JP2001355172A - Spun-bond nonwoven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a spun-bond nonwoven fabric having both excellent tensile strength and fastness to friction and an improved balance between them. SOLUTION: This spun-bond nonwoven fabric comprises a propylene-based polymer having 20-200 g/10 minutes melt flow rate, <=1.8 Mz/Mw (Mz: Z-average molecular weight, Mw: weight-average molecular weight) and <=1.5×10-4 Pa-1 steady-state compliance je0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a spunbonded nonwoven fabric made of a propylene-based polymer having specific viscoelastic properties, and more particularly to a spunbonded nonwoven fabric having an excellent balance between strength and friction fastness.

[0002]

BACKGROUND OF THE INVENTION Conventional nonwoven fabrics made of polypropylene are:
It is widely used for various purposes such as surgical gowns, disposable diapers (disposable diapers), medical and hygiene materials such as sanitary products, industrial materials such as packaging materials, industrial materials such as oil absorbents, daily miscellaneous goods for garbage bags. .

[0003] Such a polypropylene nonwoven fabric is produced by forming fibers obtained by various spinning methods into a sheet and fusing or bonding the fibers. In general, melt-kneaded polypropylene is used. It is extruded from a small spinneret, cooled and drawn to obtain a filament (fiber), which is then formed into a sheet-like web, and then embossed to partially fuse the fiber to produce a filament.

[0004] Spunbonded nonwoven fabrics are widely used as a surface material for various packaging materials and articles because they have no fluff and have excellent hair removal resistance, but the strength may still be insufficient depending on the application. As a method for obtaining a high-strength nonwoven fabric, it is possible to increase the basis weight, increase the engraved area ratio of the embossing roll, or increase the embossing temperature.However, increasing the basis weight impairs the soft feel unique to the nonwoven fabric and is economical. This is not a desirable direction. Further, if the engraved area ratio of the embossing roll is increased, it becomes closer to a film, so that the softness of the nonwoven fabric is lost, which is not preferable. An effective way to increase the strength is to increase the embossing temperature.

[0005] However, the conventional spunbonded nonwoven fabric has a problem that the nonwoven fabric has insufficient friction fastness even when the embossing temperature is increased to increase the strength. Further, when the embossing temperature was further increased, the strength was suddenly reduced.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a spunbonded nonwoven fabric which has good tensile strength and frictional fastness, and is well balanced.

[0007]

According to the present invention, in order to achieve the above object, the melt flow rate (MFR) is in the range of 20 to 200 g / 10 minutes, and Mz / Mw (M
z: Z-average molecular weight, Mw: weight-average molecular weight) is 1.8 or less, and steady-state compliance J _e ⁰ is 1.5 × 1.
Provided is a spunbonded nonwoven fabric comprising a propylene polymer having 0 ^-4 Pa ^-1 or less.

According to the present invention, the melt flow rate (MFR) is in the range of 20 to 200 g / 10 minutes, and the Mz
/ Mw (Mz: Z average molecular weight, Mw: weight average molecular weight)
There 1.8 or less, and spunbonded nonwoven fabric steady state compliance J _e ⁰ is prepared by spunbonding using a propylene-based polymer is 1.5 × 10 ^-4 Pa ^-1 or less is provided.

[0009] According to the present invention, 0.1 mg / cm ² or less as a friction fastness properties ball generation amount according filament, and a tensile strength in the longitudinal direction (MD) TS [g / 25mm ]
However, the spunbonded nonwoven fabric which satisfies the following relationship with the basis weight [g / m ² ] and MFR [g / 10 min] is provided. TS ≧ weight × 100−MFR × 5.0 (1)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The spunbonded nonwoven fabric according to the present invention will be specifically described below. The spunbonded nonwoven fabric according to the present invention is made of a propylene-based polymer having specific viscoelastic properties as described later. First, the propylene-based polymer will be described.

The propylene-based polymer used in the present invention may be a propylene homopolymer, a random copolymer of propylene and another olefin, or a block copolymer.

Other olefins that may be copolymerized with propylene include α-olefins other than propylene having 2 to 20 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
Octadecene, 1-eicosene, 3-methyl-1-butene, 3-
Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, carbon number 5 ~ 20 cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5 , 8,
8a-octahydronaphthalene and other olefins such as allyl naphthalene, allyl norbornane, styrene, dimethyl styrenes, vinyl naphthalenes, allyl toluenes, allyl benzene, vinyl cyclohexane,
Examples include vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, and dienes. These may be copolymerized with propylene in combination of two or more. Further, the propylene-based polymer may contain a unit derived therefrom as a prepolymer.

The propylene polymer used in the present invention contains units derived from such other olefins as 0 units.
Those containing in an amount of from 10 to 10 mol%, preferably from 0 to 8 mol% are preferred. Among such other olefins, ethylene, 1-butene, 1-pentene and 1-hexene are preferred, and ethylene is particularly preferred.

The propylene polymer used in the present invention has a melt flow rate (MFR; measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238) of:
20 to 200 g / 10 min, preferably 30 to 200 g / 10 min
Min, more preferably 50 to 180 g / 10 min, and still more preferably 60 to 150 g / 10 min.

The propylene polymer used in the present invention has an index of Mz / Mw (Mz: Z
Average molecular weight, Mw: weight average molecular weight) is 1.8 or less;
Preferably 1.1 to 1.78, more preferably 1.2.
It is desirable to be 1.77. Further, the molecular weight distribution (Mw / Mn) is preferably from 1.5 to 3.0, and more preferably from 1.5 to 2.5. Here, Mw, Mn, and Mz can be determined by gel permeation chromatography (GPC).

[0016] The propylene-based polymer used in the present invention, in the above range Mz / Mw, the steady state compliance J _e ⁰ is 1.5 × 10 ^-4 Pa ^-1 or less, preferably 1.0 × 10 ^{- 5 to} 1.48 × 10 ^-4 Pa ^-1 , more preferably 2.0 × 10 ^{-5 to} 1.44 × 10 ^-4 Pa ^-1 is desirable.

Here, the steady state compliance J _e ^{0 will} be described. Steady state compliance J _e ^0, the measurement of '' and G .G determined by the following equation from the "loss modulus G 'storage modulus G measured by changing the reference angular frequency ω a dynamic viscoelasticity measuring apparatus A dynamic viscoelasticity measuring device for the resin,
For example, the angular frequency ω (the range of 0.1 to 500 rad / s in the present invention) is changed using a rotary rheometer, a stress rheometer, or the like while changing the measurement temperature (the range of 160 to 260 ° C. in the present invention). It is done differently.
After that, in accordance with the time-temperature conversion rule, data on the side lower than the reference temperature (220 ° C. in the present invention) is shifted to the shorter side, and data on the side higher than the reference temperature is shifted to the longer side. A shift along the axis results in a curve, called the master curve, showing the change in G ', G "over a long time range.

This curve is made into a numerical formula by numerical calculation, and
According to equations (2) and (3), at the end of the flow region where ω → 0
Zero shear viscosity η₀And elastic modulus A_GAnd ask. Sand
The value of equation (2) is a log-log plot of G ″ against ω.
And a straight line with a slope of 1
Can be determined from the section by fitting
You. Further, the value of the equation (3) is a log-log plot
Lot, and the data of the low angular frequency side of G '
Fitting a straight line and finding from the intercept
it can. From these values, the steady state command is calculated by the following equation (4).
Compliance J _e ⁰Is calculated.

[0019]

(Equation 1)

(Equation 2)

(Equation 3)

FIGS. 1 to 4 show G ′, G ″ and complex viscosity η ^* measured in the following Examples and Comparative Examples while changing the angular frequency in the temperature range of 160 to 260 ° C. , G ″ and the absolute value | η ^* | are plotted on the vertical axis, and the angular frequency is plotted on the horizontal axis, showing a master curve at a reference temperature of 220 ° C. in which the relationship between the two is graphed. These figures show a tendency that G ′ and G ″ gradually increase with an increase in the angular velocity, and conversely, | η ^* | gradually decreases.

[0021] Figure 5, Mz / Mw steady state compliance J _e ⁰ obtained from the master curve of FIGS. 1-4
FIG. In Examples of the spunbonded nonwoven fabric according to the present invention, the propylene-based polymer used has Mz / Mw (Mz: Z-average molecular weight, Mw: weight-average molecular weight) of 1.8 or less, and a steady state compliance J.
_e ⁰ is 1.5 × 10 ⁻⁴ Pa ⁻¹ or less.

[0022] steady-state compliance J _e ⁰ to produce a nonwoven fabric by spun bond method using a propylene-based polymer in the range of the tensile strength and friction fastness both good nonwoven obtained.

In the present invention, the above-mentioned propylene polymer is
MFR, Mz / Mw, if J _e ⁰ is within the range described above, but are not limited to the manufacturing method, it is desirable that those obtained in the presence of a metallocene catalyst. As the metallocene-based catalyst, those described below are particularly preferred.

That is, the metallocene catalyst is [A] a transition metal compound belonging to Groups IV to VIB of the Periodic Table, [B] a compound capable of activating this transition metal compound [A], and (B-1) ): An organoaluminum compound, (B-2): an organoaluminum oxy compound, and (B-3): at least one compound selected from compounds which react with the transition metal compound [A] to form an ion pair; Formed from

The transition metal compound (metallocene compound) [A] used in the present invention is represented by the following formula.

Embedded image

In the formula, M ¹ represents a transition metal atom of Groups 4A to 6A of the periodic table, and specifically, zirconium, titanium, hafnium, vanadium, niobium, tantalum,
Chromium, molybdenum or tungsten, preferably zirconium, titanium or hafnium.

R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other and represent a hydrocarbon group having 1 to 20 carbon atoms;
It represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom. R ¹ , R ² , R
Of the groups represented by ³ and R ⁴ , some of the groups adjacent to each other may be bonded to form a ring together with the carbon atoms to which those groups are bonded. Note that R ¹ , R ² , R ³ and R ⁴
Are displayed in two places, respectively, for example, R ¹
And R ¹ may be the same or different groups. Of the groups represented by R, those having the same suffix represent a preferred combination when connecting them to form a ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and iconosyl;
Cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; benzyl;
Arylalkyl groups such as phenylethyl and phenylpropyl; and aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, and phenanthryl.

The ring formed by combining these hydrocarbon groups includes a benzene ring, a naphthalene ring, an acenaphthene ring,
Fused rings such as indene rings, benzene rings, naphthalene rings,
Examples include a group in which a hydrogen atom on a condensed ring group such as an acenaphthene ring or an indene ring is substituted with an alkyl group such as methyl, ethyl, propyl, or butyl.

Examples of the halogenated hydrocarbon group include a halogenated hydrocarbon group in which the above hydrocarbon group is substituted with halogen. Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl,
Trihydrocarbon-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted trimethylphenyl and the like And an aryl group.

Further, as the silicon-containing group, other than the above
SiR ₃ [where R is a halogen atom, carbon number 1-10
Or an aryl group having 6 to 10 carbon atoms].

Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and an arylalkoxy group such as phenylmethoxy and phenylethoxy. Can be

Further, as the oxygen-containing group, -OSiR
_{3 wherein} R is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

Examples of the sulfur-containing group include substituents in which oxygen of the oxygen-containing compound has been replaced with sulfur. Further, as the sulfur-containing group, other than the above-mentioned -SR [where R
Is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms].

As the nitrogen-containing group, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; phenylamino, diphenylamino,
Examples thereof include an arylamino group such as ditolylamino, dinaphthylamino, and methylphenylamino, or an alkylarylamino group.

Further, as the nitrogen-containing group, other than the above-mentioned -N
R ₂ [where R is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms].

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. Further, as the phosphorus-containing group,
PR ₂ [where R is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms].

Halogen includes fluorine, chlorine, bromine, iodine and the like. Of these, a hydrocarbon group is preferable, and in particular, a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl, a benzene ring formed by combining hydrocarbon groups, and a hydrocarbon group are combined. The hydrogen atom on the formed benzene ring is preferably a group substituted with an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl.

X ¹ and X ² may be the same or different and represent a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

The hydrocarbon group includes 1 to 20 carbon atoms.
Are preferred, and specifically, R ¹ , R ² , R ³
And include the same groups as R ^4. As the halogenated hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms is preferable. Specifically, R ¹ , R ² , R ³
And include the same groups as R ^4.

As the oxygen-containing group and the halogen atom,
The same groups or atoms as those of R ¹ , R ² , R ³ and R ⁴ can be exemplified. Examples of the sulfur-containing group include R ¹ , R ² , R ³ and R ⁴
As well as methylsulfonate, trifluoromethanesulfonate, phenylsulfonate,
Benzylsulfonate, p-toluenesulfonate,
Sulfonate groups such as trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluene Examples thereof include sulfinate groups such as sulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include the same silicon-substituted alkyl group and silicon-substituted aryl group as described above. Of these, halogen atoms and C1-20
Is preferably a hydrocarbon group or a sulfonate group.

Y¹Is a hydrocarbon group, divalent halogenated carbon
Hydride group, divalent silicon-containing group, divalent germanium-containing
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR
^Five-, -P (R^Five)-, -P (O) (R ^Five)-, -BR^Five-Or
-AlR^Five-[However, R^FiveAre the same or different
Hydrogen atom, halogen atom, hydrocarbon group,
Hydrogenated hydrocarbon group and alkoxy group].

Examples of the hydrocarbon group include those having 2 to 20 carbon atoms.
Valent hydrocarbon groups are preferred. Specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexene Examples thereof include alkylene groups such as silene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

As the halogenated hydrocarbon group, one having 1 carbon atom
And a divalent halogenated hydrocarbon group having from 20 to 20 are preferable. Specific examples include a group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene.

Examples of the divalent silicon-containing group include silylene,
Methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p- Alkylsilylene groups such as chlorophenyl) silylene; alkylarylsilylene groups; arylsilylene groups; tetramethyl-1,2-disilyl, tetraphenyl-
Alkyldisilyl groups such as 1,2-disilyl; alkylaryldisilyl groups; and aryldisilyl groups.

Examples of the divalent germanium-containing group include groups in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium. Further, the divalent silicon-containing group, divalent germanium-containing group, and divalent tin-containing group include any one of silicon, germanium, and tin among the groups represented by the following [Chemical Formula 5]. Groups.

Among these, a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group and a methylphenylsilylene group is particularly preferred. Hereinafter, the formula (I)
Specific examples of the transition metal compound represented by are shown below.

Rac-dimethylsilylene-bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, r
ac-dimethylsilylene-bis (2,4-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-tert-butylcyclopentadienyl) zirconium dichloride, isopropylidene- (4-
Methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene- (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene- (4-tert-butylcyclo (Pentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene- (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene- (4-tert-butylcyclopentadiyl (Enyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene- (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene- (3-tert-butylcyclopentadienyl Enyl) (fluorenyl) zirconium dichloride, isopropylidene- (3-tert-butylcyclopentadienyl) Fluorenyl) zirconium dichloride and the like.

Further, there can also be mentioned compounds in which zirconium in the above compounds is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten.

In the present invention, the fourth compound represented by the above formula (I)
Among the group A transition metal compounds, the following general formulas (II) and (II)
It is desirable to use at least one group 4A transition metal compound selected from the group 4A transition metal compounds represented by I) or (IV).

[0052]

Embedded image

Where M^TwoIs a transition metal of Group 4A of the periodic table
Atom, specifically titanium, zirconium, etc.
Or hafnium, preferably zirconium.
You. R ¹¹May be the same or different from each other,
And represents a hydrocarbon group of Formulas 1 to 6, specifically, methyl,
Chill, n-propyl, isopropyl, n-butyl, isobutyl
, Sec-butyl, tert-butyl, n-pentyl, neopen
Alkyl groups such as tyl, n-hexyl and cyclohexyl,
Alkenyl groups such as vinyl and propenyl;
You.

Among these, a primary alkyl group having carbon bonded to the indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable.

R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ¹¹ . R
¹³ may be the same or different from each other, and represent a hydrogen atom or an aryl group having 6 to 16 carbon atoms.
Phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl,
Indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthracenyl and phenanthryl are preferred.

These aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl and ethylphenyl , Propylphenyl, biphenyl,
α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl,
C1-C20 hydrocarbon groups such as aryl groups such as acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl and biphenylyl; and may be substituted with organic silyl groups such as trimethylsilyl, triethylsilyl and triphenylsilyl. .

X ³ and X ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, and a carbon atom having 1 to 20 carbon atoms.
A hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. Specifically, the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are the same as those described above. Atoms and groups can be exemplified.
Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy. No.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing compound has been replaced by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Trimethylbenzenesulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

Of these, halogen atoms and carbon numbers 1 to
It is preferably 20 hydrocarbon groups. Y ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, —O—, -CO-, -S-, -S
_{O -, - SO 2 -,} - NR 17 -, - P (R 17) -, - P
(O) (R ¹⁷ ) —, —BR ¹⁷ — or —AlR ¹⁷ — (where R ¹⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon having 1 to 20 carbon atoms) Group)
Is shown.

Specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4 A divalent hydrocarbon group having 1 to 20 carbon atoms, such as an alkylene group such as -cyclohexylene, or an arylalkylene group such as diphenylmethylene or diphenyl-1,2-ethylene; Halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group; methylsilylene, dimethylsilylene, diethylsilylene,
Di (n-propyl) silylene, di (i-propyl) silylene,
(Cyclohexyl) silylene, methylphenylsilylene,
Alkylsilylenes such as diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene groups, tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl, etc. Divalent silicon-containing groups such as alkyldisilyl, alkylaryldisilyl, and aryldisilyl groups; and divalent germanium-containing groups in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium.

R ¹⁷ represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. Among them, Y ² is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, and is an alkylsilylene, an alkylarylsilylene or an arylsilylene. Is more preferable.

Specific examples of the transition metal compound represented by the above general formula (II) are shown below. rac-dimethylsilylene-
Bis {1- (2-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2 -Methyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (1-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-methyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-fluorophenyl) indenyl)｝ zirconium dichloride, rac- Dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p -Bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-tolyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl -Four-
(o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene- Bis {1- (2-methyl-4- (p-benzylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-trimethylsilylenephenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-phenyl-4-phenylindenyl) デ zirconium dichloride, rac-diethylsilylene-bis ｛1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-dicyclohexylsilylene-bis ｛1- ( 2-methyl-4-phenylindenyl) zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-methyl-
4-phenylindenyl)｝ zirconium dichloride, r
ac-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-
Tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium Dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Dimethylgermylene-bis ｛1- (2-methyl-4-
Phenylindenyl) zirconium dichloride, rac-
Dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethyl Silylene-
Bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis
-(2-methyl-4-phenylindenyl) zirconium chloride SO2Me, rac-dimethylsilylene-bis {1-
(2-ethyl-4-phenylindenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-
4- (2-methyl-1-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene- Screw ｛1- (2-
Ethyl-4- (2,3-dimethylphenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-Ethyl-4- (o-chlorophenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-ethyl-4- (2,3-dichlorophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (4-trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4) -(5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2- i-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (8-methyl-9-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac -Dimethylsilylene
-Bis {1- (2-s-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-pentyl-4-phenylindenyl) )｝ Zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-n-butyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
n-butyl-4- (2-methyl-1-naphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-butyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis ｛1- (2-i-butyl-4
-(2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-neopentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- ( 2-neopentyl
-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-hexyl-4
-Phenylindenyl) zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-
Methylphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium Dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biferynyl) indenyl)} zirconium dichloride, rac-methylene-bis
-(2-Ethyl-4-phenylindenyl) コ zirconium dichloride, rac-methylene-bis ｛1- (2-ethyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-
Ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis ｛1
-(2-ethyl-4- (α-naphthyl) indenyl) デ zirconium dichloride, rac-ethylene-bis ｛1- (2-n-propyl
-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1- ( 2-ethyl-4- (α-naphthyl)
Indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2-n-propyl-4-phenylindenyl)｝ zirconium dichloride and the like.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. In the present invention, a racemic Group 4A transition metal compound represented by the general formula (II) is generally used as a catalyst component, but R-type or S-type may also be used.

Such a Group 4A transition metal compound is represented by Jo
urnal of Organometallic Chem. 288 (1985) 63-67
Page, European Patent Application Publication No. 0,320,762.

Next, the Group 4A transition metal compound represented by the general formula (III) will be described.

Embedded image

Where M^TwoIs a transition metal of Group 4A of the periodic table
Atom, specifically titanium, zirconium, etc.
Or hafnium, preferably zirconium.
You. R ^{twenty one}And R^{twenty two}Are the same or different
Well, hydrogen atom, halogen atom, carbonization of 1 to 20 carbon atoms
Hydrogen group, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon
Oxygen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or
Represents a phosphorus-containing group, specifically, a halogen atom, carbon
Hydrocarbon groups of 1 to 20; halogenated hydrocarbon groups;
As the oxygen-containing group, the oxygen-containing group and the sulfur-containing group,
This is the same as that exemplified in the general formula (II).

Examples of the nitrogen-containing group include an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino. And the like. Examples of the phosphorus-containing group include dimethylphosphino, diphenylphosphino and the like.

Among them, R ²¹ is preferably a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. R ²² is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or methyl, ethyl or propyl having 1 to 3 carbon atoms.
Is preferred.

R ²³ and R ²⁴ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms, and is specifically the same as exemplified in the above formula (II). Among them, R ²³ is preferably a secondary or tertiary alkyl group.

R ²⁴ may contain a double bond or a triple bond. X ³ and X ⁴ may be the same or different from each other, and are the same as defined in the above general formula (II).

Y ² is the same as defined in the above formula (II). Specific examples of the Group 4A transition metal compound represented by the general formula (III) are shown below.

Rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-)
n-propylindenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-cyclohexylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4- Methylcyclohexylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7- Dimethyl-4-phenyldichloromethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-dimethyl Len-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium Dichloride, rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7- Dimethyl-4-i-propylindenyl) zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis} 1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2,7-dimethyl-4-ethylindenyl)｝ zirconium dichloride, rac-di (P-tolyl) silylene-
Bis {1- (2,7-dimethyl-4-i-propylindenyl)}
Zirconium dichloride, rac-di (p-chlorophenyl)
Silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl)} Zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl 4-phenylethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenyldichloromethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2,3,7-trimethyl-4-chloromethylindenyl) {zirconium dichloride, rac-diethylsilylene-bis} 1
-(2,3,7-trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (cyclohexyl) silylene-bis ｛1- (2,3,7-trimethyl-4-i-propylindenyl) )｝ Zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2,3,7-trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2,3, 7-trimethyl-4-ethylindenyl)｝ zirconium dichloride, rac-di (p-tolyl) silylene-bis ｛1- (2,3,7-trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac -Dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-) 7-methylindenyl)｝ zirconium-bis (methanesulfonato), rac- Dimethylsilylene-bis ｛1- (2-methyl-4-
i-propyl-7-methylindenyl) zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene
-Bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,6-di- i-propylindenyl) デ zirconium dichloride, rac-dimethylsilylene-bis-1- (2-methylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4-i-propyl- 7-methylindenyl)｝ titanium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4-i-propyl-7-methylindenyl)｝ hafnium dichloride and the like.

Among these, those having a branched alkyl group such as i-propyl, sec-butyl, tert-butyl group at the 4-position are particularly preferred.

In the present invention, a racemic Group 4A transition metal compound represented by the general formula (III) is generally used as a catalyst component, but R-type or S-type may also be used.

The Group 4A transition metal compound represented by the above general formula (III) can be synthesized from an indene derivative by a known method, for example, a method described in JP-A-4-268307. .

Next, the Group 4A transition metal compound represented by the general formula (IV) will be described. The Group 4A transition metal compound represented by the general formula (IV) is a compound described in EP-549900 and Canada-2084017.

Embedded image

Where M^TwoIs a transition metal of Group 4A of the periodic table
Atom, specifically titanium, zirconium, etc.
Or hafnium, preferably zirconium.
You. R ³¹May be the same or different from each other, and hydrogen
Atom, halogen atom, preferably chlorine atom or bromine
Atom, alkyl having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms
Group, a halogenated alkyl group having 1 to 10 carbon atoms, 6 carbon atoms
-10, preferably 6-8 aryl groups, -NR_Two, −
SR, -OSiR_Three, -SiR_ThreeOr -PR_TwoGroup
And R is a halogen atom, preferably a chlorine atom, having 1 carbon atom.
-10, preferably 1-3 alkyl groups or carbon number
6-10, preferably 6-8 aryl groups].

R ^{32 to} R ³⁸ may be the same as or different from each other, and represent the same atoms or groups as those of R ^21, and at least two adjacent groups represented by R ^{32 to} R ³⁸ The groups, together with the atoms to which they are attached, may form an aromatic or aliphatic ring.

X ⁵ and X ⁶ may be the same or different from each other, and represent a hydrogen atom, carbon number 1 to 10, preferably 1 to 10.
To 3 alkyl groups, 1 to 10 carbon atoms, preferably 1 to 3
An alkoxy group, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms; An arylalkyl group having 7 to 40, preferably 7 to 10 carbon atoms, 7 to 40, preferably 7 to 1 carbon atoms;
2 represents an alkylaryl group, an arylalkenyl group having 8 to 40, preferably 8 to 12 carbon atoms, an OH group or a halogen atom. Z is

[0081]

Embedded image -O -, - CO -, - S -, - SO -, - SO 2 -, -
Ge -, - Sn -, - NR 39 -, - P (R 39) -, - P
^{(O) (R 39) -} , - BR 39 - or -AlR ³⁹ - a.

However, R ³⁹ and R ⁴⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly a methyl group and 1 to 4 carbon atoms. 10 fluoroalkyl groups, preferably CF ₃ groups, C 6-10, preferably C 6-8 aryl groups, C 6-10 fluoroaryl groups, preferably pentafluorophenyl groups, C 1-10, Preferably an alkoxy group having 1 to 4 atoms, particularly a methoxy group, an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms;
An arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, and an alkylaryl group having 7 to 40 carbon atoms and 7 to 12 carbon atoms.

R ³⁹ and R ⁴⁰ may form a ring together with the atoms to which they are bonded. M ³ is,
Denotes silicon, germanium or tin, preferably silicon or germanium.

Here, the above-mentioned alkyl group is a linear or branched alkyl group, and the halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly a fluorine atom or a chlorine atom. It is.

In the compounds represented by the general formula (IV), M ² is zirconium or hafnium;
R ³¹ is the same as each other and is an alkyl group having 1 to 4 carbon atoms; R ^{32 to} R ³⁸ may be the same or different from each other and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X ⁵ and X ⁶ may be the same or different from each other, are an alkyl group having 1 to 3 carbon atoms or a halogen atom, and Z is

[0086]

Embedded image(Where M^ThreeIs silicon and R³⁹And R⁴⁰Are each other
Which may be the same or different, having 1 to 4 carbon atoms
Or an aryl group having 6 to 10 carbon atoms)
Compounds are preferred and the substituent R³²And R³⁸Is a hydrogen atom
And R³³~ R ³⁷Is an alkyl group having 1 to 4 carbon atoms or
Is more preferably a compound which is a hydrogen atom.

Further, among the compounds represented by the general formula (IV), M ² is zirconium, and R ³¹ is
R ³² and R ³⁸ may be the same or different alkyl groups having 1 to 4 carbon atoms, and R ^{33 to} R ³⁷ may be the same or different; X ⁵ and X ⁶ are each a chlorine atom, and Z is

[0088]

Embedded image (Wherein, M ³ is silicon, and R ³⁹ and R ⁴⁰ may be the same or different from each other and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms). Compounds are preferred.

In particular, among the compounds represented by the general formula (IV), M ² is zirconium, R ³¹ is a methyl group, R ^{32 to} R ³⁸ are hydrogen atoms, X ⁵ and X ⁶ are chlorine atoms, and Z is

[0090]

Embedded image (Wherein, M ³ is silicon, and R ³⁹ and R ⁴⁰ may be the same or different and are each a methyl group or a phenyl group).

Specific examples of the transition metal compound represented by the general formula (IV) are shown below. rac-dimethylsilylene-
Bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac- Diphenylsilylene-bis ｛1- (2-
Methyl-4,5-benzoindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2-methyl-α)
-Acenaphthoindenyl) zirconium dichloride, r
ac-methylphenylsilylene-bis {1- (2-methyl-α-acenaphthoindenyl)} zirconium dichloride, rac-
1,2-ethanediyl-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (4,5-benzoindenyl)} zirconium dichloride and the like.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. In the present invention, the above-mentioned Group 4A transition metal compounds can be used in combination of two or more kinds.

In the present invention, the compound [B] capable of activating the above-mentioned transition metal compound [A] (hereinafter referred to as the component [B])
(B-1): an organoaluminum compound,
(B-2): an organoaluminum oxy compound, and (B-3):
At least one compound selected from compounds that form an ion pair by reacting with the transition metal compound [A] is used.

The organoaluminum compound (B-1) used in the present invention is represented, for example, by the following general formula [V]. R ¹ _n AlX _3-n ... [V] (In the formula [V], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to
3. In the above general formula [V], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group,
Examples include n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Such an organoaluminum compound (B-1)
As, specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum,
Trialkyl aluminum such as triisobutyl aluminum, trioctyl aluminum, tri-2-ethylhexyl aluminum, alkenyl aluminum such as isoprenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, dialkyl aluminum such as diisobutyl aluminum chloride, dimethyl aluminum bromide Alkyl aluminum sesquihalides such as halide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, methyl aluminum dichloride, ethyl aluminum dichloride, and isopropyl aluminum Dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, and the like alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (B-1), a compound represented by the following general formula [VI] can also be used. R ¹ _n AlY _3-n ... [VI] (In the formula [VI], R ¹ is the same as above, and Y is -OR
₂ , -OSiR ³³ groups, -OAIR ⁴² groups, -NR ⁵² groups,
—SiR ⁶³ group or —N (R ⁷ ) AlR ⁸² group, n is 1-2, and R ² , R ³ , R ⁴ and R ⁸ are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, and the like, and R ⁶ and R ⁷ are a methyl group, an ethyl group, and the like. )

Specifically, the following compounds can be mentioned. _{^{(1) R 1 n Al (}} OR 2) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (2) R 1 n Al}} (OSiR 3 3) 3 _-n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (O
(SiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc. (3)
^{_{R 1 n Al (OAlR 4 2}} ) a compound represented by _3-n, e.g.,
_{Et 2 AlOAlEt 2, (iso-} Bu) such as _{2 AlOAl (iso-Bu) 2} , (4) R 1 n Al (NR 5 2) a compound represented by _3-n, e.g., Me ₂ AlNEt _2, Et ₂ AlNHMe, Me ₂ AlNHE
t, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) _{2
^{Etc., (5) R 1 n Al}} (SiR 6 3) a compound represented by _3-n,
For example, (6) R ¹ _n Al such as (iso-Bu) ₂ AlSiMe ₃
^{(N (R 7) AlR 8} 2) a compound represented by _3-n, e.g., Et
₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso-
Bu) ₂ etc.

Of these, the general formula R¹ _ThreeAl, R¹ _n
Al (OR^Two)_3-n, R¹ _nAl (OAlR^Four _Two) _3-nRepresented by
Compounds are preferred, and in particular, R is an isoalkyl group, and n =
2 is preferred.

These can be used in combination.
The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known benzene-soluble aluminoxane, or a benzene-insoluble organoaluminum oxy as disclosed in JP-A-2-276807. It may be a compound.

The aluminoxane as described above can be produced, for example, by the following method. (1)
Compounds containing water of adsorption or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, primary chloride
A method in which an organoaluminum compound such as trialkylaluminum is added to a suspension of a hydrocarbon medium such as cerium hydrate to cause a reaction. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

This aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing the aluminoxane include the same compounds as those described above as the organoaluminum compound (B-1). Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred. The organoaluminum compound (B-2) can be used in combination.

Solvents used in the production of aluminoxane include benzene, toluene, xylene, cumene,
Aromatic hydrocarbons such as cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane, cyclopentane,
Alicyclic hydrocarbons such as cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated compounds And hydrocarbon solvents such as bromides. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

In the benzene-insoluble organic aluminum oxy compound used in the present invention, the Al component soluble in benzene at 60 ° C. is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. And insoluble or slightly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is determined by comparing the organoaluminum oxy compound, which corresponds to 100 milligram atoms of Al, with 10
After suspending in 0 ml of benzene and mixing at 60 ° C. for 6 hours with stirring, the mixture was filtered while hot at 60 ° C. using a G-5 glass filter equipped with a jacket, and the solid part separated on the filter was removed by 60 ° C. After washing four times with 50 ml of benzene at 50 ° C., the amount of Al atoms present in the total filtrate (x
Mmol) (x%).

The compound (B-3) (hereinafter also referred to as component (B-3)) which forms an ion pair by reacting with the transition metal compound [A] used in the present invention is described in JP-A-1-5019.
No. 50, Japanese Unexamined Patent Publication No.
-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207
And Lewis acids, ionic compounds and carborane compounds described in US Pat. No. 704, US Pat.

Examples of the Lewis acid include triphenylboron,
Tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron, tris (pentafluorophenyl) _{boron, MgCl 2, Al 2 O 3} , SiO 2 -Al 2
O _{3 and the} like can be mentioned.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocarbon. Cenium tetra (pentafluorophenyl) borate and the like can be mentioned.

Examples of the carborane compound include dodecaborane, 1-carboundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundeca) borate, and tri-n-butylammonium (Trideca hydride-7-carboundeca) borate and the like.

These can be used in combination of two or more kinds. In the present invention, as the compound [B] capable of activating the transition metal compound [A], the component (B-
1), (B-2) or (B-3) can be used in combination.

The metallocene catalyst used in the present invention is
It can be prepared by mixing the above transition metal compound [A] and component [B] in an inert hydrocarbon solvent or an olefin solvent.

As the inert hydrocarbon solvent used for preparing the metallocene catalyst, for example, propane, butane,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and hexadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and cyclooctane; and aromatic hydrocarbons such as benzene, toluene and xylene And halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, petroleum fractions such as gasoline, kerosene and light oil, and mixtures thereof.

In preparing a catalyst from each of these components,
Thus, the transition metal compound [A] has about 10 ^-8-10^-1Mol /
Liter (polymerization volume), preferably 10^-7~ 5 × 10^-2Mo
It is desirable to use it at a concentration of 1 / liter.

As the component [B], (B-1) and / or (B-
When 2) is used, the atomic ratio of aluminum in the component [B] to the transition metal of the transition metal compound [A] (A
1 / transition metal), usually 10 to 10,000, preferably 2
Used in amounts of 0-5000. When the organoaluminum compound (B-1) and the organoaluminum oxy compound (B-2) are used in combination, the aluminum atom (Al
-1) and the atomic ratio (Al-1 / Al-2) of the aluminum atom (Al-2) in (B-2) is 0.02 to 3, and more preferably 0.05 to 1.
It is desirable to use an amount of 5.

When (B-3) is used as the component [B], the molar ratio of the transition metal compound [A] to the component (B-3) ([A] / (B-3)) is It is usually used in an amount of 0.01 to 10, preferably 0.1 to 5.

The above catalyst components may be mixed in a polymerization vessel, or may be mixed in advance and added to the polymerization vessel.
When mixing these components in advance, usually -50 to 150
The contact can be performed at a temperature of preferably -20 to 120C for 1 minute to 50 hours, preferably 5 minutes to 25 hours.
Further, the mixing temperature may be changed during the mixing contact.

The metallocene catalyst used in the present invention is:
A solid catalyst in which at least one of the components [A] and [B] is supported on a granular or particulate solid (carrier) may be used.

This carrier may be an inorganic carrier or an organic carrier. As the inorganic carrier, for example, Si
Porous oxides such as O ₂ and Al ₂ O ₃ are preferably used. Examples of the organic carrier include those having 2 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.
(Co) polymers formed mainly with α-olefins of No. to 14 or vinylcyclohexane, polymers or copolymers formed mainly with styrene, and the like can be used.

The metallocene catalyst used in the present invention may be used after preliminarily polymerizing an olefin with each of the above catalyst components to form a prepolymerized catalyst. As the olefin used for the prepolymerization, olefins such as propylene, ethylene, and 1-butene are used, and these can be used in combination with other olefins.

In the present invention, in forming the metallocene catalyst, other components useful for propylene polymerization, for example, water as a catalyst component can be used in addition to the above components.

The propylene polymer used in the present invention is prepared by mixing propylene and, if necessary, other olefins described above in the presence of the above-mentioned metallocene catalyst so that the above-mentioned composition ratio is finally obtained. (Co) polymerized into

The polymerization can be carried out by any of liquid phase polymerization such as suspension polymerization and solution polymerization or gas phase polymerization. In the liquid phase polymerization method, the same inert hydrocarbon solvent as used in the above-mentioned catalyst preparation can be used, and the polymerization monomer itself such as propylene can be used as the solvent.

When carrying out the polymerization by the suspension polymerization method,
It is desirable to carry out the reaction at a temperature of -50 to 100 ° C, preferably 0 to 90 ° C, and when performing the solution polymerization method, at a temperature of 0 to 250 ° C, preferably 20 to 200 ° C. When the polymerization is carried out by a gas phase polymerization method, at a temperature of 0 to 120 ° C, preferably 20 to 100 ° C, and a normal pressure to 100 kg /
cm ^2, preferably under normal pressure to 50 kg / cm ² .

The polymerization can be carried out by any of batch, semi-continuous and continuous methods. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the obtained propylene-based polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure.

The propylene-based polymer used in the present invention may contain components other than the propylene-based polymer, if necessary, as long as the object of the invention is not impaired. Such other components include, for example, conventionally known heat stabilizers, weather stabilizers, various stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, and synthetic oils. Oil, wax and the like.

For example, stabilizers to be blended as optional components include anti-aging agents such as 2,6-di-t-butyl-4-methyl-phenol (BHT) and tetrakis [methylene-3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidebis [Phenolic antioxidants such as ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, Irganox 1010 (hindered phenol antioxidant: trade name), zinc stearate, and steer Fatty acid metal salts such as calcium phosphate and calcium 1,2-hydroxystearate, polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate Can be mentioned. These can be used in combination.

Also, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, domite, calcium sulfate, potassium titanate, barium sulfate, sulfurous acid A filler such as calcium, talc, clay, mica, asbestos, calcium silicate, montmorillonite, pentonite, graphite, aluminum powder, molybdenum sulfide and the like may be contained.

The propylene polymer and other optional components are:
Mixing can be performed using a known method. For example, as described above, kneading can be performed at the time of modifying the propylene-based polymer. Further, the propylene polymer used in the present invention can be kneaded in the presence of an organic peroxide to make the MFR of the propylene polymer a desired value. The kneading of the propylene-based polymer and the organic peroxide may be performed in the presence of the above-described optional components, and the kneading of the propylene-based polymer with the organic peroxide may be followed by mixing with the optional components. You may.

Examples of such an organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, and 1,1-bis (t-butylperoxy) cyclohexane 2,2-bis (t-butyl). Peroxy ketals such as peroxy) octane, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxy peroxide, 1,1,3,3-tetramethylbutylhydro Hydroperoxides such as peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy)
Dialkyl peroxides such as hexane (trade name: perhexin 25B), 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, and diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; t-
Peroxyesters such as butylperoxyacetate, t-butylperoxybenzoate, and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane can be exemplified. Such an organic peroxide can be used usually in an amount of 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the propylene-based polymer.

Further, oleic acid amide as an optional component,
A slip agent such as erucamide or stearamide may be blended at a ratio of 0.1 to 0.5% by weight. A spunbonded nonwoven fabric obtained by blending a slip agent with a propylene-based polymer can improve friction fastness.

The spunbonded nonwoven fabric according to the present invention comprises the above-mentioned propylene-based polymer, and the MFR, Mz / Mw, and J _e ^{0 of} the propylene-based polymer forming the nonwoven fabric.
Is also within the above range.

The spunbonded nonwoven fabric according to the present invention is obtained by producing the above-mentioned propylene-based polymer or a propylene-based polymer composition to which optional components are added, if necessary, using a conventionally known spunbonding method. Can be That is, the propylene-based polymer or its composition is melted by an extruder or the like, and a filament obtained by melt-spinning by a spunbond method is formed into a sheet-like web on a collection belt, and then subjected to an entanglement treatment. Can be

In the melt spinning by the spunbond method, for example, a propylene polymer (or composition) is heated to a temperature not lower than the melting point (or softening point) and lower than the decomposition temperature, preferably 180 to
After heating to a temperature of 260 ° C. to be in a molten state, the extruded filament filament is spun from the nozzle, and then the spun filament is cooled by a cooling fluid, and the filament is tensioned by drawing air to obtain an intended filament. Fineness. Thereafter, the spun filaments are collected on a collection belt, and entangled to obtain a spunbonded nonwoven fabric. As a method of performing the entanglement treatment, for example, a method of fusing fibers by hot embossing, a method of fusing fibers by ultrasonic waves, a method of entanglement of fibers using a water jet,
There are a method of fusing fibers by hot air through and a method of entanglement of fibers by using a needle punch. Among these entanglement methods, hot embossing is preferred in that a high-strength nonwoven fabric can be obtained.

The fiber diameter of the fibers forming the spunbonded nonwoven fabric is usually about 5 to 30 μm, preferably 1 to 30 μm.
It is about 0 to 20 μm. By using the above-mentioned propylene-based polymer, even a fiber having a finer fiber than a conventional spunbonded nonwoven fabric has good spinnability and can be manufactured stably. For example, under the spinning conditions of 1,000 filaments and a filament speed of 2500 m / min, in the case of a conventional raw material resin, thread breakage occurs 20 times or more per hour, whereas the propylene-based polymer of the present invention uses When used, it can be suppressed to 10 times or less per hour.

The basis weight of the spunbonded nonwoven fabric of the present invention is as follows:
It can be appropriately selected according to the use of the nonwoven fabric, required quality, economy, and the like. Usually, it is about 5 to 100 g / m ² , preferably about 10 to 50 g / m ² , and more preferably about 12 to 30 g / m ² .

In the present invention, the obtained long fiber filament web is entangled to increase the strength of the nonwoven fabric. In order to obtain a high-strength nonwoven fabric, a hot embossing treatment is preferable for the entanglement method. The embossed area ratio is usually 5 to 35%, preferably 10 to 30%. When the embossed area ratio is in this range, the strength can be increased without impairing the soft touch inherent in the nonwoven fabric.

The embossing temperature is usually desirably from melting point -35 ° C to -5 ° C, preferably from -30 ° C to -5 ° C, more preferably from -25 ° C to -5 ° C. As long as the temperature does not decrease the strength, the strength of the nonwoven fabric tends to increase as the embossing temperature increases. In the propylene-based polymer used in the present invention, the strength does not decrease even at a temperature higher than the embossing temperature of the conventional nonwoven fabric raw material resin, so that a higher strength nonwoven fabric can be obtained.

Although the tensile strength of the nonwoven fabric depends on the embossed area ratio, if the embossed area is within the above range, the strength increases as the basis weight of the nonwoven fabric increases under the same embossing conditions, and the MFR of the raw material resin increases. It has been found that the strength decreases as the value increases. In a preferred embodiment of the spunbonded nonwoven fabric according to the present invention, the tensile strength TS [g / 25 mm] in the machine direction (MD) is the basis weight [g / m ² ] and the MFR [g / 10
Minute] and the following relationship is satisfied. TS ≧ weight × 100−MFR × 5.0 (1) Preferably, the following relationship is satisfied. TS ≧ weight × 100−MFR × 4.0 (5) More preferably, the following relationship is satisfied. TS ≧ basis weight × 100−MFR × 3.0 (6)

Another feature of the spunbonded nonwoven fabric of the present invention is that it has excellent friction fastness.
In the present invention, for example, JIS L107
As a result of performing a friction test in accordance with No. 6, the kinks of filaments were collected with a brush and expressed as the amount of generated kinks. In a preferred embodiment of the spunbonded nonwoven fabric of the present invention, the amount of generated balls of the filament is 0.1 mg / cm ² or less, preferably 0.08 mg / cm ² or less, more preferably 0.1 mg / cm ² or less.
07 mg / cm ² or less.

The spunbonded nonwoven fabric according to the present invention as described above is particularly excellent in strength and fastness to friction, and thus is preferably used as a backsheet or packaging material for disposable diapers.

[0141]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The measuring method according to the present invention will be described below. (1) Measurement of dynamic viscoelasticity (measurement of steady state compliance) A stress rheometer (Rheo
metricsScientific Dynamic Stress Rheometer SR
-5000) using a cone plate having a diameter of 2.5 mm and an angle of 0.1 rad according to the following procedure. First, mount the sample between the cone plate and the flat plate,
And the storage modulus G ′ and the loss modulus G ″ were measured while changing the angular frequency ω.
It measured similarly at 0 degreeC and 160 degreeC. The melting point of the propylene polymer sample used is about 160 ° C, but at temperatures near the melting point, the crystallization rate is slow. Can be. Next, the temperature was raised again to 200 ° C., and reproducibility of data at 200 ° C. was confirmed.
C, 240 C, and 260 C were measured in the same manner.

According to the time-temperature conversion rule, the obtained data is converted into data for a shorter time than the reference temperature (220 ° C.) and shorter for a data higher than the reference temperature (220 ° C.). G ', shifted along the axis, over a long time range
A master curve showing the change of G ″ was drawn. This curve was converted into a mathematical expression by numerical calculation, and the zero shear viscosity η ₀ and the elastic modulus A _{G at the} end of the flow region of ω → 0 were calculated by the above equations (2) and (3). That is, the zero shear viscosity η ₀
Was obtained by plotting a logarithmic plot of G ″ with respect to ω, fitting a straight line with a slope of 1 to the data on the low angular frequency side of G ″, and calculating the intercept. The elastic modulus A _G is G ′
Was plotted against ω, a straight line with a slope of 2 was fitted to the data on the low angular frequency side of G ′, and the intercept was obtained. Wherein from these values (4) were calculated steady-state compliance J _e ⁰ by equation.

(2) Evaluation of Fastness to Friction (Measurement of Amount of Balls Skewed by Filament) A nonwoven fabric sample of 40 mm × 100 mm was subjected to 25 times under a load of 500 g using a polishing paper having a grain size of # 400 (stroke length: 20mm, stroke speed: once /
Seconds) After rubbing, filament debris adhering to the surface of the nonwoven fabric and the surface of the polishing paper are collected and weighed to determine the amount of debris per unit area. (3) Tensile test (measurement of tensile strength) A tensile test piece of 25 mm x 200 mm was sampled from the nonwoven fabric so that the longitudinal direction was the flow direction of the product, and the chuck interval was 100 mm and the tensile speed was measured by a constant-speed extension type tensile tester. 1
A tensile test was performed at 00 mm / min.

(4) Molecular weight distribution (Mw / Mn), Mz /
Measurement of Mw Molecular weight distribution (Mw / Mn) and Mz / Mw were measured by Millipore
It was measured as follows using GPC-150C manufactured by
Was. The separation column is TSK GNH HT (column size).
Column: diameter 72 mm, length: 600 mm)
The temperature was 140 ° C and the mobile phase was o-dichlorobenzene
(Wako Pure Chemical Industries) and BHT (Takeda) as an antioxidant
(Chemicals) 0.025% by weight, moving speed 1.0 ml /
Min, sample concentration 0.1 wt%, sample injection volume 500 micro
Liter and a differential refractometer was used as a detector. standard
Polystyrene has a molecular weight of Mw <1000 and Mw>
4 × 10 ⁶About Tosoh Corporation, 1000 <M
w <4 × 10⁶About Pressure Chemical Co., Ltd.
Using.

[Example 1] The following physical properties obtained using a metallocene catalyst: MFR: 26 g / 10 min, molecular weight distribution (Mw / Mn): 1.8, Mz / Mw: 1.57, melting point Tm (Measurement by DSC): 148 ° C. A propylene-based polymer having a steady-state compliance J _e ⁰ : 0.89 × 10 ⁻⁴ Pa ⁻¹ was melt-kneaded by an extruder.
Spun from a 0.6 mmφ, 1141 hole spinneret at 0.5 g per minute per hole, taken up by drawing air, and dispersed.
After being deposited, it was point-fused by embossing treatment (emboss area ratio 12%) at a different embossing temperature to give a basis weight of 2
A 2 g / m ² spunbonded nonwoven fabric was produced. Table 1 shows the evaluation results of the nonwoven fabric.

Example 2 The following physical properties obtained using a metallocene catalyst: MFR: 24 g / 10 min, molecular weight distribution (Mw / Mn): 2.9, Mz / Mw: 1.77, melting point Tm (Measurement by DSC): 149 ° C. A propylene-based polymer having a steady-state compliance J _e ^{0 of} 1.44 × 10 ⁻⁴ Pa ⁻¹ was prepared in the same manner as in Example 1 by using a spunbond nonwoven fabric having a basis weight of 22 g / m ^2. Was manufactured.
Table 1 shows the evaluation results of the nonwoven fabric.

Comparative Example 1 The following physical properties produced using a solid titanium catalyst component: MFR: 34 g / 10 min, molecular weight distribution (Mw / Mn): 2.6, Mz / Mw: 2.03, Melting point Tm (measured by DSC): 157 ° C. A propylene-based polymer having a steady-state compliance J _e ^{0 of} 2.30 × 10 ⁻⁴ Pa ⁻¹ was prepared in the same manner as in Example 1 and the basis weight was 22 g / m ² . A bonded nonwoven fabric was manufactured.
Table 1 shows the evaluation results of the nonwoven fabric.

Comparative Example 2 The following physical properties produced using a solid titanium catalyst component: MFR: 55 g / 10 min, molecular weight distribution (Mw / Mn): 2.4, Mz / Mw: 1.91, Melting point Tm (measured by DSC): 157 ° C. A propylene-based polymer having a steady-state compliance J _e ^{0 of} 1.96 × 10 ⁻⁴ Pa ⁻¹ was prepared in the same manner as in Example 1 and the basis weight was 22 g / m ² . A bonded nonwoven fabric was manufactured.
Table 1 shows the evaluation results of the nonwoven fabric.

[0150]

[Table 1]

[0151]

The spunbonded nonwoven fabric of the present invention is made of a propylene-based polymer having specific viscoelastic properties.
In particular, it has an excellent balance between strength and friction fastness, and is suitable for industrial materials such as sanitary materials such as disposable diapers and packaging materials.

[Brief description of the drawings]

FIG. 1 is a master curve showing dynamic viscoelasticity measurement results of a propylene-based polymer used in manufacturing a spunbonded nonwoven fabric of the present invention in Example 1.

FIG. 2 is a master curve showing dynamic viscoelasticity measurement results of a propylene-based polymer used for manufacturing the spunbonded nonwoven fabric of the present invention in Example 2.

FIG. 3 is a master curve showing dynamic viscoelasticity measurement results of a propylene polymer used for manufacturing a spunbonded nonwoven fabric in Comparative Example 1.

FIG. 4 is a master curve showing dynamic viscoelasticity measurement results of a propylene-based polymer used for producing a spunbonded nonwoven fabric in Comparative Example 2.

Figure 5 is a plot against steady-state compliance J _e ⁰ a Mz / Mw obtained from the master curve of FIGS.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4J100 AA02Q AA03P AA04Q AA07Q AA08Q AA15Q AA16Q AA19Q AA20Q AA21Q AB00Q AP16Q AR11Q CA04 DA04 DA42 DA47 JA11 4L047 AA14 AB03 AB10 BA08 CA19 CB01 CC05 CC03 CC03

Claims (5)

[Claims] 1. Melt flow rate (MFR; ASTM)
Mz / Mw in the range of 20 to 200 g / 10 min.
(Mz: Z average molecular weight, Mw: weight average molecular weight) is 1.
8 or less and the steady state compliance J _e ⁰ is 1.5
A spunbonded nonwoven fabric comprising a propylene polymer having a density of ^10-4 Pa- ¹ or less. 2. The spunbonded nonwoven fabric according to claim 1, wherein the propylene-based polymer is obtained in the presence of a metallocene-based catalyst. 3. The spunbonded nonwoven fabric according to claim 1, wherein the propylene-based polymer is a copolymer of propylene and another α-olefin. 4. The spunbonded nonwoven fabric according to claim 1, wherein the propylene-based polymer has a molecular weight distribution (Mw / Mn) of 1.5 to 3.0. 5. A friction durability properties, 0.1 mg / cm ² or less as filaments accordance ball generation amount, and the vertical direction (M
The tensile strength TS [g / 25 mm] of D) satisfies the following relationship with the basis weight [g / m ² ] and MFR [g / 10 min]. Spunbond non-woven fabric; TS ≧ basis weight × 100-MFR × 5.0 (1)