JP4959497B2 - Non-woven - Google Patents

Description

  The present invention relates to a nonwoven fabric. Specifically, the present invention relates to a non-woven fabric made of fibers having excellent heat-fusibility and capable of heat-sealing with a polyethylene non-woven fabric.

  Traditionally, non-woven fabric made of polypropylene has been used for various purposes such as surgical clothes, disposable diapers, sanitary products and other medical and hygiene materials, industrial materials such as packaging materials, industrial materials such as oil adsorbents, and daily goods such as garbage bags. Widely used.

  Such a nonwoven fabric made of polypropylene is produced by fusing or adhering fibers obtained by various spinning methods and then fusing or adhering the fibers into a sheet. Generally, the polypropylene is melted by a melt spinning method. It is manufactured by obtaining a filament (fiber) obtained by kneading and extruding from a spinneret, and then forming it into a sheet.

  By the way, the polypropylene that forms such a polypropylene nonwoven fabric is generally manufactured using a solid titanium-based catalyst. However, since the molecular weight distribution is wide, the spinning setting is performed when melt extrusion from a spinneret as a filament. At the temperature, the flow (molten resin) amount is too much or too little, so that the spinning stability is poor, and the resin temperature that can be spun is limited to a narrow range. Moreover, the heat-sealability of the resulting nonwoven fabric was insufficient.

  In order to improve the heat sealability of this polypropylene nonwoven fabric, it is known that polypropylene containing an ethylene copolymer component may be used as the polypropylene, and the content of this ethylene component should be increased. Is causing a new problem of stickiness.

Under such circumstances, Patent Documents 1 and 2 propose a nonwoven fabric made of polypropylene having a narrow molecular weight distribution obtained using a metallocene catalyst. Patent Document 1 describes that fibers are composed of polypropylene having an ethylene structural unit, and that fibers having a sheath portion made of an ethylene polymer are preferable. There was a problem of stickiness. Moreover, in the technique of patent document 2, the surface stickiness is reduced and the nonwoven fabric with favorable heat-sealing property is obtained. However, there has been a demand for the emergence of a non-woven fabric that is more flexible and excellent in texture, excellent in strength, and excellent in heat fusion with a polyethylene film or a non-woven fabric made of polyethylene.
JP-A-11-241224 Japanese Patent No. 3969757

  An object of the present invention is to provide a non-woven fabric that is less sticky, can be thermally bonded at a low temperature, and has an excellent balance between flexibility and mechanical strength.

The nonwoven fabric of the present invention is polymerized with a metallocene catalyst, has a melt flow rate of 0.1 to 100 g / 10 min, a melting point of 100 to 155 ° C., and a portion insoluble in room temperature n-decane (D _insol ) 90 to It is composed of 60% by weight and a part soluble in room temperature n-decane (D _sol ) of 10 to 40% by weight, the D _insol satisfies the requirements (1) to (3), and the D _sol is a requirement (4) It is characterized by comprising a propylene-based random block copolymer (A) satisfying (6).
(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 13 mol%
(3) The sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene in D _insol is 0.2 mol% or less. (4) Molecular weight distribution (Mw / Mn) obtained from GPC of D _sol 1.0-3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%.

It is preferable that the nonwoven fabric of this invention is formed from the monocomponent filament which consists of the said propylene-type random block copolymer (A).
Moreover, it is also preferable that the nonwoven fabric of this invention forms at least one part surface from the composite fiber which consists of the said propylene random block copolymer (A).

  In the nonwoven fabric of the present invention formed from a composite fiber, the composite fiber includes a sheath portion made of the propylene random block copolymer (A) and a core made of a thermoplastic resin other than the copolymer (A). Preferably, the composite fiber has an eccentric core-sheath structure.

  Moreover, in the nonwoven fabric of the present invention formed from a composite fiber, the composite fiber is composed of a fiber part composed of the propylene random block copolymer (A) and a thermoplastic resin other than the copolymer (A). It is preferable to have a side-by-side structure composed of fiber portions.

In the nonwoven fabric of the present invention, the thermoplastic resin other than the copolymer (A) is preferably one or more resins selected from polyolefin resins other than the copolymer (A).
In the nonwoven fabric of the present invention formed from a composite fiber, the composite fiber includes a sheath part or a fiber part made of the propylene random block copolymer (A) and a thermoplastic resin other than the copolymer (A). It is preferable to have the core part or the fiber part made of in a range of 50:50 to 10:90 by weight ratio.

  The nonwoven fabric of the present invention is preferably partially fused.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in heat-fusibility, there is little stickiness, thermal bonding is possible at low temperature, and the nonwoven fabric excellent in the balance of a softness | flexibility and mechanical strength can be provided.

  The nonwoven fabric of the present invention formed from monocomponent filaments is resistant to repeated tensile stress due to excellent elasticity of fibers, hardly causes residual strain, has excellent mechanical strength, and is made of polyethylene film or polyethylene nonwoven fabric. Excellent heat-fusibility.

  The nonwoven fabric of the present invention formed from a composite fiber has good flexibility and excellent texture, is well balanced with strength, and is excellent in heat fusion with a polyethylene film or polyethylene nonwoven fabric. Further, when the composite fiber exhibits an eccentric core-sheath structure or a side-by-side structure, a nonwoven fabric having further excellent flexibility and bulkiness can be provided by crimping the fibers.

Hereinafter, the present invention will be specifically described.
The nonwoven fabric of this invention consists of a propylene random block copolymer (A). That is, the nonwoven fabric of the present invention may be formed from fibers (monocomponent filaments) made of a resin containing the propylene random block copolymer (A), and also includes the propylene random block copolymer (A). You may form from the fiber (bicomponent filament) which has the part which consists of resin, and the part which consists of other resin.

  The resin containing the propylene random block copolymer (A) may contain a resin component other than the propylene random block copolymer (A) as a resin component, as long as the object of the present invention is not impaired. . Moreover, conventionally well-known various additives may be contained in resin containing a propylene-type random block copolymer (A) as needed.

<Propylene Random Block Copolymer (A)>
The propylene random block copolymer (A) constituting the nonwoven fabric of the present invention is polymerized with a metallocene catalyst, has a melt flow rate of 0.1 to 100 g / 10 min, a melting point of 100 to 155 ° C., and room temperature. consists portion insoluble in n- decane (D _insol) 90 to 60 wt% and a soluble portion (D _sol) 10 to 40 wt% in room temperature n- decane, the D _insol requirements (1) - ( 3) is satisfied, and the D _sol satisfies the requirements (4) to (6). Here, the sum of D _insol and D _sol is 100% by weight.
(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 13 mol%
(3) The sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene in D _insol is 0.2 mol% or less. (4) Molecular weight distribution (Mw / Mn) obtained from GPC of D _sol 1.0-3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%.

Such a propylene random block copolymer (A) is a propylene / ethylene random copolymer which is a propylene block copolymer obtained by copolymerizing propylene and ethylene in the first polymerization step in the presence of a metallocene catalyst system. It is obtained by producing a copolymer and subsequently producing a propylene-ethylene random copolymer rubber in the second polymerization step. The propylene random block copolymer (A) has a melt flow rate of 0.1 to 100 g / 10 min, preferably 1
0-100 g / 10 min, melting point 100-155 ° C., preferably 110-148
90 to 60% by weight, preferably 90 to 60% by weight, of a portion insoluble in room temperature n-decane having a main component of the propylene-ethylene random copolymer produced in the first polymerization step (D _insol )
80% by weight and a portion soluble in room temperature n-decane (D _sol ) based on the propylene-ethylene random copolymer rubber produced in the second polymerization step (D _sol ) 10-40% by weight, preferably 10%
20% by weight. Here, the melt flow rate in the propylene random block copolymer (A), the melting point, the weight fraction of the portion insoluble in room temperature n-decane (D _insol ),
The weight fraction of the portion soluble in room temperature n-decane (D _sol ) can be appropriately changed according to the desired properties of the blow molded article to be produced.

In the propylene random block copolymer (A) constituting the nonwoven fabric of the present invention, the D _insol satisfies the requirements (1) to (3), and the D _sol satisfies the requirements (4) to (6). Fulfill.

Hereinafter, the requirements (1) to (6) included in the propylene random block copolymer (A) according to the present invention will be described in detail.
・ Requirement (1)
The molecular weight distribution (Mw / Mn) obtained from GPC (gel permeation chromatography) of a portion (D _insol ) insoluble in room temperature n-decane of the propylene random block copolymer (A) according to the present invention is 1. It is 0 to 3.5, preferably 1.5 to 3.2, and more preferably 2.0 to 3.0. As described above, the molecular weight distribution (Mw / Mn) obtained from GPC for the portion insoluble in room temperature n-decane (D _insol ) contained in the propylene random block copolymer (A) of the present invention is as described above. The narrowing is possible because a metallocene catalyst system is used as the catalyst. And when Mw / Mn is larger than 3.5, since low molecular weight components increase, bleeding out may occur and stickiness may occur.

・ Requirement (2)
The content of the skeleton derived from ethylene in the portion (D _insol ) insoluble in room temperature n-decane of the propylene random block copolymer (A) according to the present invention is 0.5 to 13 mol%, preferably 0. 0.7 to 10 mol%, more preferably 1.0 to 8 mol%. When the content of the skeleton derived from ethylene in D _insol is less than 0.5 mol%, the melting point (Tm) of the propylene random block copolymer (A) is increased, and the heat sealability may be lowered. is there. Further, when the content of the skeleton derived from ethylene in D _insol is more than 13 mol%, the melting point of the propylene random block copolymer (A) becomes low and the rigidity at high temperature decreases. May occur.

・ Requirement (3)
The sum of the 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in the portion (D _insol ) insoluble in room temperature n-decane of the propylene random block copolymer (A) of the present invention is 0. It is 2 mol% or less, preferably 0.1 mol% or less. 2,1-insertion bond amount of propylene in D _insol and 1,3-
When the sum of the amount of insertion bonds is more than 0.2 mol%, the random copolymerizability between propylene and ethylene decreases, and as a result, propylene-ethylene in a portion (D _sol ) soluble in room temperature n-decane. Since the composition distribution of the copolymer rubber is widened, the impact resistance of the nonwoven fabric may be reduced, and the resistance to tensile stress may be reduced.

・ Requirement (4)
The molecular weight distribution (Mw / Mn) determined from GPC of the portion soluble in room temperature n-decane (D _sol ) of the propylene random block copolymer (A) according to the present invention is 1.0 to 3.5, preferably Is 1.2 to 3.0, more preferably 1.5 to 2.5. As described above, the molecular weight distribution (Mw / Mn) obtained from GPC can be narrowed as described above for the portion (D _sol ) soluble in room temperature n-decane of the propylene random block copolymer (A) of the present invention. This is because a metallocene catalyst system is used as a catalyst. And when Mw / Mn is larger than 3.5, since low molecular weight propylene-ethylene random copolymer rubber increases in D _sol , impact resistance tends to be lowered, and stickiness may occur.

・ Requirement (5)
The intrinsic viscosity [η] in 135 ° C. decalin of the portion soluble in room temperature n-decane (D _sol ) of the propylene random block copolymer (A) according to the present invention is 1.5 to 4 dl / g, preferably It is more than 1.5 dl / g and 3.5 dl / g or less, more preferably 1.8 to 3.5 dl / g, most preferably 2.0 to 3.0 dl / g. When a catalyst other than the metallocene catalyst system suitably used in the present invention is used in the production of such a random block copolymer, the propylene random block copolymer having an intrinsic viscosity [η] exceeding 1.5 dl / g. It is extremely difficult to produce (A). In particular, it is almost impossible to produce a propylene random block copolymer (A) having an intrinsic viscosity [η] of 1.8 dl / g or more. In addition, when the intrinsic viscosity [η] in 135 ° C. decalin of the intrinsic viscosity D _sol is higher than 4 dl / g, when the propylene-ethylene random copolymer rubber is produced in the second polymerization step, the ultrahigh molecular weight to the high Ethylene amount A small amount of propylene-ethylene random copolymer rubber is by-produced. Since the propylene-ethylene random copolymer rubber produced as a by-product in a small amount exists in the propylene random block copolymer (A) non-uniformly, the spinnability may be deteriorated.

・ Requirement (6)
The content of the skeleton derived from ethylene in the portion soluble in room temperature n-decane (D _sol ) of the propylene random block copolymer (A) according to the present invention is 15 to 35 mol%, preferably 18
It is -30 mol%, More preferably, it is 20-25 mol%. When the content of the skeleton derived from ethylene in D _sol is lower than 15 mol%, the impact resistance of the propylene random block copolymer (A) may be lowered. Moreover, when content of the frame _| skeleton derived from ethylene in _Dsol is higher than 35 mol%, transparency may fall, spinnability may deteriorate, and the obtained nonwoven fabric may produce stickiness.

The content of the skeleton derived from ethylene in the portion soluble in room temperature n-decane (D _sol ) of the propylene random block copolymer (A) according to the present invention is usually 17 to 28 mol%, preferably When the content is in the range of 20 to 25 mol%, the impact resistance is hardly lowered.

  The propylene random block copolymer (A) according to the present invention is preferably a propylene random block copolymer comprising propylene and a small amount of ethylene in the first polymerization step ([Step 1]) in the presence of a metallocene catalyst. Propylene random block copolymer obtained by producing propylene-ethylene copolymer rubber by copolymerizing propylene with a larger amount of ethylene than the first step in the second polymerization step ([Step 2]) It is a coalescence.

  The metallocene catalyst suitably used for the production of the propylene random block copolymer (A) includes a metallocene compound, and reacting with an organometallic compound, an organoaluminum oxy compound and a metallocene compound to form an ion pair. Metallocene catalyst comprising at least one compound selected from compounds that can be further formed and, if necessary, a particulate carrier, preferably a metallocene catalyst capable of performing stereoregular polymerization such as isotactic or syndiotactic structure Can be mentioned. Among the metallocene compounds, the following crosslinkable metallocene compounds exemplified in the international application (WO01 / 27124 pamphlet) by the applicant of the present application are preferably used.

In the above general formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are It is selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and each may be the same or different. Such hydrocarbon groups include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Linear hydrocarbon groups such as nonyl group and n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1 -Methyl-1-
Branched hydrocarbon groups such as propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl; cyclopentyl, cyclohexyl Cyclic saturated hydrocarbon groups such as cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; cyclic unsaturated hydrocarbon groups such as phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group; benzyl group , A saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group such as cumyl group, 1,1-diphenylethyl group, triphenylmethyl group; methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, Examples include heteroatom-containing hydrocarbon groups such as N, N-dimethylamino group, N-phenylamino group, pyryl group, and thienyl group. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.

In the general formula [I], substituents R ^{5 to} R ¹² may be bonded to adjacent substituents to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [I], R ¹ , R ² , R ³ and R ⁴ substituted on the cyclopentadienyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. More preferably, R ³ is a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula [I], R ^{5 to} R ¹² substituted on the fluorene ring are preferably hydrocarbon groups having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. In the substituents R ^{5 to} R ¹² , adjacent substituents may be bonded to each other to form a ring.

In the general formula [I], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element of the periodic table, more preferably carbon, silicon, or germanium, and still more preferably a carbon atom. It is. R ¹³ and R ¹⁴ substituted on Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same as or different from each other, and may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. More preferably, R ¹⁴ is an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

Further, in the metallocene compound represented by the above general formula [I], a substituent selected from R ¹ , R ⁴ , R ⁵ or R ¹² and R ¹³ or R ^{14 of the} bridging part are bonded to each other to form a ring. May be.
In the general formula [I], M is preferably a Group 4 transition metal of the periodic table, more preferably Ti, Zr, or Hf. Q is selected from the same or different combinations from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy And ethers such as ethane. At least one Q is preferably a halogen atom or an alkyl group.

Such bridged metallocene compounds include diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl). ) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride , (Methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrobenzofluorenyl) zirconium dichloride, [3- (1 ', 1', 4 ', 4 ', 7', 7 ', 10', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a- Tetrahydropentalene)] zirconium Such as chloride (the following formula [II] see) are preferably mentioned.

In the metallocene catalyst used in the present invention, an ion pair reacts with an organometallic compound, an organoaluminum oxy compound, and a transition metal compound used together with the Group 4 transition metal compound represented by the general formula [I]. At least one compound selected from the compounds that form, and a particulate carrier that is used as necessary. These are described in the above-mentioned publication (WO01 / 27124 pamphlet) or JP-A-11-315109 by the present applicant. The compounds disclosed in the publication can be used without limitation.

  The propylene random block copolymer (A) according to the present invention uses a polymerization apparatus in which two or more reaction apparatuses are connected in series, and continuously performs the following two steps ([Step 1] and [Step 2]). It is obtained by carrying out automatically.

[Step 1] copolymerizes propylene and ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 1], the propylene-based random copolymer produced in [Step 1] is made the main component of D _{insol by reducing} the amount of ethylene fed relative to propylene.

In [Step 2], propylene and ethylene are copolymerized at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 2], the propylene-ethylene copolymer rubber produced in [Step 2] becomes the main component of D _sol by increasing the amount of ethylene fed to propylene than in [Step 1]. To do.

By doing in this way, requirements (1)-(3) concerning D _insol are adjusted by adjusting polymerization conditions in [Step 1], and requirements (4)-(6) concerning D _sol are [Step 2]. It can be satisfied by adjusting the polymerization conditions.

Further, the physical properties that the propylene random block copolymer (A) according to the present invention should satisfy are often determined by the chemical structure of the metallocene catalyst used. Specifically, requirement (1) molecular weight distribution (Mw / Mn) obtained from GPC of D _insol , requirement (3) of 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in D _insol Sum, requirement (4) Molecular weight distribution (Mw / Mn) determined from GPC of D _sol and melting point of propylene random block copolymer (A) are mainly used in [Step 1] and [Step 2]. By appropriately selecting the metallocene catalyst to be obtained, it can be adjusted to meet the requirements of the present invention. The metallocene catalyst preferably used in the present invention is as described above.

Further, the content of the skeleton derived from ethylene in the requirement (2) D _insol can be adjusted by the amount of ethylene feed in [Step 1]. Requirement (5) The intrinsic viscosity [η] of D _sol in 135 ° C. decalin can be adjusted by the feed amount of a molecular weight regulator such as hydrogen in [Step 2]. Requirement (6) The content of the skeleton derived from ethylene in D _sol can be adjusted by the amount of ethylene feed in [Step 2]. Furthermore, by adjusting the amount ratio of the polymer produced in [Step 1] and [Step 2], the composition ratio of D _insol and D _sol and the melt flow of the propylene random block copolymer (A) It is possible to adjust the rate appropriately.

  In addition, the propylene random block copolymer (A) according to the present invention includes the propylene-ethylene random copolymer produced in [Step 1] of the method and the propylene produced in [Step 2] of the method. -Ethylene random copolymer rubbers may be produced individually in the presence of a metallocene compound-containing catalyst and then blended using these physical means.

<Other ingredients>
The resin containing the propylene-based block random copolymer (A), which is a molding material for the fibers constituting the nonwoven fabric of the present invention, may be added to other resins, various additives, etc. as long as the purpose of the present invention is not impaired. Can be contained.

  Examples of other resins include propylene resins (P) other than the propylene random block copolymer (A). As the propylene resin (P), a propylene homopolymer, propylene / ethylene copolymer, propylene / α-olefin copolymer, propylene / ethylene, which is different from the propylene random block copolymer (A) of the present invention. A block copolymer, a propylene / α-olefin block copolymer, a syndiotactic propylene polymer, an atactic propylene polymer and the like can be mentioned. Here, as the α-olefin, an α-olefin having 4 to 20 carbon atoms can be used.

Additives include nucleating agents, antioxidants, hydrochloric acid absorbers, heat stabilizers, light stabilizers, UV absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, medium Examples thereof include a flow improver such as a softener, a foaming agent, a plasticizer, an anti-bubble agent, a crosslinking agent and a peroxide, and a weld strength improving agent.

  The resin containing the propylene-based random block copolymer (A) used as the molding material of the fiber forming the nonwoven fabric of the present invention is not particularly limited, but each component constituting the resin may be a Henschel mixer, a Banbury, for example. After blending with a mixer such as a mixer or a tumbler mixer, the mixture can be formed into pellets using a single- or twin-screw extruder, and the obtained pellets can be used for spinning.

  The nonwoven fabric of the present invention is formed of a monocomponent filament made of the propylene random block copolymer (A) or a composite fiber having at least a part of the surface made of the propylene random block copolymer (A). .

<Monocomponent filament>
The monocomponent filament according to the present invention is a fiber having a substantially homogeneous composition formed from a resin containing the propylene random block copolymer (A). The resin containing the propylene random block copolymer (A) may be a resin composed only of the propylene random block copolymer (A), and other resins together with the propylene random block copolymer (A). It may be a resin containing resin components, additives, and the like.

The monocomponent filament according to the present invention is formed by fiberizing a resin containing the propylene-based random block copolymer (A) by a conventionally known spinning method.
Examples of the spinning method include a dry spinning method, a wet spinning method, a melt spinning method, and an emulsion spinning method. Among these, the melt spinning method is particularly preferable.

In this melt spinning method, the resin containing the propylene random block copolymer (A) is heated to a temperature not lower than the melting point (or softening point) and lower than the decomposition temperature, preferably 180 to 260 ° C., to be in a molten state. Then, a filament (fiber) can be obtained by extruding from the nozzle and winding the extruded resin while cooling. In spinning, various types of nozzles can be used, but a nozzle having an L / D value of about 10 / 0.5 to 60/3 mm is preferable. Further, the extrusion speed of the resin from the nozzle is usually 0.01 to 100 m / min, preferably 0.05.
About 10 m / min. The take-up speed of the monocomponent filament extruded at the above speed is usually 10 to 10000 m / min, preferably 100 to 5000 m / min.
It is. Therefore, the monocomponent filament extruded from the nozzle is usually drawn at the time of drawing, and the draw ratio at this time is usually 10 to 10,000, preferably 100 to 5,000.

  Monocomponent filaments obtained by spinning in this way can be subjected to treatments in post-treatment steps for the purpose of removing impurities, tension stretching, heat treatment, refining, dyeing and the like.

<Composite fiber>
The composite fiber forming the nonwoven fabric of the present invention has at least a part of the surface made of the propylene random block copolymer (A). That is, at least a part of the surface of the conjugate fiber according to the present invention is composed of a resin containing the propylene random block copolymer (A).

The composite fiber forming the nonwoven fabric of the present invention has a portion composed of a resin containing the propylene random block copolymer (A) on at least one surface.
The composite fiber according to the present invention may be a composite fiber having a portion composed of two or more kinds of resins each containing a propylene random block copolymer (A) having different properties, and three or more kinds. The composite fiber which has a part each comprised from these resin may be sufficient. Preferably, the composite fiber according to the present invention has a portion composed of a resin containing the propylene random block copolymer (A) and a portion composed of a thermoplastic resin other than the copolymer (A). A fiber (bicomponent filament) composed of two composition parts is desirable.

  The composite fiber according to the present invention is preferably such that at least a part of the fiber surface is made of a resin containing the propylene random block copolymer (A). As such a composite fiber, a core-sheath type comprising a sheath part made of a resin containing the propylene random block copolymer (A) and a core part made of a thermoplastic resin other than the copolymer (A). A fiber part made of a resin containing a structure or a propylene-based random block copolymer (A) and a fiber part made of a thermoplastic resin other than the copolymer (A) are in a parallel state. Those having a side-by-side structure are more preferable. When the composite fiber has a core-sheath structure, it may be a concentric type or an eccentric type.

  A composite fiber having a core-sheath structure or a side-by-side structure can be manufactured by a normal composite melt spinning method, and can be preferably manufactured by a spunbond method having excellent productivity. For example, a resin containing a propylene random block copolymer (A) and a thermoplastic resin other than the copolymer (A) are separately melted with an extruder or the like, and each melt is formed into a desired core-sheath structure. Alternatively, spinning can be performed by discharging from a spinneret having a composite spinning nozzle configured to discharge by forming a side-by-side structure.

Examples of the thermoplastic resin other than the copolymer (A) constituting such a composite fiber include, for example, polyolefin resins other than the copolymer (A), polyester resins such as polystyrene resin and polyethylene terephthalate, and nylon. Polyamide resin, ABS resin, polyvinyl chloride resin, and the like can be used, and one or more of these can be used. Polyolefin resins other than copolymer (A) are preferred, and polypropylenes other than copolymer (A) are preferred. Of these, a polyethylene resin and a polyethylene resin are more preferable, and among these, a polypropylene resin other than the copolymer (A) is particularly preferable.

Polypropylene resins other than the copolymer (A) that preferably constitutes the composite fiber include propylene homopolymer or propylene as a main component, and ethylene, 1-butene, 1-pentene, 1-hexene, 1 -Copolymers with α-olefins such as octene and 4-methyl-1-pentene. These homopolymers or copolymers can be used alone or in combination of two or more. Among these, it is a random copolymer of propylene and a small amount of ethylene in that the spinnability is good, the productivity is excellent, and the nonwoven fabric having good flexibility is obtained, and contains a structural unit derived from ethylene The amount is preferably 0.5 to 5 mol%. In the present invention, good spinnability means that yarn breakage does not occur during ejection from a spinning nozzle and drawing, and filament fusion does not occur. The polypropylene resin preferably has an MFR of 20 to 100 g / 10 min from the viewpoint of particularly excellent balance between spinnability and fiber strength, and particularly preferably 30 to 80 g / 10 min. In the present invention, the MFR of the polypropylene resin is measured at 230 ° C. under a load of 2.16 kg based on ASTM D1238.

  Further, this polypropylene resin preferably has a ratio Mw / Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) of 2 to 4, in terms of good spinnability and particularly excellent fiber strength. 3 or less are more preferable. In the present invention, Mw / Mn is measured by GPC (gel permeation chromatography).

In the composite fiber according to the present invention, a part (a) composed of a resin containing a propylene random block copolymer (A) and a part (b) composed of a resin other than the copolymer (A) The weight ratio of (a) to (b) ((a) :( b)) is desirably in the range of 95: 5 to 5:95, preferably 50:50 to 10:90.

<Nonwoven fabric>
The nonwoven fabric of the present invention can be produced by forming the above-described monocomponent filament or composite fiber into a sheet shape. The above-mentioned monocomponent filament or composite fiber is formed into a sheet by a conventionally known method such as a spunbond method, a melt blown method, a card machine method, etc., and a non-woven fabric is formed.

  The nonwoven fabric of the present invention may be formed from monocomponent filaments or composite fibers that are long fibers, or may be formed from monocomponent filaments or composite fibers that are short fibers.

  For example, a nonwoven fabric for oil-absorbing cloth (oil mat) can be formed by forming short fiber-shaped monocomponent filaments or composite fibers into a sheet shape with a spinning card machine. In this case, a random web formed by scattering and dropping short fiber polypropylene by an air flow may be joined (dry method), and short fiber monocomponent filaments or composite fibers may be joined with water or an adhesive. It may be dispersed in a paper machine and wet with a paper machine (wet method). In the nonwoven fabric of the present invention, monocomponent filaments or composite fibers are made of the propylene-based random block copolymer (A) so that they have excellent heat-fusibility, so that the fibers are bonded together by partially heat-sealing. It is preferable to use a non-woven fabric. The method for heat fusion is not particularly limited, but a method for heat embossing using an embossing roll is preferred.

  Also, long-fiber monocomponent filaments or composite fibers are spun by discharging from a spinneret having a spinning nozzle, cooled by a cooling fluid, and further, tension is applied to the long fibers by drawing air to obtain a predetermined fineness, which is then captured as it is. After being collected on the collecting belt and deposited to a predetermined thickness, the nonwoven fabric can be formed by a method of entanglement treatment.

  Examples of the entanglement method include a method of heat embossing using an embossing roll, a method of fusing with ultrasonic waves, a method of entanglement of fibers using a water jet, a method using hot air through, a needle punch, etc. Various methods can be used as appropriate. Among these, a method in which heat embossing is performed using an embossing roll and partially heat-sealing (thermocompression bonding) is particularly preferable in that a nonwoven fabric excellent in friction fastness can be obtained. The ratio (embossed area ratio) in the non-woven fabric of the heat-sealed portion can be determined as appropriate according to the application, and usually the range of 5 to 40% is excellent in the balance of flexibility, air permeability and friction fastness. It is preferable at the point from which a nonwoven fabric is obtained.

In the present invention, a monocomponent filament or composite fiber may be melt-spun and simultaneously a web may be formed and fused.
The nonwoven fabric according to the present invention is not particularly limited, but the basis weight is about 10 to 100 g / m ^2, preferably 15 to 50 g / m ² .

When the nonwoven fabric of the present invention is a composite fiber having an eccentric core-sheath structure, or a composite fiber having a side-by-side structure, a process of partially heat-sealing by embossing or the like or other heating process In the above, it is preferable that the composite fiber in the nonwoven fabric is crimped. In a composite fiber having an eccentric core-sheath structure or a composite fiber having a side-by-side structure, adjacent resin components having different properties may exhibit crimps due to heating due to different heat shrinkage rates. . It is preferable that the nonwoven fabric of the present invention is formed from crimped conjugate fibers because it is excellent in bulkiness and flexibility, excellent in fluff resistance, and good in tensile strength.

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

In addition, the measuring method of the physical property in an Example and a comparative example is as follows.
・ MFR (melt flow rate)
MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg).

Melting point (Tm)
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). The endothermic peak in the third step measured here was defined as the melting point (Tm).

(Measurement condition)
First step: Increase the temperature to 240 ° C at 10 ° C / min and hold for 10 min.
Second step: Decrease the temperature to 60 ° C at 10 ° C / min.

Third step: Increase the temperature to 240 ° C at 10 ° C / min.
・ Room-temperature n-decane soluble part (D _sol )
200 ml of n-decane was added to 5 g of a sample of the final product (ie, the propylene random block polymer according to the present invention) and dissolved by heating at 145 ° C. for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble part: D _insol ) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane (precipitate (A)). The precipitate (A) and acetone were separated by filtration, and the precipitate was dried. Even when the filtrate side was concentrated to dryness, no residue was observed.

The amount of n -decane soluble part was determined by the following formula.
n-decane soluble part amount (wt%) = [precipitate (A) weight / sample weight] × 100
Mw / Mn measurement [weight average molecular weight (Mw), number average molecular weight (Mn)]
Measurement was performed as follows using GPC-150C Plus manufactured by Waters. The separation columns are TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) Co., Ltd.) and 0.025% by weight of BHT (Wako Pure Chemical Industries, Ltd.) as an antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1% by weight, and the sample injection amount was 500 micron. A differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

・ Content of skeleton derived from ethylene
To measure the skeleton concentration derived from ethylene in D _insol and D _sol , 20-30 mg of sample was dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, and then carbon nuclear magnetism. Resonance analysis ( ¹³ C-NMR) was performed. Propylene, ethylene, and α-olefin were quantitatively determined from the dyad chain distribution. For example, in the case of propylene-ethylene copolymer,

Was obtained by the following calculation formulas (Eq-1) and (Eq-2).

・ Intrinsic viscosity [η]
Measurement was performed at 135 ° C. using a decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. Repeat this dilution operation two more times,
The value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (ηsp / C) (C → 0).
・ Measurement of 2,1-insertion bond and 1,3-insertion bond
^{Using 13} C-NMR, the amount of 2,1-insertion bond and the amount of 1,3-insertion bond of propylene were measured according to the method described in JP-A-7-152212.

・ Semi-crystallization time (T _1/2 )
Measurement was performed using a differential scanning calorimeter (DSC, manufactured by Seiko Instruments Inc.).
(Measurement condition)
First step: The temperature is raised to 220 ° C at 10 ° C / min and held for 3 min.

Second step: The temperature is lowered to 110 ° C at 60 ° C / min.
-Crimp number It measured based on JISL1015 regarding a filament.

Further, the number of crimps after being held at 80 ° C. for 1 minute in an air oven was also measured in accordance with JIS L1015.
・ Porosity <Evaluation of bulkiness>
The basis weight of the nonwoven fabric was W [g / m ² ], the thickness of the nonwoven fabric was L [μm], and the raw material density was d [g / cm ³ ].

Porosity [vol%] = {(L− (W / d)) / L} × 100
However, the thickness of the non-woven fabric is such that a load of 20 g / cm ² is put on 10 non-woven fabrics and 1
It is a value obtained by dividing the thickness measured after standing for 0 second by 10. The raw material density is a density (according to ASTM D1505) of a molded product obtained by press-molding a nonwoven fabric at 200 to 230 ° C.

・ KOSHI value <Evaluation of flexibility>
Using a KES-FB system manufactured by Kato Tech Co., Ltd., measurements for each test of tension, shear, compression, surface friction, and bending were performed under knit high sensitivity conditions as measurement conditions. The measurement result was measured under knit underwear (summer) conditions to obtain a KOSHI value. A KOSHI value indicates that the smaller the value, the better the flexibility.

・ FUKURAMI value <Evaluation of bulkiness>
Using a KES-FB system manufactured by Kato Tech Co., Ltd., measurements for each test of tension, shear, compression, surface friction, and bending were performed under knit high sensitivity conditions as measurement conditions. The measurement result was measured under knit underwear (summer) conditions to obtain a FUKURAMI value. The larger the value of the FUKURAMI value, the greater the thickness.

-Tensile elongation The tensile test was performed under the conditions of the width of the nonwoven fabric test piece 25 mm, the distance between chucks 100 mm, and the tensile speed 100 mm / min, and the elongation percentage of the test piece at the maximum tensile load was defined as the tensile elongation (%).

・ Fuzzing (Brush test) <Evaluation of wear resistance>
In accordance with JIS L1076, three non-woven test specimens of 25 cm in the flow direction (MD) of the non-woven fabric and 20 cm in the transverse direction (CD) perpendicular to the non-woven fabric are collected and attached to the sample holder of the brush and sponge type tester. It was pressed against the felt instead of the sponge and rubbed at a speed of 58 min ^-1 (rpm) for 5 minutes. Evaluation was performed by visual determination of the sample after friction, and the determination result was expressed as a score according to the following criteria. Larger values indicate less fuzz.
5: No fuzz,
4: Almost no lint,
3: Some fuzz is seen,
2: Fluffy,
1: The fuzz is severely broken.

-Heat-sealing strength Ten sheets of 10 cm long x 5 cm wide non-woven fabric samples were cut out with the flow direction as vertical, stacked on top of each other, and heat-sealed by a hot plate heat sealing machine.

At this time, the upper seal bar was 5 mm wide, and the lower seal bar was 25 mm wide and 2 mm silicon rubber was pasted. The sealing conditions were a sealing temperature of 125 ° C. at the upper stage, 120 ° C. at the lower stage, a sealing pressure of 2 kg / cm ² , and a sealing time of 1.0 second.

The heat-sealed sample was subjected to a tensile test with a tensile tester at a gauge length of 100 mm and a tensile speed of 300 mm / min to evaluate the heat seal strength.
[Production Example 1]
(1) Production of solid catalyst support 300 g of SiO ₂ was sampled in a 1-liter branch flask and 800 ml of toluene.
Into a slurry.

The slurry was then transferred to a 5 liter four-necked flask and 260 ml of toluene was added.
2830 ml of methylaluminoxane (hereinafter MAO) -toluene solution (Albemarle 10 wt% solution) was introduced into the solution, and the mixture was stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the replacement rate reached 95%.
(2) Production of solid catalyst component (support of metal catalyst component on carrier)
Diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-di-t) synthesized according to the description of WO2004 / 08775 in a 4-liter flask having a volume of 5 liters in a glove box -Butylfluorenyl) zirconium dichloride (M1) was weighed 2.0 g. Take the flask out of the glove box, 0.46 liters of toluene and (1)
Then, 1.4 liters of the MAO / SiO ₂ / toluene slurry prepared in (1) was added under nitrogen and stirred for 30 minutes to carry.

The obtained diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% in n-heptane. Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.
(3) Production of prepolymerized catalyst 202 g of the solid catalyst component prepared in the above (2), 109 ml of triethylaluminum, and 100 liters of heptane were introduced into an autoclave equipped with a stirrer having an internal volume of 200 liters and kept at an internal temperature of 15 to 20 ° C. 2020 g of ethylene was introduced and reacted with stirring for 180 minutes.

After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 2 g / liter. This prepolymerized catalyst contained 10 g of polyethylene per 1 g of the solid catalyst component.
(4) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, the catalyst slurry produced in (3) is used as a solid catalyst component, 3.6 g / hour, triethylaluminum 2 .2 g / hour was continuously fed, and polymerization was performed in a full liquid state in which no gas phase was present in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization reactor, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-1). The resulting propylene random block copolymer (A-1) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-1) are shown in Table 1. In Table 1, a propylene random block copolymer or the like is represented as a propylene copolymer.

[Production Example 2]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum (2.2 g / hour) was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerization reactor. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization reactor, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.1 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 54 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-2). The resulting propylene random block copolymer (A-2) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-2) are shown in Table 1.

[Production Example 3]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum was continuously supplied at 2.2 g / hour, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization reactor, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.1 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-3). The resulting propylene random block copolymer (A-3) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-3) are shown in Table 1.

[Production Example 4]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum (2.2 g / hour) was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerization reactor. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase portion was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase portion was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 63 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-4). The resulting propylene random block copolymer (A-4) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-4) are shown in Table 1.

[Production Example 5]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 2.6 g / hour as a solid catalyst component. 1.6 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization reactor, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 3.7 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.3 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase portion was 3.7 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.3 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase portion was 3.7 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.3 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-5). The resulting propylene random block copolymer (A-5) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-5) are shown in Table 1.

[Production Example 6]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum (2.2 g / hour) was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerization reactor. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization reactor, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.1 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 48 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-6). The resulting propylene random block copolymer (A-6) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-6) are shown in Table 1.

[Production Example 7]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 2.7 g / hour as a solid catalyst component. 1.6 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization reactor, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at a rate of 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.2 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-7). The resulting propylene random block copolymer (A-7) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-7) are shown in Table 1.

[Production Example 8]
(1) Preparation of solid titanium catalyst component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Subsequently, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.

After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry, and a part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.
(2) Preparation of prepolymerization catalyst 56 g of transition metal catalyst component, 8.0 g of triethylaluminum, and 80 liters of heptane were introduced into an autoclave with a stirrer having an internal volume of 200 liters, and the internal temperature was kept at 5 ° C. and 560 g of propylene was inserted for 60 minutes. The reaction was carried out with stirring. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted by adding heptane so that the transition metal catalyst component concentration was 0.7 g / liter. This prepolymerized catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.
(3) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, 30 kg / hour of propylene, 0.4 kg / hour of ethylene, 300 Nliter / hour of hydrogen, 0.4 g / hour of catalyst slurry as a solid catalyst component, triethylaluminum 2 0.7 g / hour and 1.8 g / hour of dicyclopentyldimethoxysilane were continuously fed, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the annular reactor was 65 ° C., and the pressure was 3.6 MPa / G. The catalyst in this reaction is a ZN catalyst.

The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 100 liters, and further polymerization was carried out. Propylene was supplied to the polymerization vessel at 15 kg / hour, ethylene was supplied at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 15.0 mol%. Polymerization temperature 63 ° C, pressure 3.4
Polymerization was performed at MPa / G.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 liters, and the slurry was gasified and subjected to gas-solid separation. After that, a polypropylene homopolymer powder was sent to a 480 liter gas phase polymerization vessel, and ethylene / Propylene block copolymerization was performed. Propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.30 (molar ratio), hydrogen / (ethylene + propylene) = 0.068 (molar ratio). Was fed continuously. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.2 MPa / G to obtain a propylene random block copolymer (A-8).

The resulting propylene random block copolymer (A-8) was vacuum dried at 80 ° C.
The properties of the resulting propylene random block copolymer (A-8) are shown in Table 1.
[Production Example 9]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerizer having an internal volume of 58 liters, propylene is 57 kg / hour, hydrogen is 2.5 Nliter / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component at 5.0 g / hour. For 2.3 hours, 2.3 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 2.6 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization reactor, propylene was supplied at 50 kg / hr, ethylene was supplied so that the ethylene concentration in the gas phase was 1.4 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 11 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.4 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.4 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-ethylene random copolymer (R-1). The resulting propylene-ethylene random copolymer (R-1) was vacuum dried at 80 ° C. The properties of the resulting propylene-ethylene random copolymer (R-1) are shown in Table 1.

[Production Example 10]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerizer having an internal volume of 58 liters, propylene is 57 kg / hour, hydrogen is 2.5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 4.9 g / For 2.3 hours, 2.3 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 2.7 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization vessel, propylene was supplied at 50 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 3.9 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.28 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 11 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 3.9 mol%, and hydrogen was supplied at 0.28 mol% in the gas phase part. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.5 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-ethylene random copolymer (R-2). The resulting propylene-ethylene random copolymer (R-2) was vacuum dried at 80 ° C. The properties of the resulting propylene-ethylene random copolymer (R-2) are shown in Table 1.

[Production Example 11]
(1) Preparation of solid titanium catalyst component 952 g of anhydrous magnesium chloride, 4420 ml of n-decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, heated to 130 ° C. and stirred for 1 hour to dissolve phthalic anhydride.

  The homogeneous solution thus obtained was cooled to 23 ° C., and then 750 ml of this homogeneous solvent was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and this temperature was maintained and stirred for 2 hours. Continued.

Next, the solid part was collected by hot filtration, and the solid part was suspended again in 2750 ml of titanium tetrachloride, and then heated again at a temperature of 110 ° C. for 2 hours.
After the heating, the solid part was again collected by hot filtration and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.

The solid titanium catalyst component prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition.
The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.
(2) Preparation of prepolymerization catalyst 56 g of transition metal catalyst component, 8.0 g of triethylaluminum, and 80 liters of heptane were introduced into an autoclave with a stirrer having an internal volume of 200 liters, and 560 g of propylene was introduced at an internal temperature of 5 ° C. for 60 minutes. The reaction was carried out with stirring. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice.

The obtained prepolymerization catalyst was resuspended in purified heptane and adjusted by adding heptane so that the transition metal catalyst component concentration was 0.7 g / liter. This polymerization catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.
(3) Main polymerization In a vessel polymerization vessel with an internal volume of 100 liters, 1.1 g / hour of catalyst slurry as a solid catalyst component, 4.5 g / hour of triethylaluminum, and 12.5 g / hour of cyclohexylmethyldimethoxysilane were continuously used. Then, propylene was supplied at 110 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 0.8 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.65 mol%. Polymerization was performed at a polymerization temperature of 65 ° C. and a pressure of 2.7 MPa / G. The catalyst in this reaction is a ZN catalyst.

The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization apparatus, propylene is 18 kg / hour, ethylene is ethylene concentration in the gas phase part is 3.4 mol%, 1-butene is in the gas phase part is 1-butene concentration is 2.7 mol%, and hydrogen is in the gas phase part. Was supplied so that the hydrogen concentration was 1.8 mol%. Polymerization temperature 65 ° C, pressure 2.5 MPa
Polymerization was carried out at / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random copolymer (r-1). The resulting propylene random copolymer (r-1) was vacuum dried at 80 ° C. The properties of the resulting propylene random copolymer (r-1) are shown in Table 1.

In the following examples and comparative examples, Irgnox3114 [Ciba Geigy Co., Ltd.] is used as a phenolic antioxidant for the propylene random block copolymer and propylene random copolymer obtained in each of the above production examples. 0.05 parts by weight of Irgfos168 [Ciba Geigy Co., Ltd.] as a phosphorus-based antioxidant, 0.05 parts by weight of calcium stearate as a hydrochloric acid absorbent, and melt kneaded, and Perhexa 25B [Explosive Akzo Were used for degrading with MFR adjusted to 60 g / 10 min.

In this example, MFR adjustment was carried out by degra decomposition. However, even if MFR was adjusted by polymerization, the molecular weight distribution of propylene-based copolymer based on metallocene catalyst was sufficiently narrow so that molecular weight characteristics were not greatly affected. The physical properties of the obtained nonwoven fabric are not greatly affected. Therefore, there is no problem even if a high MFR propylene copolymer obtained by direct polymerization is used.

[Example 1]
(Nonwoven fabric with monocomponent filament)
The propylene random block copolymer (A-1) obtained in Production Example 1 was melt-kneaded as described above, and the MFR-adjusted resin was melt-kneaded at 230 ° C. with an extruder, and a spinning nozzle (pore diameter: 0.6mmφ, number of holes: 1093hole <320mm × 120mm, staggered arrangement>), extruded at a discharge rate of 0.5g / min / hole, and melt stretched with air soccer while applying cooling air (18 ° C) The collected continuous filament of 2.5 denier is collected on the collecting belt directly to form a web. The web was heat-bonded with an embossing roll and a flat roll having an embossed area ratio of 10% under the conditions of a linear pressure of 50 N / mm and a temperature of 120 ° C. to obtain a nonwoven fabric having a basis weight of 25 g / m ² . Table 2 shows the characteristics of the obtained nonwoven fabric. In Table 2, a propylene random block copolymer or the like is represented as a propylene copolymer.

[Example 2]
(Nonwoven fabric with monocomponent filament)
The propylene random block copolymer (A-5) obtained in Production Example 5 was melt-kneaded as described above, and the MFR-adjusted resin was melt-kneaded at 230 ° C. with an extruder, and a spinning nozzle (pore size: 0.6mmφ, number of holes: 1093hole <320mm × 120mm, staggered arrangement>), extruded at a discharge rate of 0.5g / min / hole, and melt stretched with air soccer while applying cooling air (18 ° C) The collected continuous filament of 2.5 denier is collected on the collecting belt directly to form a web. The web was thermocompression bonded with an embossing roll and a flat roll having an embossed area ratio of 10% under the conditions of a linear pressure of 50 N / mm and a temperature of 105 ° C. to obtain a nonwoven fabric having a basis weight of 25 g / m ² . Table 2 shows the characteristics of the obtained nonwoven fabric.

[Example 3]
(Nonwoven fabric with concentric composite fiber)
The propylene random block copolymer (A-1) obtained in Production Example 1 was melt-kneaded as described above, and MFR-adjusted resin and homopolypropylene (S119 [prime polymer] Tm = 159 ° C., MFR = 63 g / 10 min) with an extruder at 230 ° C., respectively, with the propylene random block copolymer (A-1) as the sheath and S119 as the core (sheath / core = 3/7) (Weight ratio)), a composite fiber spinning nozzle (hole diameter: 0.6 mmφ, concentric type, number of holes: 1093 holes <320 mm × 120 mm, staggered arrangement>), extruded at a discharge rate of 0.5 g / min / hole, A continuous bicomponent filament having a fineness of 2.5 denier obtained by melting and drawing with air soccer while applying cooling air (18 ° C.) is directly collected on a collection belt to form a web. The web was heat-pressed with an embossing roll and a flat roll having an embossed area ratio of 10% under conditions of a linear pressure of 50 N / mm and a temperature of 120 ° C. to obtain a composite fiber nonwoven fabric having a basis weight of 25 g / m ² . Table 2 shows the characteristics of the obtained nonwoven fabric.

[Example 4]
(Nonwoven fabric with concentric composite fiber)
The propylene random block copolymer (A-5) obtained in Production Example 5 was melt-kneaded as described above, MFR-adjusted resin, and homopolypropylene (S119 [prime polymer] Tm = 159 ° C., MFR = 63 g / 10 min) with an extruder at 230 ° C., respectively, with the propylene random block copolymer (A-1) as the sheath and S119 as the core (sheath / core = 3/7) (Weight ratio)), a composite fiber spinning nozzle (hole diameter: 0.6 mmφ, concentric type, number of holes: 1093 holes <320 mm × 120 mm, staggered arrangement>), extruded at a discharge rate of 0.5 g / min / hole, A continuous bicomponent filament having a fineness of 2.5 denier obtained by melting and drawing with air soccer while applying cooling air (18 ° C.) is directly collected on a collection belt to form a web. The web was heat-pressed with an embossing roll and a flat roll having an embossed area ratio of 10% under the conditions of a linear pressure of 50 N / mm and a temperature of 105 ° C. to obtain a composite fiber nonwoven fabric having a basis weight of 25 g / m ² . Table 2 shows the characteristics of the obtained nonwoven fabric.

[Example 5]
(Nonwoven fabric with eccentric composite fiber)
In Example 3, a composite fiber nonwoven fabric was obtained in the same manner as in Example 3 except that an eccentric type nozzle (core / sheath offset: 0.2 mm) was used as the composite fiber spinning nozzle. Table 3 shows the properties of the obtained nonwoven fabric. In Table 3, a propylene random block copolymer or the like is represented as a propylene copolymer.

[Example 6]
(Nonwoven fabric with eccentric composite fiber)
In Example 4, a composite fiber nonwoven fabric was obtained in the same manner as in Example 4 except that an eccentric type nozzle (core / sheath offset: 0.2 mm) was used as the composite fiber spinning nozzle. Table 3 shows the properties of the obtained nonwoven fabric.

[Example 7]
(Non-woven fabric with side-by-side composite fiber)
In Example 3, a composite fiber nonwoven fabric was obtained in the same manner as in Example 3 except that a side-by-side nozzle was used as the composite fiber spinning nozzle. Table 3 shows the properties of the obtained nonwoven fabric.

[Example 8]
(Non-woven fabric with side-by-side composite fiber)
In Example 4, a composite fiber nonwoven fabric was obtained in the same manner as in Example 4 except that a side-by-side nozzle was used as the composite fiber spinning nozzle. Table 3 shows the properties of the obtained nonwoven fabric.

[Comparative Example 1]
(Nonwoven fabric with monocomponent filament)
In Example 1, instead of the resin (A-1), the propylene random block copolymer (R-1) obtained in Production Example 9 was melt-kneaded as described above, and the MFR-adjusted resin was used. Except for the above, a nonwoven fabric was obtained in the same manner as in Example 1. Table 2 shows the characteristics of the obtained nonwoven fabric.

[Comparative Example 2]
(Nonwoven fabric with monocomponent filament)
In Example 1, instead of the resin (A-1), the propylene random block copolymer (R-2) obtained in Production Example 10 was melt-kneaded as described above, and the MFR-adjusted resin was used. Except for the above, a nonwoven fabric was obtained in the same manner as in Example 1. Table 2 shows the characteristics of the obtained nonwoven fabric.

[Comparative Example 3]
(Nonwoven fabric with monocomponent filament)
In Example 1, instead of the resin (A-1), the propylene random block copolymer (A-8) obtained in Production Example 8 was melt-kneaded as described above, and the MFR-adjusted resin was used. Except for the above, spinning was carried out in the same manner as in Example 1, but the spinning property was poor and the nonwoven fabric could not be collected.

[Comparative Example 4]
(Nonwoven fabric made of composite fiber)
In Example 5, instead of the resin (A-1), the propylene random block copolymer (R-1) obtained in Production Example 9 was melt-kneaded as described above, and an MFR-adjusted resin was used. Produced a nonwoven fabric in the same manner as in Example 5. Table 3 shows the properties of the obtained nonwoven fabric.

[Comparative Example 5]
(Nonwoven fabric made of composite fiber)
In Example 5, instead of the resin (A-1), the propylene random block copolymer (R-2) obtained in Production Example 10 was melt-kneaded as described above, and an MFR-adjusted resin was used. Produced a nonwoven fabric in the same manner as in Example 5. Table 3 shows the properties of the obtained nonwoven fabric.

  The non-woven fabric of the present invention can be suitably used for various non-woven fabric applications such as surgical clothes, disposable diapers, sanitary napkins and other clothing and hygiene materials, industrial materials such as packaging materials, and daily goods. Moreover, a heat seal body can be easily formed with a polyethylene non-woven fabric, a polyethylene sheet, etc., and can be suitably used as a composite material.

Claims (9)

Polymerized with a metallocene catalyst, a melt flow rate of 0.1 to 100 g / 10 min, a melting point of 100 to 155 ° C., and a portion insoluble in room temperature n-decane (D _insol ) 90 to 6
It is composed of 0% by weight and a portion soluble in room temperature n-decane (D _sol ) of 10 to 40% by weight, the D _insol satisfies the requirements (1) to (3), and the D _sol is the requirement (4) A non-woven fabric comprising a propylene random block copolymer (A) satisfying (6).
(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 13 mol%
(3) The sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene in D _insol is 0.2 mol% or less. (4) Molecular weight distribution (Mw / Mn) obtained from GPC of D _sol 1.0-3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%.   The nonwoven fabric according to claim 1, wherein the nonwoven fabric is formed from a monocomponent filament made of the propylene random block copolymer (A).   The nonwoven fabric according to claim 1, wherein at least a part of the surface is formed from a composite fiber made of the propylene random block copolymer (A).   The composite fiber has a core-sheath type structure including a sheath part made of the propylene random block copolymer (A) and a core part made of a thermoplastic resin other than the copolymer (A). The nonwoven fabric according to claim 3.   The nonwoven fabric according to claim 4, wherein the composite fiber has an eccentric core-sheath structure.   The composite fiber has a side-by-side structure composed of a fiber part made of the propylene random block copolymer (A) and a fiber part made of a thermoplastic resin other than the copolymer (A). The nonwoven fabric according to claim 3.   The thermoplastic resin other than the copolymer (A) is at least one resin selected from polyolefin resins other than the copolymer (A). Non-woven fabric.   The composite fiber is 50 by weight ratio of a sheath or fiber part made of the propylene random block copolymer (A) and a core or fiber part made of a thermoplastic resin other than the copolymer (A). It has in the range of: 50-10: 90, The nonwoven fabric in any one of Claims 4-7 characterized by the above-mentioned.   The nonwoven fabric according to any one of claims 1 to 8, which is partially fused.