the present invention thus obtained is thin and has high rigidity so that it can be thinned, has an automatic packaging suitability, for example, a film having a thickness of 5 to 30 μm having practical strength. can get. Further, since the haze value is 10% or less, preferably 8% or less at this thickness, details such as decoration and design on the surface of the package can be easily visually confirmed. Further, it is desirable that the tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, and impact fracture mass of the film are approximately in the following ranges, respectively.
In addition, for transparency, for example, in transparent packaging, a barcode pattern on the surface of an object to be packaged is often read directly with a barcode reader through the packaging film, but the film according to the present invention is also similar. Transparent enough to be read.
[0041]
【Example】
EXAMPLES Next, although this invention is demonstrated through an Example, this invention is not limited at all by these Examples.
[Test methods]
density
Conforms to JIS K6922-2.
MFR
Conforms to JIS K6922-2.
FCI measurement method
The FCI measurement method of the high-density polyethylene resin (A) according to the present invention is as follows.
The measuring device uses a rotating rheometer UDS-200 manufactured by Paar Physica Co., Ltd., and MP306 (a flat plate having a diameter of 25 mm) is used as a fixing jig. The measurement temperature is 190 ° C., the strain is 10%, the distance between the plates is 2.1 mm, and the complex viscosity η at a frequency of 0.1 rad / s.* 0 . 1And the complex viscosity η at a frequency of 10 rad / s* 10Measure. FCI is η* 0 . 1And η* 10It is calculated from the logarithm ratio.
Mw / Mn measurement method
The Mw / Mn measuring method of the linear low density polyethylene resin (C) according to the present invention is as follows.
The measuring apparatus uses Gels permeation chromatography 150Cplus manufactured by Waters Co., Ltd., two Shodex HT-806Ms manufactured by Showa Denko Co., Ltd. are connected in series to the column, and a detector manufactured by Miran Co., Ltd. is used. A differential refractometer 1A type is used. The measurement temperature is 140 ° C., and the eluent is a 1,2,4-trichlorobenzene dissolved in 0.05% by mass of 2,4,6-trimethylphenol, and is operated at a flow rate of 1.0 ml / min. . The sample is weighed out at 3.0 mg, dissolved in 3.0 ml of the solvent having the same composition as the eluent and shaken at 150 ° C. for 2 hours, and the injection volume of the sample solution is 300 μl. Mw / Mn is calculated from the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by the above measurement.
TREF measurement method
First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) is added so that the sample concentration is 0.05 mass%, and is heated and dissolved at 140 ° C. 5 ml of this sample solution is poured into a column filled with glass beads while keeping the column at 135 ° C., cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the glass bead surface. . Next, the sample is sequentially eluted while increasing the column temperature at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent was set to the wave number 2925 cm of the asymmetric stretching vibration of methylene.-1Is continuously detected by measuring the absorption with respect to an infrared detector. From this value, the concentration of the sample in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. According to the TREF analysis, since a change in elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, a relatively fine peak that cannot be detected by a fractionation method can be detected.
[0042]
[Used resin]
(A) High density polyethylene resin
Table 1 below shows the brand and physical properties of the high-density polyethylene resin used.
[Table 1]
[0043]
(B) High-pressure radical method ethylene (co) polymer resin
A high-pressure radical method low-density polyethylene resin was used as the high-pressure radical method ethylene (co) polymer resin. Brands and physical properties are shown in Table 2.
[Table 2]
[0044]
(C) Linear low density polyethylene resin
[Preparation of solid catalyst]
In a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, tetrapropoxyzirconium (Zr (OPr)Four) 26 g, 22 g of indene and 88 g of methylbutylcyclopentadiene were added, 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining at 90 ° C., and then reacted at the same temperature for 2 hours. After cooling to 40 ° C., 2424 ml of a toluene solution of methylalumoxane (concentration: 3.3 mmol / ml) was added and stirred for 2 hours. Next, silica (surface area of 300 m) previously calcined at 450 ° C. for 5 hours.2/ G) After adding 2000 g and 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]
Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 65 ° C., total pressure 2 MPa · Gauge (20 kgf / cm2In G), ethylene and 1-hexene were copolymerized. The solid catalyst was continuously supplied, and ethylene, 1-hexene, hydrogen and the like were supplied so as to maintain a predetermined molar ratio, and polymerization was performed to obtain an ethylene / 1-hexene copolymer (C1 to C4). . The measurement results of the physical properties of the copolymer are shown in Table 3 below.
Moreover, the following were used as LLDPE (referred to as C5) by Ziegler catalyst, and the physical properties are shown in Table 3 below.
Ethylene / 1-hexene copolymer
Density: 0.922g / cm3
MFR: 0.90g / 10min
Brand: J-Rex LL A607F (manufactured by Nippon Polyolefin Co., Ltd.)
[0045]
[Table 3]
[0046]
Processing conditions for film moldings
A film molded product obtained using the polyethylene resin composition of the present invention could be molded under the following conditions by an air-cooled inflation molding method.
The extruder used was an EX-55 type extruder manufactured by Plako Co., Ltd., and the screw combined therewith was a full flight type 55 mmφ screw (compression ratio 2.3). The die for forming an air-cooled inflation film uses a 75 mmφ (lip 1.2 mm) manufactured by Tommy Machinery Co., Ltd., under conditions of a molding temperature of 220 ° C. and a take-off speed of 10.3 m / min, a film width of 360 mm, a film thickness A 20 μm film was obtained.
In addition, those with good film formation stability during molding of an air-cooled inflation film were classified as “◯”, and those with poor film formation stability were classified as “Δ”.
[0047]
Physical properties of polyethylene resin composition
A method for measuring physical properties of a molded film obtained using the polyethylene resin composition of the present invention is as follows.
Tensile elastic modulus: measured at 23 ° C. in accordance with JIS K6922-2.
Tensile fracture stress: measured at 23 ° C. according to JIS K6922-2
Tensile fracture nominal strain: Measured at 23 ° C. in accordance with JIS K6922-2.
Tear strength: Measured at 23 ° C. according to JIS K7128-2 (Elmendorf method).
Impact fracture mass: Measured at 23 ° C. in accordance with JIS K7124-1 (Method A).
Haze: Measured according to JIS K7136.
[0048]
(Examples 1-3)
MFR 0.20 g / 10 min, density 0.950 g / cm3, High density polyethylene resin (A1) with FCI of 1.12, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.90 g / 10 min, density 0.920 g / cm3, Mw / Mn is 2.7, T75-T2519.0 ° C. linear low density polyethylene (ethylene / 1-hexene copolymer) (C1) was dry blended in the ratios shown in Table 4 and formed into a film by the above-mentioned air-cooled inflation film forming method. Got the body. The film was measured for tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze, and the results are shown in Table 4.
[0049]
[Table 4]
[0050]
(Examples 4 to 6)
MFR 0.20 g / 10 min, density 0.950 g / cm3, High density polyethylene resin (A1) with FCI of 1.12, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.90 g / 10 min, density 0.905 g / cm3, Mw / Mn is 2.8, T75-T25Is a dry blend of linear low density polyethylene (ethylene / 1-hexene copolymer) (C2) having a temperature of 21.5 ° C. at the ratio shown in Table 5 and film-formed by the above-mentioned air-cooled inflation film-forming method. Got the body. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 5.
[0051]
(Comparative Example 1)
MFR 0.20 g / 10 min, density 0.950 g / cm3Using a high-density polyethylene resin (A1) having an FCI of 1.12 as a raw material, a film molded body was obtained by the air-cooled inflation film molding method described above. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 5.
[0052]
(Comparative Example 2)
MFR is 0.40 g / 10 min, density is 0.953 g / cm.3, FCI 1.10 high density polyethylene resin (A2), MFR 0.40 g / 10 min, density 0.992 g / cm3The high pressure radical method low density polyethylene resin (B2) was dry blended at the ratios shown in Table 5, and a film molded body was obtained by the air-cooled inflation film molding method described above. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 5.
[0053]
[Table 5]
[0054]
(Example 7)
MFR 0.20 g / 10 min, density 0.950 g / cm3, High density polyethylene resin (A1) with FCI of 1.12, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 3.5 g / 10 min, density 0.920 g / cm3, Mw / Mn is 2.8, T75-T2519.9 ° C. linear low density polyethylene (ethylene / 1-hexene copolymer) (C3) was dry blended in the ratios shown in Table 6 and formed into a film by the air-cooled inflation film forming method described above. Got the body. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 6.
[0055]
(Example 8)
MFR 0.20 g / 10 min, density 0.950 g / cm3, High density polyethylene resin (A1) with FCI of 1.12, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.70 g / 10 min, density 0.905 g / cm3, Mw / Mn is 2.9, T75-T25Is a dry blend of linear low density polyethylene (ethylene / 1-hexene copolymer) (C4) having a temperature of 20.3 ° C. at the ratio shown in Table 6 and film-formed by the above-mentioned air-cooled inflation film-forming method. Got the body. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 6.
[0056]
Example 9
MFR 0.20 g / 10 min, density 0.950 g / cm3, High density polyethylene resin (A1) with FCI of 1.12, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.90 g / 10 min, density 0.992 g / cm3, Mw / Mn is 4.8, T75-T25Is a dry blend of linear low density polyethylene (ethylene / 1-hexene copolymer) (C5) using a Ziegler catalyst at 24.7 ° C. in the ratios shown in Table 6, and the aforementioned air-cooled inflation film forming method A film molded body was obtained. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 6.
[0057]
(Example 10)
MFR 0.20 g / 10 min, density 0.950 g / cm3, High density polyethylene resin (A1) with FCI of 1.12, MFR of 2.0 g / 10 min, density of 0.924 g / cm3High pressure radical method low density polyethylene resin (B3), MFR 0.90 g / 10 min, density 0.920 g / cm3, Mw / Mn is 2.7, T75-T2519.0 ° C. linear low density polyethylene (ethylene / 1-hexene copolymer) (C1) is dry blended in the ratios shown in Table 6 and film-formed by the above-mentioned air-cooled inflation film-forming method. Got the body. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 6.
[0058]
[Table 6]
[0059]
(Comparative Examples 3 and 4)
MFR 0.20 g / 10 min, density 0.950 g / cm3, High density polyethylene resin (A1) with FCI of 1.12, MFR of 0.90 g / 10 min, density of 0.920 g / cm3, Mw / Mn is 2.7, T75-T2519.0 ° C. linear low density polyethylene (ethylene / 1-hexene copolymer) (C1) is dry blended at the ratios shown in Table 7 and film-formed by the above-mentioned air-cooled inflation film-forming method. Got the body. The film was measured for tensile elastic modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze, and the results are shown in Table 7.
[0060]
(Example 11)
MFR 0.70 g / 10 min, density 0.956 g / cm3, High density polyethylene resin (A3) with FCI of 1.09, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.90 g / 10 min, density 0.920 g / cm3, Mw / Mn is 2.7, T75-T2519.0 ° C. linear low density polyethylene (ethylene / 1-hexene copolymer) (C1) is dry blended at the ratios shown in Table 7 and film-formed by the above-mentioned air-cooled inflation film-forming method. Got the body. The film was measured for tensile elastic modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze, and the results are shown in Table 7.
[0061]
(Example 12)
MFR 1.2g / 10min, density 0.956g / cm3, FCI 1.08 high density polyethylene resin (A4), MFR 0.25 g / 10 min, density 0.992 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.90 g / 10 min, density 0.920 g / cm3, Mw / Mn is 2.7, T75-T2519.0 ° C. linear low density polyethylene (ethylene / 1-hexene copolymer) (C1) is dry blended at the ratios shown in Table 7 and film-formed by the above-mentioned air-cooled inflation film-forming method. Got the body. The film was measured for tensile elastic modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze, and the results are shown in Table 7.
[0062]
[Table 7]
[0063]
(Reference Example 1)
MFR is 1.0 g / 10 min, density is 0.950 g / cm.3, High density polyethylene resin (A5) with FCI of 1.13, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.90 g / 10 min, density 0.920 g / cm3, Mw / Mn is 2.7, T75-T2519.0 ° C. linear low density polyethylene (ethylene / 1-hexene copolymer) (C1) is dry blended in the ratios shown in Table 8 and film-formed by the above-mentioned air-cooled inflation film-forming method. Got the body. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 8.
[0064]
(Comparative Example 5)
MFR 0.70 g / 10 min, density 0.956 g / cm3, High density polyethylene resin (A3) with FCI of 1.09, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.90 g / 10 min, density 0.905 g / cm3, Mw / Mn is 2.8, T75-T25Is a dry blend of linear low density polyethylene (ethylene / 1-hexene copolymer) (C2) having a temperature of 21.5 ° C. in the ratio shown in Table 8 and film-formed by the above-described air-cooled inflation film-forming method. Got the body. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 8.
[0065]
(Examples 13 to 14)
MFR 0.70 g / 10 min, density 0.956 g / cm3, High density polyethylene resin (A3) with FCI of 1.09, MFR of 0.25 g / 10 min, density of 0.922 g / cm3High pressure radical method low density polyethylene resin (B1), MFR 0.90 g / 10 min, density 0.905 g / cm3, Mw / Mn is 2.8, T75-T25Is a dry blend of linear low density polyethylene (ethylene / 1-hexene copolymer) (C2) having a temperature of 21.5 ° C. in the ratio shown in Table 8 and film-formed by the above-described air-cooled inflation film-forming method. Got the body. The tensile modulus, tensile fracture stress, tensile fracture nominal strain, tear strength, impact fracture mass, and haze of the film were measured, and the results are shown in Table 8.
[0066]
[Table 8]
[0067]
Evaluation results
As is clear from the above examples and comparative examples, the polyethylene resin composition of this example has high transparency (haze), high rigidity (tensile modulus), high strength (impact fracture mass (strength), etc.) Can provide a well-balanced film. On the other hand, the high density polyethylene resin alone of Comparative Example 1 is inferior in transparency and film forming stability. In addition, the two-component composition of the high-density polyethylene resin and the low-density polyethylene resin of Comparative Example 2 has a low impact fracture mass (strength), and as seen in Comparative Examples 3 and 4, the high-density polyethylene resin and the linear composition. The two-component composition of low-density polyethylene resin has a difficulty in processability. When the FCI value of Reference Example 1 is not in an appropriate range, the transparency may be low, and the impact fracture mass (strength) may be low. Further, as seen in Comparative Example 5, it can be seen that if the blending ratio of the three-component composition is not within the range of the present invention, the impact fracture mass (strength) is low and the rigidity is also lowered.
[0068]
【The invention's effect】
As described above, the polyethylene resin composition of the present invention comprises a high-density polyethylene resin (A), a high-pressure radical ethylene (co) polymer resin (B), and a linear low-density polyethylene resin (C). By selecting the range, it is possible to provide a well-balanced film having high transparency (haze), high rigidity (tensile modulus), and high strength (such as impact fracture mass (strength)) as the film. By using this composition, it becomes possible to reduce the thickness particularly, and for example, a film having a thickness of 5 to 30 μm can be obtained with practical strength. Thus, the thickness can be reduced, the transparency can be further improved by the thinning of the film, and the barcode can be easily read.
Moreover, since it shape | molds from a resin material with favorable workability, film shaping | molding of an inflation film etc. can be performed easily.
Furthermore, it can also be used in a container form as appropriate.
[Brief description of the drawings]
FIG. 1 is a graph showing an elution temperature-elution amount curve by TREF of a linear low density polyethylene resin (C) according to the present invention.
FIG. 2 is a graph showing an elution temperature-elution amount curve by TREF of an ethylene / α-olefin copolymer using a typical metallocene catalyst.
FIG. 3 is a graph showing T in an elution temperature-elution amount curve by TREF of a linear low density polyethylene resin (C) according to the present invention.75, T25FIG.

Claims (5)

  1. The melt flow rate is 0.1 to 10 g / 10 min, the density is in the range of 0.940 to 0.965 g / cm 3 , and the viscosity curve index (FCI) and the melt flow rate (MFR) are −0.063 × log. (MFR) + 1.10 ≧ FCI ≧ −0.046 × log (MFR) +1.06 high-density polyethylene resin (A) 60-90 mass%, melt flow rate 0.1-10 g / 10 min High pressure radical ethylene (co) polymer resin (B) in the range of 1 to 39% by mass, melt flow rate of 0.1 to 10 g / 10 min, density of 0.900 to 0.935 g / cm 3 A polyethylene resin composition comprising 1 to 39% by mass of a certain linear low density polyethylene resin (C) (here, the total amount of A, B and C is 100% by mass).
  2. The polyethylene resin composition according to claim 1, wherein the linear low density polyethylene resin (C) has a molecular weight distribution (Mw / Mn) in the range of 1.5 to 3.5.
  3. The polyethylene resin composition according to claim 1 or 2, wherein the linear low-density polyethylene resin (C) satisfies the following requirements (a) and (b).
    (B) There are a plurality of elution temperature-elution amount curve peaks by continuous temperature rising elution fractionation method (TREF), and (b) temperature T 25 at which 25% of the total elution amount is eluted, T 75 −T 25, which is a difference from the temperature T 75 at which 75% of the sample is eluted, satisfies the following formula in relation to the density d.
    −300 × d + 285 ≦ T 75 −T 25 ≦ −670 × d + 644
  4. The linear low-density polyethylene resin (C) comprises ethylene and α-olefin using a single-site catalyst including an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table. The polyethylene resin composition according to any one of claims 1 to 3 , which is a linear low-density polyethylene resin obtained by polymerization.
  5. The molded object which consists of a polyethylene resin composition in any one of Claim 1 to 4 .
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CA2667459C (en) 2006-10-23 2015-01-20 Dow Global Technologies Inc. Polyethylene compositions, methods of making the same, and articles prepared therefrom
US8101685B2 (en) 2008-12-15 2012-01-24 Exxonmobil Chemical Patents Inc. Thermoplastic elastomer polyolefin in-reactor blends and molded articles therefrom
US8497325B2 (en) 2008-12-15 2013-07-30 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends and films therefrom
US8022142B2 (en) * 2008-12-15 2011-09-20 Exxonmobil Chemical Patents Inc. Thermoplastic olefin compositions
US8227547B2 (en) 2008-12-15 2012-07-24 Exxonmobil Chemical Patents Inc. Foamable thermoplastic reactor blends and foam article therefrom
US8410217B2 (en) 2008-12-15 2013-04-02 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends
JP5937431B2 (en) * 2012-06-12 2016-06-22 Jfeケミカル株式会社 Resin composition and cured product thereof
JP5948183B2 (en) * 2012-08-23 2016-07-06 株式会社細川洋行 Blow molded container and resin composition for blow molded container
JP6311562B2 (en) * 2013-10-10 2018-04-18 東ソー株式会社 Polyethylene resin composition, laminate comprising the same, and medical container using the laminate
RU2684098C2 (en) * 2014-10-09 2019-04-04 ВЕРСАЛИС С.п.А. Cross-linking composition containing polyethylene and its application for rotational moulding
CN104708874A (en) * 2015-04-12 2015-06-17 李燕 Formula for preparing environment-friendly plastic water hose
DE102017114488A1 (en) 2017-06-29 2019-01-03 Schaeffler Technologies AG & Co. KG Planetary gear with lubrication grooves and through hole in the rolling cage

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