JP2002003662A - Polyethylene resin composition and its film, porous film and molded articles and method of manufacturing the porous film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene resin composition which improves masking property of a thin film obtained and also to provide a method of manufacturing molded articles such as a film, a porous film which are excellent in moldability, flexibility, air permeability, moisture permeability or the like. SOLUTION: This polyethylene resin composition includes a resin ingredient having an ethylene (co)polymer satisfying the following requirements (a)-(d) as a main ingredient, calcium carbonate and a white masking agent; and the molding articles using the polyethylene resin composition is disclosed. (a) density: 0.86-0.97 g/cm3, (b) MFR: 0.1-50 g/10 minutes, (c) molecular weight distribution (Mw/Mn):1.5-4.5, (d) Both the difference T75-T25 between temperature T25 wherein 25% of the whole is eluted and temperature T75 wherein 75% of the whole is eluted, each of the temperatures being obtained from the integrated elusion curve of an elution temperature - elution quantity curve by a continuous temperature rise elution and fractionation method (TREF), and density (d) satisfy the following formula: T75-T25<=-670×d+644.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyethylene resin containing a large amount of calcium carbonate, which is used for a garbage bag, a porous film or a porous sheet (hereinafter collectively referred to as a porous film). Composition, a molded article using the composition, particularly a film using the composition,
The present invention relates to a garbage bag, a porous film, a material for sanitary goods, a molded article such as a house wrap, and a method for producing a porous film using the film. More specifically, a polyethylene resin composition that can improve the concealing properties of a down-gauged thin film, greatly reduce the size of the eyes during molding, enable long-term continuous operation, and improve productivity. About things. In addition, a film which is rich in flexibility and is suitable for a garbage bag or the like, which is obtained by stretching the film, and has a high tear strength, particularly in the longitudinal direction, and a porous film, a house wrap, and a hygienic material which is rich in breathability and moisture permeability. The present invention relates to a molded article that can be used in the fields of clothing materials, sanitary products, medical products, filtration materials, building materials, and the like.

[0002]

2. Description of the Related Art Heretofore, films such as garbage bags, porous films, house wraps and the like have used polyethylene resin compositions containing a large amount of calcium carbonate, which is almost the same as the resin. As the polyethylene resin, a linear low-density polyethylene is generally used.

When a polyethylene resin composition containing such a large amount of calcium carbonate is formed into a film,
Poor dispersibility of calcium carbonate, deterioration of resin, etc.
There is a problem that a large amount of precipitates called eyes are generated on a die lip or the like, and the precipitates come into contact with the film surface to generate pinholes. In addition, since it is necessary to remove these eyes periodically, there is a problem that long-time continuous operation cannot be performed. In addition, there were problems such as insufficient film strength and surface roughness of the film due to poor dispersion of calcium carbonate.

[0004] Furthermore, when producing a porous film, there is a problem that the film is torn by stretching. Also,
A conventional polyethylene resin composition using a linear low-density polyethylene has a problem that stretching at a low magnification cannot be performed due to poor stretchability. On the other hand, when stretched at a high magnification, there are problems such as a decrease in the tear strength of the porous film and poor flexibility.

[0005] Therefore, in order to overcome the occurrence of eye spots and the like,
Various attempts have been made so far. For example, it has been proposed to mix a fatty acid metal salt such as calcium stearate with a composition of linear low-density polyethylene and calcium carbonate. However, the effect of reducing fatty acids by fatty acid metal salts such as calcium stearate,
It was not satisfactory enough. Further, the demand for improvement in productivity due to the recent increase in speed cannot be followed, and further improvement has been demanded.

In recent years, further improvement in productivity has been demanded, and the speed of forming a porous film has been further increased. Along with this, a down-gauge thin film is produced while maintaining strength and flexibility. However, such a down-gauge thin film has poor concealing properties and has a problem that the contents can be seen through.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the concealing property of a thin film, and to further improve the moldability (draw resonance, neck-in, sequential stretchability), flexibility, and ventilation. Resin composition capable of producing films with excellent balance of mechanical strength (tear strength, film impact), etc., excellent in water resistance, moisture permeability, solvent resistance, chemical resistance, films satisfying the above physical properties, porous films And a method for producing a porous film. Another object of the present invention is to provide a polyethylene resin composition capable of producing a film satisfying the above-mentioned physical properties by enabling continuous operation of the film for a long period of time by reducing the occurrence of blemishes. is there.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a resin component containing an ethylene / α-olefin copolymer which satisfies specific conditions as a main component, It has been found that the above object can be achieved by using a polyethylene resin composition containing calcium carbonate and a white hiding agent, and the present invention has been completed.

That is, the polyethylene resin composition of the present invention comprises (A) 100 to 60% by weight of an ethylene (co) polymer satisfying the following requirements (a) to (d); (Co) a resin component containing 0 to 40% by weight of a polymer, and 30 to 200 parts by weight based on 100 parts by weight of the resin component.
It is characterized by containing calcium carbonate in parts by weight and 0.1 to 10 parts by weight of a white hiding agent based on 100 parts by weight of the resin component. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate (MFR) 0.1 to 50 g
/ 10 min (c) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (d) 25% of the total obtained from the integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) The difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which dissolves and the temperature T _{75 at} which 75% dissolves satisfies the relationship of the following (formula 1) (formula 1): T ₇₅ -T ₂₅ ≦ −670 × d + 644

The white hiding agent is preferably titanium white (TiO ₂ ). Further, it is preferable that the polyethylene resin composition of the present invention further contains a monovalent metal salt of a higher fatty acid, a phosphorus-based antioxidant, and a phenol-based antioxidant. In addition, (B)
The other ethylene (co) polymer is desirably a high pressure radical method low density polyethylene. The high-pressure radical method low-density polyethylene has an MZ average molecular weight of 40.
It is desirable that the number be in the range of 10,000 to 900,000.

It is desirable that the ethylene (co) polymer (A) is an ethylene (co) polymer (A1) which 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 desirable that the ethylene (co) polymer (A) is an ethylene (co) polymer (A2) which further satisfies the following requirements (g) and (h).
(G) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF), and T ₇₅ -T ₂₅ and the density d satisfy the relationship of the following (Equation 4). 4) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (h) One or two melting point peaks And the highest melting point T _ml and density d satisfy the relationship of the following (Equation 5). (Equation 5) T _ml ≧ 150 × d−17 Also, the (A2) ethylene (co) polymer is It is further desirable to satisfy 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) ethylene (co) polymer is 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. Desirably. Further, the molded article of the present invention, the polyethylene resin composition, an extrusion molding method,
It is characterized by being formed by any one of injection molding, hollow molding, compression molding and thermoforming. Also,
The molded article of the present invention may be a film or a sheet. Further, the molded article of the present invention may be a laminate having a layer containing the film or sheet and a layer made of another substrate.

Further, a garbage bag according to the present invention is characterized by comprising the above-mentioned molded body. Further, the porous film of the present invention is characterized in that the molded body is stretched 1.05 to 3 times. The material for sanitary goods of the present invention is characterized by containing the above-mentioned porous film. Moreover, the film for house wrap of the present invention is characterized by containing the above-mentioned porous film.

Further, in the method for producing a porous film according to the present invention, the polyethylene resin composition is formed into a film or sheet, and the film or sheet is formed into a film or sheet.
The film is stretched 1.05 to 3 times at a temperature of ° C. Further, in the method for producing a porous film of the present invention, the polyethylene resin composition is formed into a film or a sheet, and the film or the sheet is used in a first step.
The film is stretched 1.05 to 2.0 times at an annealing temperature of 5 to 60 ° C., and is further expanded at a temperature of 80 to 110 ° C. by 2 in the second step.
It is characterized by being stretched twice or more.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The (A) ethylene (co) polymer according to the present invention is an ethylene homopolymer or a copolymer of ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms. The α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 12 carbon atoms, and specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene , 1-decene, 1-dodecene and the like. The content of these α-olefins is usually 30 mol% or less in total, preferably 20 mol%.
It is desirable to select within the range.

The (a) density of the ethylene (co) polymer (A) according to the present invention is 0.86 to 0.97 g / cm ³ , preferably 0.89 to 0.94 g / cm ³ , more preferably It is in the range of 0.90 to 0.93 g / cm ³ . When the density is in this range, calcium carbonate is excellent in acceptability, and the decrease in strength is small even when calcium carbonate is incorporated in a large amount. When the density is less than 0.86 g / cm ³ , the tear strength and the moisture permeability are deteriorated. When the density is more than 0.97 g / cm ³ , there is a possibility that uneven stretching may occur or flexibility may be impaired.

The (A) ethylene (co) polymer (b) of the present invention has an MFR of 0.1 to 50 g / 10 min, preferably 0.3 to 30 g / 10 min, more preferably 0.5 to 20 g / min. The range is 10 minutes. If the MFR is less than 0.1 g / 10 min, the moldability is poor, and
If it exceeds 0 g / 10 min, impact resistance, mechanical strength, etc. will be reduced.

The (c) molecular weight distribution Mw / Mn of the ethylene (co) polymer (A) according to the present invention is from 1.5 to 4.5, preferably from 2.0 to 4.0, more preferably from 2.0 to 4.0. 2.
It is in the range of 3-3.5. If Mw / Mn is less than 1.5, the moldability is poor, and if it exceeds 3.5, the impact resistance is poor. Here, the molecular weight distribution Mw / Mn is calculated by determining the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and determining the ratio Mw / Mn.

(A) Ethylene (co) polymer according to the present invention
Is, for example, as shown in FIG.
Integral dissolution of elution temperature-elution amount curve by another method (TREF)
Temperature T at which 25% of the whole eluted from the curve_{twenty five}And all
The temperature T at which 75% of the body elutes ₇₅And the difference T₇₅-T_{twenty five}and
The density d satisfies the following relationship (Equation 1). (Equation 1) T₇₅-T_{twenty five}≦ −670 × d + 644 T₇₅-T_{twenty five}And the density d do not satisfy the relationship of the above (Equation 1)
In such a case, the low-temperature heat sealability is poor.

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 at a constant flow rate through this column, the column temperature was raised to 50 ° C.
The sample is sequentially eluted while heating at a constant rate of ° C./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 (co) polymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. T
According to the REF analysis, the change in the elution rate with respect to the temperature change can be continuously analyzed with a very small amount of sample, so that relatively fine peaks that cannot be detected by the fractionation method can be detected.

The (A) ethylene (co) polymer in the present invention further comprises (A1) an ethylene (co) polymer which satisfies the requirements of (e) and (f) described below, or (g) And (A2) an ethylene (co) polymer satisfying the requirements of (h).

The (E1) ODCB-soluble content X (% by weight) at 25 ° C., the density d, and the MFR of the (A1) ethylene (co) polymer according to the present invention are expressed by the following formulas (2) and (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 component having a high branching degree and a low molecular weight contained in the ethylene (co) polymer, which causes a decrease in heat resistance and stickiness of the surface of the molded product, and a problem of hygiene. It is desirable that this content be low because it causes blocking of the inside of the molded article and the like. O
The amount of DCB solubles is affected by the α-olefin content and molecular weight of the entire copolymer, ie, density and MFR. Therefore, these indices density, MFR and OD
The fact that the amount of the CB-soluble component satisfies the above relationship indicates that the uneven distribution of the α-olefin contained in the whole copolymer is small.

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

Here, as shown in FIG. 2, the ethylene (co) polymer (A1) was subjected to a continuous heating elution fractionation method (TR).
In the elution temperature-elution amount curve obtained by EF), a specific ethylene / α-olefin copolymer has a plurality of peaks substantially. On the other hand, the ethylene copolymer shown in FIG. 3 has an elution temperature determined by a continuous heating elution fractionation method (TREF).
This is an ethylene / α-olefin copolymer having substantially one peak in the elution amount curve, and corresponds to a conventional typical metallocene catalyst-based ethylene copolymer.

The (A2) ethylene (co) polymer according to the present invention is an ethylene homopolymer or ethylene and a C4 to C4 polymer.
An α-olefin copolymer having 12 carbon atoms, preferably an α-olefin having 5 to 10 carbon atoms;
-Pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. In addition, the content of these α-olefins,
Usually 30 mol% or less in total, preferably 3 to 20 mol%
It is desirable to select within the following range.

As shown in FIG. 1, the (A2) ethylene (co) polymer according to the present invention has one peak of the elution temperature-elution amount curve by (g) continuous heating elution fractionation method (TREF). Yes, T ₇₅ -T ₂₅ and the density d satisfy the relationship of the following (Equation 4). (Equation 4) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 T ₇₅ −T ₂₅ and the density d If the relationship of the above (Equation 4) is not satisfied, the heat seal strength and the heat resistance will be inferior.

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

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

As shown in FIG. 1, the ethylene copolymer (A2) has one TREF peak as shown in FIG. Formula (4) is not satisfied, and is distinguished from a conventional typical metallocene-based catalyst-based ethylene copolymer.

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

The ethylene (co) polymer (A) according to the present invention is more preferably a copolymer obtained using a catalyst comprising the following C1 to C5. The ethylene / α-olefin copolymer obtained with this catalyst is particularly excellent in mechanical strength (tear strength). C1: Compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹⁴ _-pq (where Me ¹ represents zirconium, titanium or hafnium, and R ¹ and R ² each have 1 to 24 carbon atoms) X ¹ represents a halogen atom, p and q are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively; C2: general formula Me ² R ³ _m (OR ⁴ ) a compound represented by _n X ² _zmn (wherein Me ² is an element in Groups I to III of the periodic table, R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or A hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table), z indicates a valence of Me ² , and m and n are each 0 ≦ m ≦ z, an integer satisfying the range of 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z), C3: having a conjugated double bond C4: Modified organoaluminum compound and / or boron compound containing an Al-O-Al bond obtained by reacting an organoaluminum compound with water, C5: Contacting inorganic carrier and / or particulate polymer carrier with each other A catalyst obtained by the reaction.

The details will be described below. The above catalyst component C1
In the formula of the compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹⁴ _-pq , Me ¹ represents zirconium, titanium or hafnium, and the types of these transition metals are not limited. There can be used a plurality of them, but it is particularly preferable that the copolymer contains zirconium having excellent weather resistance.
R ¹ and R ² are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 12 carbon atoms.
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, xylyl group, mesityl group, indenyl group, naphthyl group And an aralkyl group 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 ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine. p and q are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively.

Examples of the compounds represented by the general formula of the catalyst component C1 include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodichloroconium, tetrabutoxy zirconium, tetrabutoxy titanium, tetrabutoxy hafnium In particular, Zr (OR) ₄ compounds such as tetrapropoxy zirconium and tetrabutoxy zirconium are preferred, and two or more of these may be used in combination.

The general formula Me ² R ³ _m (O
In the formula of the compound represented by R ⁴ ) _n X ² _zmn , Me ² represents an element in Groups I to III of the periodic table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, and aluminum. R ³ and R ⁴ each represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms;
More preferably, it is 1 to 8, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group; an alkenyl group such as a vinyl group and an allyl group; a phenyl group, a tolyl group, and a xylyl 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 compounds represented by the general formula of the catalyst component C2 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, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, and ethyl aluminum sesqui Organic compounds such as chloride, diethylaluminum ethoxide and diethylaluminum hydride Derivatives such as iodonium compounds.

The organic cyclic compound having a conjugated double bond of the catalyst component C3 includes one ring having two or more, preferably 2 to 4, more preferably 2 to 3, conjugated double bonds. Or a cyclic hydrocarbon compound having 2 or more and having a total carbon number of 4 to 24, preferably 4 to 12; wherein the cyclic hydrocarbon compound is partially a hydrocarbon residue of 1 to 6 (typically, A cyclic hydrocarbon compound substituted with an alkyl group or an aralkyl group having 1 to 12 carbon atoms; 2 or more conjugated double bonds, 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 C3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-
Indene, 4,7-dimethylindene, butylcyclopentadiene, 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, C4: Al—O—Al obtained by the reaction between an organoaluminum compound and water
Modified organoaluminum compounds and / or boron compounds containing bonds are used. Specific examples of the modified organoaluminum compound containing an Al-O-Al bond obtained by the reaction between the organoaluminum compound and water include an aluminoxane, which is usually obtained by reacting an alkylaluminum compound with water. Modified organic aluminum oxy compounds are exemplified. The modified organoaluminum oxy compound usually has 1 to 100
And preferably containing 1 to 50 Al-O-Al bonds. The modified organoaluminum 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. As the boron compound, decaborane, dicarbamoyl nona _{borane, Ag [CB 1 1 H 12} ], Ph 3 C [C 2 B
₉ H ₁₂ ], Ph ₃ C [Co (C ₂ B ₉ H ₁₂ ) ₂ ], Ph ₃ [CB
₁₁ H ₁₂ ], Ph (CH ₂ ) ₂ NH [C ₂ B ₉ H ₁₂ ], Ph (C
H ₂ ) ₂ NH [CB ₁₁ H ₁₂ ], Ph (CH ₂ ) ₂ NH [Co (C
₂ B ₉ H ₁₁ ) ₂ ]. Preferable examples include at least one type of boron selected from N, N'-dimethylanilium tetra (pentafluorophenyl) borate, trityltetrakispentafluoroborate, ferrocenium tetrakispentafluoroborate, trispentafluoroborane and the like. Compounds.

The inorganic carrier of the catalyst component C5 and / or
Particulate polymer carriers include carbonaceous materials, metals, and metal oxides.
Object, metal chloride, metal carbonate or a mixture of these
Or a thermoplastic resin, a thermosetting resin, or the like. Nothing
Suitable metals that can be used for equipment carriers include
Examples include iron, aluminum, and nickel. concrete
Contains SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, Ti
O_Two, B_TwoO_Three, CaO, ZnO, BaO, ThO_TwoEtc.
Include mixtures thereof, and SiO 2_Two-Al_TwoO_Three, S
iO_Two-V_TwoO_Five, SiO_Two-TiO_Two, SiO _Two-V_TwoO_Five,
SiO_Two-MgO, SiO_Two−Cr_TwoO_ThreeAnd the like.
Among them, SiO_TwoAnd Al_TwoO_ThreeFrom the group consisting of
Those containing at least one selected component as a main component
preferable.

As the organic compound, any of a thermoplastic resin and a thermosetting resin can be used, and specific examples thereof include particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, Examples include polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably they are used as a pretreatment by using an organic aluminum compound or a modified organic aluminum oxy compound containing an Al—O—Al bond. Can be used as the component C5 after the contact treatment.

The ethylene (co) polymer (A) according to the present invention is produced by a gas phase method, a slurry method, a solution method or the like, and is not particularly limited, such as a one-stage polymerization method or a multi-stage polymerization method. The ethylene (co) polymer (A) according to 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 1
The content can be 0 ppm or less, preferably 5 ppm or less, and more preferably substantially not contained (ND: 2 ppm or less). By using such a halogen-free ethylene (co) polymer such as chlorine, there is no need to use a conventional halogen neutralizer, and the chemical stability and hygiene are excellent. , Medical,
A molded article suitably used in the field of sanitary articles and the like can be provided.

(B) Other ethylene series (co) according to the present invention
As the polymer, Ziegler type catalyst etc.
Examples thereof include a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms by a low pressure method and other known methods, and an ethylene (co) polymer by a high pressure radical polymerization method.

Ethylene and carbon number 3 by a high / medium / low pressure method using a Ziegler type catalyst or the like and other known methods.
And a copolymer with an α-olefin having a density of 0.1 to 0.1.
Linear low density polyethylene (hereinafter referred to as LLDPE) of 91 to 0.94 g / cm ³ , having a density of 0.86 to 0.91
g (hereinafter referred to as VLDPE) ultra low density polyethylene / cm ^3, ethylene-propylene copolymer rubber having a density of 0.86~0.91g / cm ^3, ethylene-propylene-
Includes ethylene / α-olefin copolymer rubber such as diene copolymer rubber.

The LLDPE using the Ziegler-type catalyst refers to ethylene • α- 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.

VLD using the Ziegler type catalyst
PE is an ethylene / α-olefin copolymer having a density in the range of 0.86 to 0.91 g / cm ³ , preferably 0.88 to 0.905 g / cm ³ , and LLDPE and ethylene / α-olefin. Copolymer rubber (EPR, EPD
M) is a polyethylene exhibiting intermediate properties.

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 ethylene-based (co) polymer obtained by the high-pressure radical polymerization method includes ethylene homopolymer (low-density polyethylene) obtained by the high-pressure radical polymerization method, ethylene / vinyl ester copolymer, and ethylene and α, β-unsaturated Copolymers with a carboxylic acid or a derivative thereof can be given.
The low-density polyethylene is produced by a known high-pressure radical polymerization method, and may be any of a tubular method and an autoclave method.

The above-mentioned ethylene / vinyl ester copolymer is produced by a high-pressure radical polymerization method and contains ethylene as a main component, vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearin It is a copolymer with vinyl ester monomers such as vinyl acid and vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate. A copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferred. Further, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight.

Typical copolymers of the above-mentioned copolymers of ethylene and α, β-unsaturated carboxylic acid or its derivative include ethylene / (meth) acrylic acid or its alkyl ester copolymer. These comonomers include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and acrylate-n -Butyl, methacrylic acid-n-
Butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate,
Glycidyl acrylate, glycidyl methacrylate and the like can be mentioned. Of these, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl. In particular, the content of the (meth) acrylate is in the range of 3 to 20% by weight, preferably 5 to 15% by weight.

Among the other ethylene-based (co) polymers (B), a high-pressure radical-process low-density polyethylene is most preferable because of its excellent moldability. The MZ average molecular weight of the high-pressure radical method low-density polyethylene is preferably 400,000 to 900,000. If the MZ is less than 400,000, the melt tension is low and the moldability deteriorates. Also, 9
If it exceeds 10,000, the torque of the extruder increases. here,
The MZ average molecular weight means the Z average molecular weight.

The average particle size of the calcium carbonate according to the present invention is not more than 20 μm, and in the case of a porous film, it is not more than 0.1 μm.
It is desirable that the size be selected in the range of 3 to 10 μm, preferably 0.5 to 5 μm. If the particle size is large, the mechanical strength of the film is reduced, especially in the case of a porous film, the film tends to be stretched and broken during production, and the obtained film has a large pore size and is inferior in function as a porous film. Becomes When adding calcium carbonate to the resin component, it is preferable to previously treat the surface of the filler in order to improve dispersibility. As a surface treatment agent,
Examples include higher fatty acids and metal salts thereof, or acid amides, titanate coupling agents, waxes, oils, and the like. Among these, calcium carbonate surface-treated with a higher fatty acid is preferred in terms of dispersibility.

Examples of the white hiding agent according to the present invention include anatase type titanium white (TiO ₂ ), rutile type titanium white (TiO ₂ ), zinc white (ZnO), antimony oxide, zinc sulfide, calcium silicate, and basic calcium carbonate. And the like. Among these, titanium white (TiO ₂ ), which is small and has a strong hiding power, is most preferable.

The polyethylene resin composition of the present invention comprises
(A) 100 to 60% by weight, preferably 95 to 65% by weight, of an ethylene (co) polymer and (B) 0 to 40% by weight, preferably 5 to 35% by weight of another ethylene (co) polymer. Resin component, calcium carbonate, and a white hiding agent.

The mixing ratio of (A) the ethylene (co) polymer and (B) the other ethylene (co) polymer is appropriately selected depending on the purpose, application and the like. Taking into account the tear strength, (A) the ethylene (co) polymer is selected in the range of 95 to 60% by weight, and the (B) component high pressure radical method low density polyethylene is selected in the range of 5 to 40% by weight. Is preferred.

In the porous film, in consideration of air permeability and moisture permeability, it is generally preferable that the amount of calcium carbonate added is large. However, as the amount of calcium carbonate is increased, the strength of the film tends to decrease, and moldability such as stretchability tends to decrease. Therefore, the polymer used for the film is preferably a polymer that can be filled with calcium carbonate at a high level and has a small decrease in film strength. In this respect, the resin component according to the present invention is more excellent in these properties than other polymers, which is why it is preferably used in the present invention.

In the polyethylene resin composition of the present invention, the amount of calcium carbonate is 30 to 200 parts by weight, preferably 50 to 150 parts by weight, per 100 parts by weight of the resin component.
Parts by weight, more preferably 70 to 120 parts by weight.
If the calcium carbonate content exceeds 200 parts by weight, the moldability of the film will be poor, and if it is less than 30 parts by weight, the incineration of the garbage bag and the permeability and moisture permeability of the porous film may be insufficient.

The compounding amount of the white hiding agent is 0.1 to 10 parts by weight, preferably 1 to 7 parts by weight, more preferably 1 to 5 parts by weight.
It is selected in the range of parts by weight. When the compounding amount is less than 0.1, there is a possibility that sufficient concealing property cannot be secured, and even if the compounding amount exceeds 10 parts by weight, it is difficult to further improve the effect.

It is preferable to further add a monovalent metal salt of a higher fatty acid, a phosphorus-based antioxidant and a phenol-based antioxidant to the polyethylene resin composition of the present invention.
The monovalent metal salt of the higher fatty acid, stearic acid, palmitic acid, higher fatty acids such as oleic acid, lithium,
It is a salt with monovalent metals such as sodium and potassium.
Among them, at least one selected from the group consisting of sodium stearate, potassium stearate, lithium stearate and lithium 1,2-hydroxystearate is particularly preferable because the eye is particularly excellent in preventing effect, and lithium stearate is particularly preferable. preferable.

The amount of the monovalent metal salt of the higher fatty acid is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the resin component in consideration of moldability. More preferably, it is 0.5 to 1.0 part by weight. If the amount of the monovalent metal salt of the higher fatty acid is less than 0.1 part by weight, the effect of suppressing the generation of blemishes is poor, and even if the amount exceeds 5 parts by weight, no further improvement in the effect is observed.

The polyethylene resin composition of the present invention further comprises 0.1 to 1% by weight of a phosphorus-based antioxidant,
Preferably 0.1-0.5% by weight, and phenolic antioxidant 0.1-1% by weight, preferably 0.1-0.1%.
By using 5% by weight together, continuous operation can be dramatically improved.

Examples of the phosphorus-based antioxidants include, for example, 3,
5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, bis (2,6-di-t-butyl-4-methylphenoxy) diphosphospiroundecane, bis (stearyl) diphosphospiroundecane, Cyclic netpentanetetrayl bis (nonylphenylphosphite), bis (nonylphenylphenoxy) diphosphospiroundecan, 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide, tris (2 , 4-di-t-butylphenyl) phosphite,
2,4,6-tri-t-butylphenyl-2-butyl-
2-ethyl-1,3-propanediol phosphite,
2,2'-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methyl-phenyl]
Ethyl phosphite, bis (2,4-di-t-butylphenoxy) diphosphospiroundecan, trilauryltrithiophosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite 5 -T-butylphenyl) butane, 2,2′-ethylidenebis (4,6
-Di-t-butylphenyl) fluorophosphite,
4,4'-isopropylidene diphenol alkyl (C
12-C15) phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) -di-tridecyl phosphite, diphenylisodecyl phosphite, diphenyl mono (tridecyl) phosphite, tris- ( Mono & di mixed nonylphenyl) phosphite, phenyl-bisphenol A pentaerythritol diphosphite, di (laurylthio) pentaerythritol diphosphite, tetrakis (2,6-di-t-butyl-)
4-n-octadecyloxycarbonylethyl-phenyl) -4,4'-biphenylene-diphosphonite, tetrakis [2,6-di-tert-butyl-4- (2,
4'-di-t-butylphenyloxycarbonyl) -phenyl] -4,4'-biphenylene-di-phosphonite), tricetyltrithiophosphite, di-t-butylphenyl-m-cresylphosphonite Of tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, cyclic butylethylpropanediol-2,
4,6-tri-butylphenyl phosphite, tris-
[2- (2,4,8,10-tetrabutyl-5,7-dioxa-6-phospho-dibenzo- {a, c} cyclohepten-6-yl-oxy) ethyl] amine, bis (3
Ethyl 5-di-t-butyl-4-hydroxybenzylphosphonate) calcium, 3,9-bis {2,4-bis (1-methyl-1-phenylethyl) phenoxy}-
2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane and the like.

Among them, tris (2,4-di-t-butylphenyl) phosphite and tetrakis (2,4-di-t-) are excellent in the effect of improving continuous operation.
(Butylphenyl) -4,4'-biphenylenediphosphonite and two kinds selected from bis [2,4-bis (1,1-dimethylethyl) -6-methyl-phenyl] ethyl phosphite It is particularly preferable to use them.

Examples of the phenolic antioxidant include:
2,6-di-t-butyl-4-methylphenol, tocopherol, 4-hydroxymethyl-2,6-di-t-
Butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methoxyphenol, octadecyl-3- (4'-hydroxy-
3 ', 5'-di-t-butylphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-oxamidobis [ethyl 3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4 , 4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (2-t-
Butyl-5-methylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), N, N '
-Hexamethylenebis (3,5-di-t-butyl-4-
Hydroxyhydrocinnamate), hexamethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinnamate, 1,1,3-tris (2-methyl-4-
(Hydroxy-5-t-butylphenyl) butane, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, pentaerythritol tetrakis- [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] (also known as tetrakis [methylene-3- (3 ′, 5 ′)
-Di-t-butyl-4'-hydroxyphenyl) propionate] methane), bis [3,3-bis (4'-hydroxy-3'-t-butylphenyl) butanoic acid] glycol ester, 1,4-benzene Biscarboxylic acid bis [2
-(1,1-dimethylethyl) -6-[[3- (1,1
-(Dimethylethyl) -2-hydroxy-5-methylphenyl] methyl] -4-methylphenyl] ester, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5 -Tris (4-t-
Butyl-3-hydroxy-2,6-dimethylbenzyl)
Isocyanurate, 2- [1- (2-hydroxy-
3,5-di-t-pentylphenyl) ethyl] -4,6
-Di-t-pentylphenyl acrylate, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-
(Hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis [2- {3- (3-t-butyl-4-
[Hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,4,8,10-
And tetraoxaspiro [5,5] undecane.

Among them, pentaerythritoltetrakis-
[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionate] is preferably used and trade name Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd., 3,
9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}
-1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane) is particularly preferably used.

The polyethylene resin composition of the present invention may contain, if necessary, an antistatic agent, an antioxidant, a lubricant, an antifogging agent, an organic or inorganic pigment, and an ultraviolet absorber as long as the properties of the present invention are not substantially impaired. Known additives such as a dispersant and the like can be added.

The melt tension of the polyethylene resin composition of the present invention is in the range of 1.5 to 10 g, preferably 5 to 10 g. If the melt tension is less than 1.5 g, draw resonance will occur and stretching will be uneven. When the melt tension exceeds 10 g, the torque of the extruder increases.

The molded article of the present invention is a molded article obtained by molding the polyethylene resin composition of the present invention by any one of extrusion molding, injection molding, hollow molding, compression molding and thermoforming. . As molded products, films, sheets, garbage bags made of films, porous films, house wraps,
Materials for sanitary articles and the like can be mentioned.

When the film is melt-molded in the present invention, it is preferable that the polyethylene resin composition is previously melt-kneaded. There are various methods, for example,
Melting and kneading with an open roll, a Banbury mixer, or a pressure kneader may be used. However, since these are generally batch operations and are inferior in productivity, a method using a continuous extruder is preferred. As the continuous extruder, a full-flight screw extruder may be used, but kneading may be insufficient. Therefore, it is desirable to use an extruder equipped with a kneading mechanism or a multi-screw extruder. The method for forming the film is not particularly limited. That is, a method appropriately selected from a method such as an inflation molding method using a circular die or a T-die molding method using a T die may be used.

The garbage bag of the present invention is a garbage bag formed from a film formed from the polyethylene resin composition of the present invention. The melt molding of the film is performed by a method usually used for forming a film of a thermoplastic resin. In the molding using the polyethylene resin composition of the present invention, continuous operation is possible. In addition, the formed film satisfies various physical properties, such as easy incineration, which have been conventionally required for a garbage bag, and has an advantage of not only having a good balance of those physical properties, but also having good flexibility and tear strength. Having.

The garbage bag of the present invention can be manufactured, for example, as follows. First, pellets prepared by kneading a predetermined amount of (A) an ethylene (co) polymer, (B) another ethylene (co) polymer, calcium carbonate powder, a monovalent metal salt of a higher fatty acid, etc. by an extruder are mixed. Make it. Alternatively, preferably, (A) pellets of an ethylene (co) polymer, and (A) an ethylene (co) polymer or (B) another ethylene-based (co) polymer produced by the above method, calcium carbonate,
A pellet of a masterbatch composed of a monovalent metal salt of a higher fatty acid is prepared. Next, a stabilizer or the like is added to the pellets, if necessary, and these are mixed by a mixer (Henschel mixer, V blender, ribbon mixer, tumbler mixer, etc.), and then blown by a blown film molding method or a T-die molding method. 20-150μ
A film having a thickness of m is formed. A garbage bag is manufactured by a bag making machine using the obtained film.

The thickness of the garbage bag of the present invention varies depending on the application, but usually 20 to 8 when used as a household garbage bag.
0 μm, 50-1 when used as other large garbage bags
50 μm. When the thickness is less than 20 μm, the strength is low because the thickness is too thin, the tensile strength is insufficient, and the film is easily torn.
If the thickness exceeds 0 μm, the bag becomes too hard and difficult to handle, which is not preferable.

The garbage bag of the present invention has a tensile strength of JIS K
The value in the machine direction (MD) is 250 kg / cm ² or more and the value in the transverse direction (CD) is 2
It is 50 kg / cm ² or more.

The polyethylene resin composition used in the garbage bag of the present invention may contain repellents for animals and the like, deodorants and deodorants, fragrances and the like as additives unique to the garbage bag.
Garbage bags are left outdoors with garbage in them before being collected, and may be broken by cats and birds. In order to avoid this or to prevent the odor of the contents from being emitted to the outside, the above additives are added or coated or impregnated before use. When these are added, they may be made into a masterbatch similarly to calcium carbonate, or may be added individually. When applying or impregnating, it is performed in the form of a film or a bag.

The porous film of the present invention is produced by melt-molding the polyethylene resin composition of the present invention into a film, and then stretching the film, and includes a sheet-like porous film. . The stretching method is generally broadly classified into a uniaxial stretching method and a biaxial stretching method. In the present invention, any of these methods is possible. As the uniaxial stretching method, a roll stretching method or the like is usually used. When using such a stretching method, it is preferable to suppress the necking phenomenon of the film as much as possible, and for that purpose, measures such as making the roll interval as close as possible and suppressing shrinkage in the width direction of the film due to pinch rolls or static electricity. May take. Also,
The biaxial stretching method is roughly classified into a single-stage method and a two-stage method, and any method can be used. There are various types of stretching such as a tenter type and a tubular type, but in the present invention, they can be used without any particular limitation.

The stretching is performed at a temperature of 50 ° C. to 110 ° C., preferably 60 ° C. to 105 ° C. Stretching temperature is 5
If the temperature is lower than 0 ° C., stretching unevenness occurs and a good film cannot be obtained. On the other hand, when the temperature exceeds 110 ° C., stretching can be performed well, but the obtained film has poor porosity. In general, the stretching temperature of a synthetic resin such as polyethylene is set near the melting point of the synthetic resin. For this reason, it is the current state that the stretchability is improved by adding a liquid compound, but in the present invention, stretching can be performed at a low temperature as described above, and without adding a liquid compound. There is a great feature in that a preferable porous film can be obtained.

The stretching ratio is appropriately determined based on the balance between mechanical properties required for the porous film and air permeability and moisture permeability. For applications requiring high air permeability, it is desirable to carry out at a high draw ratio of about 5 to 6 times. However, in this case, the tear strength of the film may be degraded, and in particular, a film which is apt to be longitudinally torn may be obtained when the film is uniaxially stretched. Is preferred. In the case of such a magnification, a general method causes uneven stretching, but in the present invention, the film can be easily stretched, so that a film having excellent properties can be obtained.

The most preferred stretching method is as follows: in the first step, an annealing temperature of 45 to 60 ° C. and 1.05 to 2.0.
It is desirable from the viewpoint of moisture permeability that the film is stretched to 0 times and then stretched at a temperature of 80 to 110 ° C. to a desired final magnification of 2 times or more in the second step.

The resulting porous film can be used as it is, but can be annealed to suppress post-shrinkage. The annealing temperature is preferably between the stretching temperature and the melting point of the ethylene (co) polymer (A). The moisture permeability of the porous film of the present invention is preferably 500 to 20.
000 g / m ² · 24 hr, more preferably 20
00~15000g / m ² · 24hr, further preferably in a range of 3000~10000g / m ² · 24hr. The tear strength of the porous film of the present invention is preferably 5
kgf / cm or more, more preferably 8.5 kgf / cm
That is all. Tensile modulus of the porous film of the present invention is preferably in the range 1000~2000kgf / cm ^2, more preferably of 1200~1800kgf / cm ^2.

The porous film of the present invention has a tackifier,
Antioxidants, antifoggants, organic or inorganic pigments, nucleating agents,
Known additives such as a foaming agent, a flame retardant, and a cross-linking agent can be added to the extent that the object of the present invention is not substantially impaired.

The house wrap film of the present invention is a film used on the wall, ceiling, floor, etc. of a house to prevent dew condensation in the house, and includes a house wrap sheet. Examples of the film for a house wrap of the present invention include a laminate of the porous film or the porous sheet described above and a substrate made of a breathable reinforcing material such as paper, woven fabric, or nonwoven fabric. Substrates include polyolefin-based nonwoven fabric and split-fiber nonwoven fabric (trade name: Nisseki Warif,
Nishiishi Goju Products Co., Ltd.), high-density polyethylene nonwoven fabric (trade name: Tyvek, manufactured by DuPont) and the like are preferably used.

The material for sanitary goods of the present invention is formed from a sheet containing the above porous film. In general, for example, it is formed from a breathable base material formed of an integrated body such as a nonwoven fabric such as a woven fabric and a spun bond, and a back sheet including a high water absorbing agent and the porous film. Examples of the superabsorbent include synthetic polymer-based water-absorbing polymers such as starch, cellulose, polyacrylic acid, poval, and polyoxyethylene. The material for sanitary products of the present invention is suitably used for diapers, sanitary products, and the like.

[0089]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

The physical properties were measured according to the following test methods. [Density] Based on JIS K6760. [MFR] Based on JIS K6760. [Measurement of T _ml by DSC] A sheet having a thickness of 0.2 mm was formed by hot pressing, and a sample of about 5 mg was punched out of the sheet. This sample was kept at 230 ° C. for 10 minutes and then cooled to 0 ° C. at 2 ° C./min. Then, again at 10 ° C./min.
C., and the temperature at the top of the highest temperature peak that appeared was defined as the highest peak temperature T _ml .

[Mw / Mn] GPC (150C type manufactured by Waters) was used, and ODCB at 135 ° C. was used as a solvent. The column used was GMH _HR- H (S) from Tosoh. [TREF] Keep the column at 140 ° C and inject the sample,
After the temperature was lowered to 25 ° C. at a rate of 0.1 ° C./min to deposit the polymer on glass beads, the column was heated under the following conditions, and the concentration of the polymer eluted at each temperature 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 x 12 cmL (filled with glass beads), sample concentration: 1 mg / ml

[Melt tension (MT)] The stress when the molten 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: resin temperature 190 ° C., extrusion speed 20 mm / min, winding speed 1
5 m / min. [Halogen concentration] Measured by X-ray fluorescence and measured at 10 ppm
When the above chlorine was detected, it was used 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.

[Melting Tension] After filling a cylinder with a sample at a measuring temperature of 190 ° C., the tensile stress applied to the load cell when the plunger was lowered at a low speed was measured. [Film appearance] The appearance of the film was visually observed by T-die molding, and the state was observed. ：: Uniform state △: White vertical streaks (slightly in the eyes) slightly appeared on the film. X: A state in which white vertical streaks (eye or eyes) frequently appeared on the film. [Total light transmittance] Measured using a haze system in accordance with JIS K 7105.

[OIT] OIT method: Oxygen induction time Using an apparatus (manufactured by Seiko Instruments Inc.) in which an SSC5020 disk station and a thermal analysis module DSC200 were connected, 5 mg of a sample was placed in an aluminum pan, and 100 cc / min. At a flow rate of 50 ° C./min. To raise the temperature from 30 ° C to 210 ° C. Then, after leaving at 210 ° C. for 5 minutes, the nitrogen gas was changed to oxygen gas and the gas was changed to 100 cc / min. At the start of the calorific value increase. [ΔYI] ΔYI method: (50 ° C. oven life) The difference (ΔYI: yellowness) of the yellow index (YI: yellowness) between the film at the time of molding and the standard white plate was measured at 10 cm intervals in the film direction using an SM color computer. Ten points were measured and the average value was calculated. After the film was left in an oven at 50 ° C. for 48 hours, the difference in YI was measured in the same manner, and ΔYI (yellowness) of the film before the oven and the film after the oven was measured. [Easily incinerated: flammable] In accordance with ASTM D635.

[Moisture Permeability] In accordance with JIS Z 0208 (cup method). [Tear strength] Based on ASTM D 1922-61T. [Tensile modulus] According to ASTM D882. [Molding processability] Molding processability was determined by the degree of neck-in and draw resonance of the molten resin extruded by T-die molding. ○: Appropriate △: Some draw resonance occurred ×: Inappropriate (neck-in, draw resonance occurred)

[Shrinkage Ratio] A sample having a width of 10 mm and a length of 200 mm was cut out in the M direction of the film. next,
A mark having a distance between mark lines of 100 mm was placed at the center of the sample. This sample was placed in a silicone oil bath at 85 ° C. for 30 seconds, and the distance between the marked lines after removal was measured and expressed as a shrinkage (%). [Continuous operability at the time of forming a porous film] When the film obtained by the T-die forming is subjected to a stretching treatment, the film is stretched in the longitudinal direction, and the continuous operation time until the operation is stopped (h
r).

The resins used in Examples and Comparative Examples are shown below. The (A) ethylene (co) polymer ((A1) ethylene (co) polymer and (A2) ethylene (co) polymer) according to the present invention was produced by the following method.

[(A1) Production of ethylene (co) polymer] (Preparation of solid catalyst) In a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen and tetraethoxyzirconium (Zr (OEt) ₄ ) 22 g, 75 g of indene and 88 g of methylbutylcyclopentadiene were added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C.
The reaction was performed at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration 2.5 mmol /
3200 ml) and stirred for 2 hours. Next, 2000 g of silica (manufactured by Grace, # 952, surface area: 300 m ² / g), which had been calcined at 450 ° C. for 5 hours, was added, followed by stirring at room temperature for 1 hour, followed by nitrogen blowing and drying under reduced pressure at 40 ° C. A solid catalyst (a) having good properties was obtained.

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

(Preparation of solid catalyst) Toluene 1000 purified under nitrogen was placed in a catalyst preparation device equipped with an electromagnetic induction stirrer.
ml, tetraethoxyzirconium (Zr (OEt)
₄ ) 22 g and 74 g of indene were added, 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and the mixture was reacted at the same temperature for 2 hours. 4
After cooling to 0 ° C., 3200 ml of a toluene solution of methylalumoxane (concentration: 2.5 mmol / ml) was added and 2
Stirred for hours. Next, silica (manufactured by Grace, # 952, surface area 300) previously calcined at 450 ° C. for 5 hours
m ² / g), and after stirring at room temperature for 1 hour,
Nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (b) having good fluidity.

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

[(A2) Production of ethylene (co) polymer] (Preparation of solid catalyst) In a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen and tetrabutoxyzirconium (Zr (OBu) ₄ ) 22 g, indene 40 g and methylpropylcyclopentadiene 21 g were added, 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and then the mixture was reacted at the same temperature for 2 hours. After cooling to 40 ° C,
Toluene solution of methylalumoxane (concentration 2.5mm
1 / ml) and stirred for 2 hours. Next, silica (manufactured by Grace, # 952, surface area: 300 m ² / g) 2000 previously calcined at 450 ° C. for 5 hours
After stirring for 1 hour at room temperature, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (c) having good fluidity.

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

[Production of Ethylene-Hexene-1 Copolymer (mLLDPE) Using General Metallocene Catalyst] Purified toluene was placed in a pressurized reactor equipped with a stirrer purged with nitrogen, and then 1-hexene was added. A mixed solution of (n-butylcyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) was added (Al / Zr molar ratio = 500), and then heated to 80 ° C. to prepare a metallocene catalyst. Then, ethylene was added, and while continuously polymerizing ethylene, polymerization was carried out while maintaining the total pressure at 6 kg / cm ³ , and ethylene-hexene-1 copolymer (mLL
DPE). The physical properties are shown in Table 1.

[0105]

[Table 1]

[(B) Other Ethylene (Co) polymer] High-pressure radical method low-density polyethylene (LDPE (1)) Density = 0.920 g / cm ³ , MFR = 0.5 g / 10
min, MZ = 800,000 High pressure radical method low density polyethylene (LDPE (2)) Density = 0.924 g / cm ³ , MFR = 2.0 g / 10
min, MZ = 100,000 Ethylene / 1-butene copolymer (LLDPE) with Ziegler type catalyst Density = 0.930 g / cm ³ , MFR = 2.0 g / 10
min Ethylene / 1-butene copolymer (VLDPE) with Ziegler type catalyst Density = 0.900 g / cm ³ , MFR = 1.0 g / 10
min high density polyethylene (HDPE) density = 0.951 g / cm ³ , MFR = 1.1 g / 10
min Ethylene / propylene copolymer rubber (EPR) Trade name: EP07P, manufactured by JSR Corporation

[Others] Polybutene (Wax) Trade name: Nisseki Polybutene HV-300, calcium carbonate (CaCO ₃ ) manufactured by Nippon Petrochemical Co., Ltd. Trade name: SST40 (manufactured by Dowa Calfine Co., Ltd.), average particle size: 1.1 μm rutile type titanium white (TiO ₂ ) lithium stearate (StLi) Calcium stearate (StCa) manufactured by Kosei Co., Ltd. Phenolic antioxidant manufactured by Kosei Co., Ltd. Product name: Sumilizer GA-80 (Sumitomo Chemical Co., Ltd.) )) Phosphorus antioxidant Trade name: Irgfos 168 (Tris (2,4-di-tert-butylphenyl) phosphite manufactured by Ciba Specialty Chemical Co., Ltd.)

Example 1 sLLDPE (A11), L
20 parts by weight of DPE (1), 100 parts by weight of calcium carbonate, 3.0 parts by weight of titanium white, 0.5 parts by weight of lithium stearate, 0.2 parts by weight of GA-80 and Ir
After 0.2 parts by weight of gfos 168 were uniformly mixed with a Henschel mixer for about 30 seconds, the mixture was kneaded at 190 ° C. using a 30 mmφ biaxial kneading extruder to obtain pellets of the polyethylene resin composition. The melt tension of this composition was measured. Table 2 shows the results.

Using the pellets, a film was formed and various physical properties were evaluated. The production of the porous film was performed under the following conditions and evaluated. Table 2 shows the results. (T-die molding) Equipment: T-die = 1350mm, CR (clearance) =
1 mm, extrusion amount: 80 kg / hr (stretching treatment) Molding temperature: stretching 1.5 times at the annealing temperature of 55 ° C. in the first step, stretching twice at 90 ° C. in the second step, taking-off speed: 1
8m / min

Example 2 The same procedure as in Example 1 was carried out except that the phenolic antioxidant and the phosphorus antioxidant were not added. Table 2 shows the results. The continuous operability during the production of the porous film was slightly inferior to Example 1. Example 3 sLLDPE (A11) was replaced with sLLDPE
Except having changed to (A12), it carried out similarly to Example 1. Table 2 shows the results.

Example 4 sLLDPE (A11) was replaced with s
The same operation as in Example 1 was performed except that LLDPE (A2) was used. Table 2 shows the results. Example 5 The same operation as in Example 1 was performed except that LDPE (1) was changed to LDPE (2). Table 2 shows the results. Compared to Example 1, there were difficulties in melt tension, tear strength, and moldability.

Example 6 The procedure of Example 1 was repeated, except that the amount of sLLDPE (A11) was changed to 90 parts by weight and the amount of LDPE (1) was changed to 10 parts by weight. Table 2 shows the results. [Example 7] The same operation as in Example 1 was performed except that sLLDPE (A11) was changed to mLLDPE. Table 2 shows the results
Shown in

[0113]

[Table 2]

Comparative Example 1 The procedure of Example 1 was repeated except that the resin component was changed to 60 parts by weight of LLDPE and 40 parts by weight of VLDPE, and calcium stearate was used instead of lithium stearate. Table 3 shows the results. Melt tension, film appearance, tear strength, moldability, and continuous operation during porous film production were poor.

Comparative Example 2 The procedure of Comparative Example 1 was repeated except that the resin components were changed to 80 parts by weight of LLDPE and 20 parts by weight of Wax. Table 3 shows the results. Melt tension, film appearance, moisture permeability, tear strength, moldability, and continuous operation during porous film production were poor.

Comparative Example 3 The procedure of Comparative Example 1 was repeated except that the resin components were changed to 80 parts by weight of LLDPE and 20 parts by weight of EPR. Table 3 shows the results. Melt tension, film appearance, moisture permeability, tear strength, tensile modulus, moldability, and continuous operation during porous film production were poor.

Comparative Example 4 The procedure of Comparative Example 1 was repeated except that the resin component was changed to 60 parts by weight of HDPE and 40 parts by weight of LDPE (1). Table 3 shows the results. Film appearance, tear strength and moldability were poor.

[Comparative Example 5] (A11) The same procedures as in Comparative Example 1 were carried out except that the ethylene (co) polymer was changed to 50 parts by weight and the LDPE (1) was changed to 50 parts by weight. Table 1 shows the results. Melt tension, film appearance, tear strength, and continuous operability during production of a porous film were inferior.

Comparative Example 6 The same operation as in Example 1 was performed except that lithium stearate was not added. Table 3 shows the results. The film appearance and continuous operability during production of the porous film were poor.

[Comparative Example 7] The same operation as in Example 1 was carried out except that titanium white was not added. Table 3 shows the results.
The total light transmittance was poor.

[0121]

[Table 3]

[0122]

As described above, the polyethylene resin composition of the present invention comprises (A) 100 to 60% by weight of an ethylene (co) polymer satisfying the above requirements (a) to (d) and ( B) 0-40% by weight of other ethylene (co) polymer
And 30 to 200 parts by weight of calcium carbonate per 100 parts by weight of the resin component;
Since 0.1 to 10 parts by weight of the white hiding agent is contained with respect to 00 parts by weight, the hiding power of the thin film can be improved. In addition, it has good moldability (draw resonance, neck-in, sequential stretchability), excellent flexibility, breathability, moisture permeability, solvent resistance, chemical resistance, mechanical strength (tear strength, film impact), etc. It is possible to produce a film having an excellent balance of the above.

Further, a film using the above-mentioned polyethylene resin composition has concealability, moldability, flexibility, air permeability,
It is excellent in moisture permeability, solvent resistance, chemical resistance, excellent in balance of mechanical strength and the like, and can be suitably used for garbage bags and porous films. Such porous films are used for clothing articles (golf wear, ski wear, raincoats, hats, etc.), sanitary articles (paper diapers, sanitary articles, etc.), medical supplies (filters, bandages, etc.), industrial filter agents (water treatment, etc.). It has a wide range of uses, such as for cleaning, air purification, various separators, etc., and building materials (house wrap, dew condensation prevention sheet, etc.).

When the white hiding agent is titanium white (TiO ₂ ), the hiding power of a thin film is further improved. Further, if the monovalent metal salt of a higher fatty acid, a phosphorus-based antioxidant and a phenol-based antioxidant are further added to the polyethylene resin composition of the present invention, the occurrence of blemishes during film formation is reduced. In addition, continuous operability can be further improved. In addition, (B)
If the other ethylene-based (co) polymer is a high-pressure radical method low-density polyethylene, the extrudability during film formation is excellent. When the MZ average molecular weight of the high-pressure radical method low-density polyethylene is 400,000 to 900,000, the extrudability at the time of film formation is excellent and the film has excellent mechanical strength.

When the ethylene (co) polymer (A) is an ethylene (co) polymer that further satisfies the above requirements (e) and (f), the heat resistance of the film can be improved. Hygiene and rigidity are improved. The (A) ethylene (co) polymer further comprises the above (g) and (h)
If the (A2) ethylene (co) polymer satisfies the requirement, the film has improved heat resistance, heat seal strength, and low temperature heat sealability. Further, when the (A2) ethylene (co) polymer further satisfies the above requirement (i), the processability of the film is further improved. Further, if the (A) ethylene (co) polymer is produced in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table,
The mechanical properties, heat sealing properties, heat blocking properties and heat resistance of the film are further improved.

The molded article of the present invention is obtained by molding the polyethylene resin composition by any one of extrusion molding, injection molding, hollow molding, compression molding and thermoforming. Therefore, molding processability is good, concealment,
Excellent flexibility, breathability, moisture permeability, solvent resistance, chemical resistance,
Excellent balance of mechanical strength etc. Further, since the garbage bag of the present invention is made of the molded article, the concealing property, flexibility, air permeability, moisture permeability, solvent resistance, excellent in chemical resistance, excellent in balance of mechanical strength and the like, Low heat generation during incineration,
Easy incineration.

Further, since the porous film of the present invention is obtained by stretching the molded product 1.05 to 3 times, the molding processability is good, and the concealing property, flexibility, air permeability, and moisture permeability are good. ,
Excellent resistance to solvents and chemicals, and excellent balance of mechanical strength. Further, since the material for sanitary goods of the present invention contains the porous film, the material has excellent concealing properties, flexibility, air permeability, moisture permeability, solvent resistance, chemical resistance, and excellent balance in mechanical strength and the like. Further, since the film for a house wrap of the present invention contains the porous film, it is excellent in concealing properties, flexibility, air permeability, moisture permeability, solvent resistance, chemical resistance, and excellent balance in mechanical strength and the like.

In the method for producing a porous film according to the present invention, the polyethylene resin composition is formed into a film or sheet, and the film or sheet is formed into a film or sheet.
Since it is a method of stretching 1.05 to 3 times at a temperature of ° C., it is excellent in concealing properties, moldability, flexibility, air permeability, moisture permeability, solvent resistance, chemical resistance, mechanical strength and the like. A porous film having an excellent balance can be stably obtained. Also,
In the method for producing a porous film of the present invention, the polyethylene resin composition is formed into a film or sheet, and the film or sheet is subjected to an annealing temperature of 45 to 60 ° C. in a first step at an annealing temperature of 1.05 to 2.0 times. If it is a method in which the film is stretched and further stretched twice or more at a temperature of 80 to 110 ° C. in the second step, the moisture permeability can be easily adjusted.

[Brief description of the drawings]

FIG. 1 is a graph showing an elution temperature-elution amount curve of an ethylene (co) polymer (A) or (A2) according to the present invention.

FIG. 2 is a graph showing an elution temperature-elution amount curve of the (A1) ethylene (co) polymer according to the present invention.

FIG. 3 is a graph showing an elution temperature-elution amount curve of an ethylene (co) polymer with a general metallocene catalyst.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/22 C08K 3/22 3/26 3/26 5/13 5/13 5/49 5/49 / / B29K 23:00 B29K 23:00 105: 04 105: 04 105: 16 105: 16 509: 00 509: 00 B29L 7:00 B29L 7:00 F term (reference) 4F071 AA14X AA15 AA18 AA20X AA76 AA81 AA88 AB18 AB21 AE09 AH03 AH04 4F074 AA17 AA20 AA25 AC17 AC26 CA01 CA02 CA03 CA04 CA06 CA07 DA33 4F210 AA04A AA04C AA04D AA07A AB06 AB11 AB16 AB19 AG01 AG20 AH54 AR06 QC01 QC05 QD04 QD16 QD25 QG01 BB2 EB01 BB08 BB02 FB096 FD078 FD097 GB00 GB01 GC00 GL00

Claims (18)

[Claims] (A) 100 to 60% by weight of an ethylene (co) polymer satisfying the following requirements (a) to (d) and (B) 0 to 40% by weight of another ethylene (co) polymer. And 3 parts per 100 parts by weight of the resin component.
0 to 200 parts by weight of calcium carbonate and 100 resin components
A polyethylene resin composition comprising 0.1 to 10 parts by weight of a white hiding agent based on parts by weight. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate (MFR) 0.1 to 50 g
/ 10 min (c) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (d) 25% of the total obtained from the integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) The difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which dissolves and the temperature T _{75 at} which 75% dissolves satisfies the relationship of the following (formula 1) (formula 1): T ₇₅ -T ₂₅ ≦ −670 × d + 644 2. The method according to claim 1, wherein the white hiding agent is titanium white (T
iO ₂₎ a polyethylene resin composition according to claim 1, wherein the a. 3. The polyethylene resin composition according to claim 1, further comprising a monovalent metal salt of a higher fatty acid, a phosphorus-based antioxidant and a phenol-based antioxidant. 4. The polyethylene resin composition according to claim 1, wherein the (B) other ethylene (co) polymer is a high-pressure radical method low-density polyethylene. 5. The polyethylene resin composition according to claim 4, wherein the high pressure radical method low density polyethylene has an MZ average molecular weight of 400,000 to 900,000. 6. The ethylene (co) polymer (A) further satisfies the following requirements (e) and (f) (A1):
2. An ethylene (co) polymer.
6. The polyethylene resin composition according to any one of claims 5 to 5. (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) 7. The ethylene (co) polymer (A) further satisfies the following requirements (g) and (h) (A2):
2. An ethylene (co) polymer.
6. The polyethylene resin composition according to any one of claims 5 to 5. (G) One peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF), and T ₇₅ -T ₂₅ and the density d satisfy the relationship of the following (Equation 4) (Equation 4) 4) When d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ 0 (h) One or two melting point peaks And the highest melting point T _ml and density d satisfy the relationship of the following (Equation 5) (Equation 5) T _ml ≧ 150 × d−17 8. The (A2) ethylene (co) polymer,
The polyethylene resin composition according to claim 7, further satisfying the following requirement (i). (I) Melt tension (MT) and melt flow rate (MFR) satisfy the following (Equation 6) (Equation 6) logMT ≦ −0.572 × logMFR +
0.3 9. The (A) ethylene (co) polymer produced in the presence of a catalyst containing at least an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table. The polyethylene resin composition according to any one of claims 1 to 8, wherein 10. The polyethylene resin composition according to claim 1, which is molded by any one of extrusion molding, injection molding, blow molding, compression molding and thermoforming. A molded article characterized in that: 11. The molded article according to claim 10, which is a film or a sheet. 12. The molded article according to claim 11, which is a laminate having a layer containing the film or sheet and a layer made of another substrate. 13. A garbage bag comprising the molded article according to claim 11. 14. The molded article according to claim 11, wherein
A porous film characterized by being stretched three times. 15. A material for sanitary goods, comprising the porous film according to claim 14. 16. A film for a house wrap, comprising the porous film according to claim 14. 17. (A) 100 to 60% by weight of an ethylene (co) polymer satisfying the following requirements (a) to (d) and (B) 0 to 40% by weight of another ethylene (co) polymer And 3 parts per 100 parts by weight of the resin component.
0 to 200 parts by weight of calcium carbonate and 100 resin components
A polyethylene resin composition containing 0.1 to 10 parts by weight of a white hiding agent with respect to parts by weight is formed into a film or sheet, and the film or sheet is formed at a temperature of 50 to 110 ° C. by 1.05 to 3 times. A method for producing a porous film, comprising stretching. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate (MFR) 0.1 to 50 g
/ 10 min (c) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (d) 25% of the total obtained from the integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) The difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which dissolves and the temperature T _{75 at} which 75% dissolves satisfies the relationship of the following (formula 1) (formula 1): T ₇₅ -T ₂₅ ≦ −670 × d + 644 18. (A) 100 to 60% by weight of an ethylene (co) polymer satisfying the following requirements (a) to (d) and (B) 0 to 40% by weight of another ethylene (co) polymer And 3 parts per 100 parts by weight of the resin component.
0 to 200 parts by weight of calcium carbonate and 100 resin components
A polyethylene resin composition containing 0.1 to 10 parts by weight of a white hiding agent with respect to parts by weight is formed into a film or sheet, and the film or sheet is subjected to an annealing temperature of 45 to 60 ° C. in a first step. A method for producing a porous film, wherein the film is stretched 0.05 to 2.0 times, and further stretched 2 times or more at a temperature of 80 to 110 ° C in the second step. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate (MFR) 0.1 to 50 g
/ 10 min (c) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5 (d) 25% of the total obtained from the integrated elution curve of elution temperature-elution amount curve by continuous heating elution fractionation method (TREF) The difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which dissolves and the temperature T _{75 at} which 75% dissolves satisfies the relationship of the following (formula 1) (formula 1): T ₇₅ -T ₂₅ ≦ −670 × d + 644