JP6267525B2 - Multilayer nonwoven fabric - Google Patents

Description

  The present invention relates to a multilayer nonwoven fabric. More specifically, the present invention relates to a multilayer nonwoven fabric having an excellent elastic recovery rate and elongation at break, and having a good touch and feel, and a textile product using the multilayer nonwoven fabric.

  In recent years, elastic fibers and elastic nonwoven fabrics have been used for various applications such as sanitary products such as disposable diapers and sanitary products, clothing materials, bandages, and packaging materials. Disposable diapers, sanitary products, etc. are used in direct contact with the body. Therefore, from the viewpoints of a good fit on the body and ease of movement of the body after wearing, moderate elasticity and elastic recovery Is required.

Patent Document 1 discloses an elastic fiber obtained by blending an elastomer such as an olefin copolymer or a styrene block copolymer and another resin component as an elastic fiber to which elastic resilience is imparted. However, since these elastomers are incompatible with polypropylene and are non-crystalline, when these elastomers and polypropylene are mixed to form elastic fibers, the elastomers bleed on the fiber surface. Therefore, the elastic nonwoven fabric made of this elastic fiber has a sticky feeling, and the fiber product using this elastic nonwoven fabric has a problem that the touch is bad.
In Patent Document 2, a spunbond nonwoven fabric including fibers composed of a composition composed of low crystalline polypropylene and high crystalline polypropylene is arranged in the outermost layer, and a melt blown layer composed of fibers using 100% by mass of high crystalline polypropylene is used as an inner layer. A multi-layered nonwoven fabric is disclosed. However, there is a need for further improvements in elastic recovery, tensile properties, and particularly elongation at break.

JP 2003-129330 A International Publication No. 2011/030893

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a multilayer nonwoven fabric having an excellent elastic recovery rate and elongation at break, and having a good touch and feel, and a fiber product using the multilayer nonwoven fabric. It is.

  As a result of intensive studies, the present inventors have found that the above-described object can be achieved by a multilayer nonwoven fabric obtained by specific molding conditions using a propylene-based resin having an appropriate elastic modulus for the meltblown nonwoven fabric layer. . That is, a multilayer nonwoven fabric having a melt blown nonwoven fabric composed of a resin composition containing a specific propylene-based resin in at least one inner layer of the multilayer nonwoven fabric is excellent in elastic recovery and elongation at break, has reduced stickiness, and is used as a material for the multilayer nonwoven fabric. It was found to be suitable. Furthermore, it has been found that the elastic recovery rate is further improved by mechanically stretching the multilayer nonwoven fabric. The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [7].
[1] A three-layer or more multilayer nonwoven fabric composed of two outer layers and an inner layer sandwiched between them, wherein at least one of the inner layers satisfies the following (a) and (b): A multilayer nonwoven fabric which is a melt blown nonwoven fabric comprising a resin composition containing 100% by mass.
(A) Weight average molecular weight (Mw) = 5,000 to 1,000,000
(B) [mmmm] = 20-60 mol%
[2] The multilayer nonwoven fabric according to [1], wherein the propylene-based resin satisfies the following (c) and (d).
(C) Molecular weight distribution (Mw / Mn) = 1.5-3.0
(D) [rrrr] / (1- [mmmm]) ≦ 0.1
[3] The multilayer nonwoven fabric according to [1] or [2], wherein the propylene-based resin satisfies the following (e) to (g).
(E) Melting point (Tm−D) = 30 to 140 ° C.
(F) Melting endotherm (ΔH−D) = 5 to 60 J / g
(G) Crystallinity = 1-40%
[4] The multilayer nonwoven fabric according to any one of [1] to [3], wherein the resin composition contains 95 to 100% by mass of the propylene-based resin.
[5] The multilayer nonwoven fabric according to any one of [1] to [4], wherein the outer layer is a spunlace nonwoven fabric or a spunbond nonwoven fabric.
[6] The multilayer nonwoven fabric according to any one of [1] to [5], which is molded by an off-line manufacturing method.
[7] A fiber product using the multilayer nonwoven fabric according to any one of [1] to [6].

  ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding elastic recovery rate and breaking elongation, the multilayer nonwoven fabric with a favorable touch and touch, and the textiles using this multilayer nonwoven fabric can be provided.

It is a figure which shows the one aspect | mode regarding the lamination | stacking method for obtaining the multilayer nonwoven fabric of this invention. It is a figure which shows the one aspect | mode regarding the lamination | stacking method for obtaining the multilayer nonwoven fabric of this invention. It is a figure which shows the one aspect | mode regarding the lamination | stacking method for obtaining the multilayer nonwoven fabric of this invention. It is a figure which shows the one aspect | mode regarding the lamination | stacking method for obtaining the multilayer nonwoven fabric of this invention.

[Multilayer nonwoven fabric]
The multilayer nonwoven fabric of the present invention is a multilayer nonwoven fabric of three or more layers composed of two outer layers and an inner layer sandwiched between them, and at least one of the inner layers satisfies the following (a) and (b) It is a melt blown nonwoven fabric made of a resin composition containing 90 to 100% by mass of a propylene resin.
In the present specification, a melt blown nonwoven fabric made of a resin composition containing 90 to 100% by mass of a propylene-based resin that satisfies (a) and (b) is also simply referred to as “M”, and (a) and (b) A layer other than a meltblown nonwoven fabric made of a resin composition containing 90 to 100% by mass of a propylene-based resin that satisfies the above is also simply referred to as “X” or “X layer”.
In this specification, the spunlace nonwoven fabric is also simply referred to as “Sp”, and the spunbond nonwoven fabric is also simply referred to as “S”.
Hereafter, each component used for this invention and a manufacturing method are demonstrated one by one.

<Propylene-based resin>
The propylene-based resin used in the present invention satisfies the following (a) and (b). The following (a) and (b) can be adjusted according to the selection of the catalyst and the reaction conditions when producing the propylene-based resin. The same applies to (c) to (f) described later. Hereinafter, in the present specification, when simply referred to as a propylene resin, it represents a propylene resin satisfying the following conditions (a) and (b) used in the present invention.
Although it does not specifically limit as propylene-type resin which does not satisfy | fill the conditions of following (a) and (b), The highly crystalline polypropylene etc. which are mentioned later are mentioned.
(A) Weight average molecular weight (Mw) = 5,000 to 1,000,000
The propylene-based resin used in the present invention has a weight average molecular weight of 5,000 to 1,000,000. If the weight average molecular weight is less than 5,000, the viscosity of the propylene-based resin is too low and the strength is lowered. On the other hand, if the weight average molecular weight exceeds 1,000,000, the viscosity of the propylene-based resin becomes too high and the spinnability is lowered. From such a viewpoint, the weight average molecular weight is preferably 10,000 to 300,000, more preferably 20,000 to 200,000, still more preferably 30,000 to 150,000, and still more preferably 40,000. ~ 150,000.

(B) [mmmm] = 20-60 mol%
The propylene-based resin used in the present invention has a [mmmm] (mesopentad fraction) of 20 to 60 mol%. If [mmmm] is less than 20 mol%, solidification after melting is very slow, making it difficult to continuously form a multilayer nonwoven fabric or insufficient strength of the nonwoven fabric. Moreover, when [mmmm] exceeds 60 mol%, since the degree of crystallinity is too high, the meltblown nonwoven fabric becomes too hard, and the elastic recovery rate of the meltblown nonwoven fabric and the multilayer nonwoven fabric decreases. From such a viewpoint, [mmmm] is preferably 30 to 55 mol%, more preferably 35 to 55 mol%, and still more preferably 40 to 50 mol%.

The propylene-based resin preferably further satisfies the following (c) and (d), and further preferably satisfies the following (e) to (g).
(C) Molecular weight distribution (Mw / Mn) = 1.5-3.0
The propylene-based resin used in the present invention has a molecular weight distribution (Mw / Mn) of preferably 1.5 to 3.0, more preferably from the viewpoint of spraying and laminating a meltblown layer to another nonwoven fabric layer. Is 1.5 to 2.5, more preferably 1.5 to 2.3.

(D) [rrrr] / (1- [mmmm]) ≦ 0.1
The propylene-based resin used in the present invention preferably has [rrrr] / (1- [mmmm]) of 0.1 or less. [Rrrr] / (1- [mmmm]) is an index indicating the uniformity of the regularity distribution of the propylene-based resin. When this value is satisfied, it does not cause stickiness that occurs when a mixture of a highly stereoregular polypropylene and an atactic polypropylene is formed like a conventional polypropylene produced using an existing catalyst system. From such a viewpoint, [rrrr] / (1- [mmmm]) is more preferably 0.05 or less.

The mesopentad fraction [mmmm] and the racemic pentad fraction [rrrr] in this specification are based on the method proposed by A. Zambelli et al. In “Macromolecules, 6, 925 (1973)”. It is a meso fraction and a racemic fraction in a pentad unit in a polypropylene molecular chain measured by a methyl group signal of a ¹³ C-NMR spectrum. As the mesopentad fraction [mmmm] increases, the stereoregularity increases.

(E) Melting point (Tm−D) = 30 to 140 ° C.
The melting point (Tm-D) of the propylene-based resin used in the present invention is preferably 30 to 140 ° C. from the viewpoints of elastic properties and moldability. When the melting point (Tm-D) is 30 ° C. or higher, the solidification rate is increased and the continuous moldability is improved, and when the melting point (Tm-D) is 140 ° C. or lower, the flexibility is not lowered and good elastic recovery is achieved. Sex is obtained. From such a viewpoint, the temperature is preferably 40 to 130 ° C, more preferably 50 to 120 ° C, still more preferably 55 to 100 ° C, and still more preferably 60 to 90 ° C.
In the present invention, the melting point (Tm-D) is a value obtained by the method described in Examples described later.

(F) Melting endotherm ΔH−D = 5 to 60 J / g
The melting endotherm ΔH-D of the propylene-based resin used in the present invention is preferably 5 to 60 J / g from the viewpoints of elastic properties, strength, and moldability. When the melting endotherm ΔH-D is 5 J / g or more, good nonwoven fabric strength is obtained, the solidification rate is increased, and the continuous moldability is improved. When the melting endotherm ΔH-D is 60 J / g or less, good elasticity recovery is obtained without lowering flexibility. From such a viewpoint, it is preferably 10 to 60 J / g, more preferably 10 to 55 J / g, still more preferably 15 to 55 J / g, and still more preferably 20 to 50 J / g.
In the present invention, the melting endotherm ΔH-D is a value obtained by the method described in Examples described later.

(G) Crystallinity = 1-40%
The degree of crystallinity of the propylene-based resin used in the present invention is preferably 1 to 40% from the viewpoint of elastic properties and moldability. When the crystallinity is 1% or more, good nonwoven fabric strength can be obtained, the solidification speed is increased and the continuous moldability is improved, and when the crystallinity is 40% or less, the flexibility is not lowered. Good elastic recovery is obtained. From such a viewpoint, it is preferably 2 to 35%, more preferably 3 to 30%, still more preferably 5 to 30%, and still more preferably 10 to 25%.
In the present invention, the degree of crystallinity is calculated using the method described in Examples described later.

By using it as a resin composition containing 90 to 100% by mass of a propylene resin satisfying the above (a) and (b), a raw material composition suitable for the production of the target multilayer nonwoven fabric can be obtained.
In addition, as a propylene-type resin used by this invention, if the said (a) and (b) are satisfy | filled, it is a copolymer using the comonomer other than propylene in the range which does not impair the objective of this invention, Also good. In this case, the amount of comonomer is usually 2% by weight or less. As comonomer, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene etc. are mentioned, In this invention, 1 type, or 2 or more types can be used among these.

  Examples of the method for producing the propylene resin used in the present invention include a method using a metallocene catalyst. Examples of the metallocene catalyst include (A) a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure via two crosslinking groups and (B) a promoter. Illustratively, the general formula (I)

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. , A ligand selected from substituted heterocyclopentadienyl groups, which form a bridged structure via A ¹ and A ² , and they may be the same or different, X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of X may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. And a compound (B-1) and an aluminoxane (B-2) that can react with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. And a catalyst for polymerization containing a promoter component (B) selected from

  Specific examples of the transition metal compound represented by formula (I) include (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3 -Phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2 , 1'-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2'-dimethyl) Rylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-) Isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1 ′ -Dimethylsilylene) bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) di Conium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylene Ridene) -bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2 Examples include '-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride and the like, and those obtained by replacing zirconium in these compounds with titanium or hafnium.

  Other examples of transition metal compounds in metallocene catalysts include, for example, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl). ) (2,4-dimethyl-4H-5,6,7,8-tetrahydro-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-methyl-4H-1- Azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-methyl-4H-5,6,7,8-tetrahydro-1-azurenyl)] hafnium, dichloro [dimethylsilylene (9- Fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, dichloro [Dimethylsilylene (cyclopentadienyl) (2-n-propyl-4-methyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (cyclopentadienyl) (2-isopropyl-4-methyl-4H- 1-azurenyl)] hafnium, dichloro [dimethylgermylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium, and metallocene compounds in which the metal atom in the above compound is replaced by zirconium Can be mentioned. Further, dimethylsilylene (2-methyl-4-phenyl-indenyl) (2- (2-furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-phenyl-4-hydroazurenyl) (2 -(2- (5-methyl) -furyl) -4-phenyl-4-hydroazurenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-phenyl-4-hydroazurenyl) (2-methyl-4- (2- ( 5-methyl) -thienyl) -4-hydroazurenyl) zirconium dichloride, dimethylsilylene (2-methyl-benzoindenyl) (2- (2- (5-methyl) -furyl) -benzoindenyl) zirconium dichloride, dimethylsilylene (2-methyl-4- (2-thienyl) -indenyl) ( -Isopropyl-4- (2-thienyl) -indenyl) zirconium dichloride, dimethylsilylene (2-methyl-4- (2- (5-methyl) -thienyl) -indenyl) (2-isopropyl-4- (2- ( 5-methyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylene (2-methyl-4- (2- (5-t-butyl) -thienyl) -indenyl) (2-isopropyl-4- (2- (5 -T-butyl) -thienyl) -indenyl) zirconium dichloride and metallocene compounds having a tetrahydroindenyl skeleton in place of the indenyl skeleton in the above-mentioned compounds.

  Next, as the component (B-1) in the component (B), dimethylanilinium tetrakispentafluorophenyl borate, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, Examples include tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, and benzyl (tri-n-butyl) ammonium tetraphenylborate.

  (B-1) may be used alone or in combination of two or more. On the other hand, examples of the aluminoxane as the component (B-2) include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane. These aluminoxanes may be used alone or in combination of two or more. Moreover, you may use together the said (B-1) 1 type or more and (B-2) 1 type or more of component.

  As the polymerization catalyst, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of component (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutyl. Aluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride, etc. are mentioned. These organoaluminum compounds may be used alone or in combination of two or more. Here, in the polymerization of propylene, at least one of the catalyst components can be supported on a suitable carrier and used.

The polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used, but a bulk polymerization method and a solution polymerization method are particularly preferable. preferable. The polymerization temperature is usually from −100 to 250 ° C., and the ratio of the catalyst to the reaction raw material is preferably from 1 to 10 ⁸ , particularly preferably from 100 to 10 ⁵ , in terms of the raw material monomer / the component (A). Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is usually atmospheric pressure to 20 MPa (gauge).

(Highly crystalline polypropylene)
The highly crystalline polypropylene used in the melt blown nonwoven fabric made of a resin composition containing 90 to 100% by mass of the propylene resin satisfying the above (a) and (b) is not particularly limited as long as the effects of the present invention are not impaired. For example, a propylene homopolymer, a propylene random copolymer, a propylene block copolymer, etc. are mentioned. The high crystalline polypropylene usually has a melt flow rate (MFR) of 20 to 3,000 g / 10 min, more preferably 30 to 2,000 g / 10 min, still more preferably 50 to 2,000 g / 10 min, and still more preferably. Is 500 to 2,000 g / 10 min, and usually has a melting point of 150 to 167 ° C, preferably 155 to 167 ° C, more preferably 160 to 167 ° C.

(Resin composition)
The resin composition used in the present invention contains 90 to 100% by mass of the propylene resin satisfying the above (a) and (b), preferably 95 to 100% by mass, more preferably 98 to 100% by mass, Preferably it is 100 mass%. When the propylene-based resin is less than 90% by mass, an excellent elastic recovery rate cannot be obtained.
The resin other than the propylene-based resin that satisfies the above (a) and (b) is not particularly limited, and examples thereof include the highly crystalline polypropylene.
The resin composition used in the present invention has a melt flow rate (hereinafter referred to as MFR) of preferably 20 to 3,000 g / 10 min, and a melting endotherm (ΔH-D) of preferably 10 to 80 J / g. It is a thing.
When the MFR of the resin composition is 20 g / 10 min or more, spinnability and coatability are improved. On the other hand, when the MFR is 3,000 g / 10 min or less, yarn breakage is less likely to occur during the nonwoven fabric forming process. From such a viewpoint, the MFR of the resin composition is preferably 30 to 2,000 g / 10 min, more preferably 50 to 2,000 g / 10 min, and still more preferably 500 to 2,000 g / 10 min.
When the melting endotherm of the resin composition is 10 J / g or more, the crystallization of the resin composition does not become too slow, and the non-woven fabric is hardly sticky. On the other hand, if the melting endotherm is 80 J / g or less, crystallization does not become too fast and shots due to yarn breakage are less likely to occur. From such a viewpoint, the melting endotherm of the resin composition is preferably 15 to 60 J / g, more preferably 20 to 50 J / g.

The said resin composition may contain various additives, such as another thermoplastic resin and a mold release agent, in the range which does not inhibit the effect of this invention.
Examples of the other thermoplastic resins include olefin polymers other than the propylene resin, and specifically, polypropylene, propylene-ethylene copolymer, propylene-ethylene-diene copolymer, polyethylene, ethylene / α- Examples include olefin copolymers, ethylene-vinyl acetate copolymers, hydrogenated styrene elastomers, and the like. Moreover, polyester, polyamide, polylactic acid, etc. are also mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

  The above-mentioned mold release agent refers to an additive for improving peelability so that the formed nonwoven fabric does not adhere to a roll or a conveyor of a molding machine. The mold release agent contained in the resin composition is referred to as an internal mold release agent, and the internal mold release agent refers to an additive that is added to the resin raw material to improve the peelability of the nonwoven fabric. The external mold release agent to be described later refers to an additive for directly applying to a roll or conveyor of a molding machine to improve the peelability of the nonwoven fabric.

As internal mold release agent, organic carboxylic acid or metal salt thereof, aromatic sulfonate salt or metal salt thereof, organic phosphate compound or metal salt thereof, dibenzylidene sorbitol or derivative thereof, rosin acid partial metal salt, inorganic fine particles, Imido acid, amic acid, quinacridones, quinones or a mixture thereof may be mentioned.
Examples of the metal in the metal salt of the organic carboxylic acid include Li, Ca, Ba, Zu, Mg, Al, and Pb. Examples of the carboxylic acid include octylic acid, palmitic acid, lauric acid, stearic acid, and behen. Acid, montanic acid, 12-hydroxystearic acid, oleic acid, isostearic acid, ricinoleic acid and other fatty acids, benzoic acid, p-tb-benzoic acid and other aromatic acids, specific examples include benzoic acid Examples include aluminum salt, aluminum salt of pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate and the like.
Specific examples of the dibenzylidene sorbitol or derivatives thereof include dibenzylidene sorbitol, 1,3: 2,4-bis (o-3,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o- 2,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-ethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-chlorobenzylidene) sorbitol and 1,3 : 2,4-dibenzylidene sorbitol and the like, and more specifically, Gelall MD and Gelall MD-R manufactured by Shin Nippon Rika Co., Ltd. are exemplified.
Examples of the rosin acid partial metal salt include Pine Crystal KM1600, Pine Crystal KM1500, and Pine Crystal KM1300 manufactured by Arakawa Chemical Industries, Ltd.
As the inorganic fine particles, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, magnesium oxide, Pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, molybdenum sulfide and the like can be mentioned. Synthetic silica may be used as the silica, and examples include silicia manufactured by Fuji Silysia Co., Ltd., and mizukasil manufactured by Mizusawa Chemical Industry Co., Ltd.
Examples of the amide compounds include erucic acid amide, oleic acid amide, stearic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, stearyl erucamide and oleyl palmitoamide, adipic acid dianilide, suberic acid dianilide. Etc.
Examples of the organophosphate metal salt include ADEKA STAB NA-11 and ADK STAB NA-21 manufactured by ADEKA Corporation.

These internal mold release agents can be used individually by 1 type or in combination of 2 or more types. In the present invention, among these internal mold release agents, erucic acid amide, dibenzylidene sorbitol, 1,3: 2,4-bis (o-3,4-dimethylbenzylidene) sorbitol, 1,3: 2,4 -Bis (o-2,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-ethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-chlorobenzylidene) Those selected from sorbitol and 1,3: 2,4-dibenzylidene sorbitol are preferred.
In the resin composition, the content of the internal release agent is preferably 10 to 10000 mass ppm, more preferably 100 to 5000 mass ppm, based on the resin mixture excluding the additive. When the content of the internal mold release agent is 10 mass ppm or more, the function as a mold release agent is expressed, and when it is 10000 mass ppm or less, the balance between the function as the mold release agent and the economical efficiency is improved.

  As various additives other than the mold release agent, conventionally known additives can be blended. For example, foaming agents, crystal nucleating agents, anti-glare stabilizers, ultraviolet absorbers, light stabilizers, heat stabilizers, antistatic agents. Agent, flame retardant, synthetic oil, wax, electrical property improver, anti-slip agent, anti-blocking agent, viscosity modifier, anti-coloring agent, anti-fogging agent, lubricant, pigment, dye, plasticizer, softener, aging Additives such as an inhibitor, a hydrochloric acid absorbent, a chlorine scavenger, an antioxidant, and an anti-tacking agent can be mentioned.

<Configuration of multilayer nonwoven fabric>
The multilayer nonwoven fabric of the present invention is a multilayer nonwoven fabric of three or more layers composed of two outer layers and an inner layer sandwiched between them, and at least one of the inner layers satisfies the above (a) and (b) It is a melt blown nonwoven fabric made of a resin composition containing 90 to 100% by mass of a resin.
For example, a layer other than the meltblown layer is a spunlace nonwoven fabric and a spunbonded nonwoven fabric, and is laminated with a meltblown nonwoven fabric made of a resin composition containing 90 to 100% by mass of a propylene-based resin satisfying the above (a) and (b). May be. A multilayer nonwoven fabric made of a melt blown nonwoven fabric made of a resin composition containing 90 to 100% by mass of a propylene-based resin satisfying the above (a) and (b) at least one of the inner layers has an excellent elastic recovery rate and elongation at break. Good touch and feel.
The multilayer nonwoven fabric can be manufactured to have a structure such as XMX (for example, SpMSp, SMS, SpMS, etc.), XMMX, XMXX, XXMXX, XXMMX, XXMMXX, XMMMX, XXMMMX, XMXMX, and the like. Here, each “X” in the multilayer nonwoven fabric may be the same or different. In some embodiments, at least the M layer and its one adjacent layer are bonded together, and in other embodiments, at least the M layer and its two adjacent layers are bonded. When such adhesion between the M layer and the X layer is desirable, the cooling air flow at the time of forming the M layer is attenuated and / or heated to bond the formed M layer and fibers in the M layer. The bonding ability of the M layer and the fibers in the M layer to the X layer can be maintained.
As a preferred multilayer nonwoven fabric configuration, from the viewpoint of balance with moldability, cost, and properties of multilayer nonwoven fabric, XMX configuration is preferable, and among them, moldability, cost, and balance with properties of multilayer nonwoven fabric. To SMS, SpMSp and SpMS, more preferably SMS and SpMSp. Also, the basis weight of the multilayer nonwoven fabric is preferably 10 to 200 g / m ^2, more preferably 15 to 180 g / m ^2, more preferably from 20~160g / m ^2.
Further, from the viewpoint of obtaining an excellent elastic recovery rate, preferably, the weight per unit area of all the M layers is equal to or larger than the per unit area of all X layers, and more preferably, the weight per unit area of all M layers. The configuration is larger than the basis weight of all the X layers.

(Melt blown nonwoven fabric comprising a resin composition containing 90 to 100% by mass of a propylene resin satisfying (a) and (b): M layer)
The M layer of the non-woven fabric is a melt blown comprising a resin composition containing 90 to 100% by mass, preferably 95 to 100% by mass, more preferably 98 to 100% by mass, and still more preferably 100% by mass, of the above-described propylene resin. It is a nonwoven fabric.
A conventionally known method can be employed as the melt blow method. For example, a melt-kneaded resin composition is extruded from a single hole (orifice) and then brought into contact with a high-speed heated gas stream to form fine fibers, which are collected on a porous support (for example, a net conveyor). It can be manufactured by making it into a nonwoven fabric and subjecting it to heat fusion treatment if necessary. The average fiber diameter of the fibers forming the meltblown nonwoven fabric is preferably 0.01 to 30 μm, more preferably 0.05 to 20 μm, still more preferably 0.1 to 15 μm, still more preferably 0.2 to 10 μm. It is. A nonwoven fabric produced by the melt blow method has excellent barrier properties and a good texture because the average diameter of the fibers constituting the nonwoven fabric is small.
The basis weight of the melt blown layer is preferably 5 to 120 g / m ² , more preferably 10 to 110 g / m ² , and still more preferably 20 to 100 g / m ² .

As the melt blown nonwoven fabric molding apparatus, preferably, the molding apparatuses shown in the following (1) and (2) can be used.
(1) A plurality of single holes (orifices) through which molten resin is discharged are arranged in a straight line, and a high-speed heated gas flow is discharged adjacent to each orifice through which the molten resin is discharged. A gas supply orifice is disposed, and a die designed in such a manner that the molten resin discharged from the orifice from which the molten resin is discharged is stretched by a high-speed heated gas flow discharged from the gas supply orifice. Having a molding device.
Examples thereof include those described in JP-A-56-159336, US Pat. No. 5,476,616, and US Patent Application Publication No. 2004/0209540. Hereinafter, in this specification, it is also simply referred to as “MB device type 1”.
(2) A plurality of single holes (orifices) through which molten resin is discharged are arranged in a line on a straight line, and a high-speed heated gas flow is provided so as to face and sandwich the line where the single holes are arranged. Two or more gas supply slits for discharging the gas are disposed, and the molten resin discharged from the orifice is in a straight line with the high-speed heated gas flow discharged from the gas supply slit and colliding with it. Molding device with a designed die.
Examples thereof include those described in JP-A No. 54-103466, JP-A No. 11-200135, and US Pat. No. 3,849,291. Hereinafter, in this specification, it is also simply referred to as “MB device type 2”.

  As a specific process of melt blow, for example, a resin composition melted by an extruder is transferred to a quantitative melt pump (for example, a gear pump), and the melted resin composition is specially melted at a stable production rate by the melt pump. Send to blow mold. At this time, the temperature of the molten resin is preferably 300 ° C. or less, more preferably 270 ° C. or less, further preferably 240 ° C. or less, and still more preferably 230 ° C. or less, although it depends on the melt blow molding apparatus used. The molten resin composition exiting the mold is brought into contact with a high-speed heated gas stream. This high-speed heated gas stream stretches the filament and further solidifies the filament with cooling air. At this time, although the temperature of the high-speed heated gas flow depends on the melt blow molding apparatus used, for example, when the melt blow apparatus of the MB apparatus type 1 is used, molding can be performed at the same temperature as the temperature of the molten resin. Moreover, when using the melt blow apparatus of the said MB apparatus type 2, it can shape | mold in the temperature range preferably 20-50 degreeC high with respect to the temperature of molten resin. Further, the discharge amount per single hole is 0.1 to 3.0 g / min, but from the viewpoint of obtaining finer fibers and the viewpoint of moldability, the discharge amount per single hole is preferably 0.1. It is -0.6g / min, More preferably, it is 0.1-0.5g / min. All the above fiber forming steps are usually performed within a few centimeters of the mold. Mold design is important to effectively produce quality products. The fabric is formed by directly blowing the filament to another nonwoven fabric (X layer) formed on the pore-forming belt, and the distance (DCD) between the die and the porous forming belt is preferably 150 to 550 mm, More preferably, it is 200-400 mm. Moreover, in order to obtain the finest fiber possible, it is required to use a resin composition having a very high MFR of 200 g / 10 min or more, but at a higher processing temperature, a low MFR of about 20 g / 10 min. The resin composition can also be used.

(Layers other than melt-blown nonwoven fabric made of a resin composition containing 90 to 100% by mass of a propylene-based resin that satisfies (a) and (b): X layer)
The production method of the X layer of the multilayer nonwoven fabric is not particularly limited as long as it is a nonwoven fabric. For example, a spunbond nonwoven fabric, a spunlace nonwoven fabric, a card nonwoven fabric, an airlaid nonwoven fabric, a flash spun nonwoven fabric, a wet nonwoven fabric, the above (a) and (b Various non-woven fabrics such as a melt-blown non-woven fabric other than a melt-blown non-woven fabric made of a resin composition containing 90 to 100% by mass of a propylene-based resin satisfying the above) can be used. A spunbonded nonwoven fabric or a spunlaced nonwoven fabric is preferred, and a spunlaced nonwoven fabric is more preferable from the viewpoint of improving the elastic recovery rate, feel and feel.

Although the raw material of the nonwoven fabric used for X layer is not specifically limited, Olefin-type polymers other than the said propylene-type resin are mentioned, Specifically, a polypropylene, a propylene-ethylene copolymer, a propylene-ethylene-diene copolymer is mentioned. , Polyethylene, ethylene / α-olefin copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene elastomer and the like. Moreover, polyester, polyamide, polylactic acid, etc. are also mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.
Also, the basis weight when used as the outer layer is preferably from 5 to 100 g / m ^2, more preferably 7~50g / m ^2, more preferably from 8~35g / m ^2.
Moreover, the fiber diameter of the fiber which comprises the nonwoven fabric used by X layer becomes like this. Preferably it is 0.1-50 micrometers, More preferably, it is 0.5-40 micrometers, More preferably, it is 1.0-30 micrometers.

(Lamination method of multilayer nonwoven fabric)
Although one aspect | mode of the lamination | stacking method of the said multilayer nonwoven fabric is not limited to these examples, For example, an aspect as shown in FIGS. 1-4 is mentioned.
For example, as shown in FIG. 1, in order to obtain the configuration of the XMX laminated body 8, first, the material 3 constituting the X layer is unwound and conveyed on a pore forming belt (net conveyor) 7, and then On the pore forming belt 7, the melt blown fiber 2 constituting the M layer is discharged from the melt blow die 1, the M layer is laminated on the X layer, and immediately after that, another X layer prepared in advance is constituted. The material 4 is fed out, and the X layer formed from the material 4 constituting the X layer is quickly laminated on the laminated body of the X layer and the M layer, and conveyed on the pore forming belt 7 to be pressurized or Under non-pressurized conditions, each X layer of the outer layer and M layer of the inner layer may be heat-fused and integrated with the M layer of the inner layer in a state before solidification to obtain the XMX laminate 8, After laminating the X layer, the M layer, and the X layer as described above, for example, a smooth roll (S-roll) By heating and pressing through a patterned roll (embossing roll) 5 and 6, by fusing the layers, may be a method of obtaining a XMX laminate 8.

Further, in one aspect of the method for laminating the multilayer nonwoven fabric shown in FIG. 2, the materials 3 and 4 constituting the two X layers passing below or in front of the melt blow die 1 of the melt blown nonwoven fabric molding apparatus. The melt blown fibers 2 constituting the molten M layer are discharged to laminate the M layers symmetrically, and preferably, the outer X layers and the inner M layers are brought into contact with each other almost simultaneously. Under the pressurized or non-pressurized condition, the outer X layers and the inner M layer are heat-fused and integrated with the inner M layer in a state before solidification to obtain the XMX laminate 8. After the X layer, the M layer, and the X layer are laminated as described above, for example, they are heated through a smooth roll (S-roll) or patterned rolls (embossing rolls) 5 and 6. By pressing, each layer is fused, and XMX It is also possible to obtain a Sotai 8.
In another embodiment shown in FIG. 3, the melt blown fibers 2 constituting the molten M layer are discharged to laminate the M layer on the material 3 constituting the first X layer, and then The material 4 constituting the second X layer is brought into contact with the coated surface of the M layer of the first X layer. Orientation of the meltblowing die 1 with respect to smooth rolls (S-rolls) and patterned rolls (embossing rolls) 5 and 6 (each X passing below or in front of the meltblown fibers 2 constituting the M layer being formed) The angle to the layer) and / or its position (linear position along the axis of each X layer passing below or in front of the meltblown fibers 2 constituting the M layer being formed) is shown in FIGS. Can be adjusted to any degree between the two extreme values.

In addition, for the X layer, a nonwoven fabric is manufactured in advance by a spunlace method or a spunbond method, and a multilayer nonwoven fabric is formed by discharging and blowing the melt blown fibers 2 constituting the M layer between the two nonwoven fabrics to be the X layer. Alternatively, the X layer is formed on the pore forming belt (net conveyor) 7 by the spunbond method or the like, and then the M layer is laminated on the X layer, and the X layer is further formed on the M layer. A multilayer nonwoven fabric may be formed by thermocompression bonding of a multilayer body in which layers are laminated (online manufacturing method).
As an embodiment of the on-line manufacturing method, the example of FIG. 4 can be given. In FIG. 4, the spunbond fibers 10 constituting the S layer are first discharged and conveyed from the spunbond die 9 onto the pore-forming belt (net conveyor) 7, and subsequently, on the pore-forming belt 7. The melt blown fiber 2 constituting the M layer is discharged from the melt blow die 1 and the M layer is laminated on the S layer. Immediately thereafter, the spunbond fiber 10 constituting the S layer is formed from the other spunbond die 9. The spunbond fibers 10 constituting the S layer are quickly laminated on the laminate of the S layer and the M layer, and conveyed on the pore forming belt 7, for example, a smooth roll (S-roll) or pattern Each layer is fused by heating and pressurizing through the formed rolls (embossing rolls) 5 and 6 to obtain the XMX laminate 8.
From the viewpoint of obtaining excellent elastic recoverability, it is preferable to obtain a multilayer nonwoven fabric by an off-line production method.

  In any case, the multilayer nonwoven fabric in which the M layers are laminated is not heated or heated while being applied with a slight pressure, and is not heated (hereinafter also referred to as “S-roll”). Or it can be obtained by passing through a nip between heated and patterned rolls (eg embossing rolls), or a combination of two or more thereof. By providing a method for producing the multilayer nonwoven as described herein, it is preferred that the adhesive is substantially absent from the multilayer nonwoven, in order to secure the layers together in the multilayer nonwoven. , Which means that no adhesive is used.

  A method of bonding with an adhesive such as a hot-melt adhesive or a solvent-based adhesive can also be adopted, but when a hot-melt adhesive is used, for example, a vinyl-based adhesive, a polyvinyl alcohol-based resin-based adhesive, Examples thereof include rubber adhesives such as styrene-butadiene and styrene-isoprene. In the case of using a solvent-based adhesive, for example, a rubber-based adhesive such as styrene-butadiene, styrene-isoprene, or urethane, a resin-based organic solvent such as vinyl acetate or vinyl chloride, or an aqueous emulsion adhesive. Can be mentioned. Among these adhesives, rubber-based hot melt adhesives such as styrene-isoprene and styrene-butadiene are preferable in that they do not impair the properties of the multilayer nonwoven fabric.

(annealing)
As one aspect of the multilayer nonwoven fabric of the present invention, in addition to the above-described method, it can also be produced by performing an annealing step.
Annealing can be performed after the fibers in each nonwoven fabric are formed, after each nonwoven fabric is produced from the fibers, and after the multilayer nonwoven fabric is produced. Annealing partially relieves the internal stress of the drawn fiber and restores the elastic recovery properties of the resin composition in the fiber. Annealing significantly changes the internal crystal structure and the relative order of the amorphous and semi-crystalline phases and restores elastic properties. For example, fiber annealing at a temperature of 40 ° C. or higher and slightly lower than the crystal melting point of the resin composition is suitable for restoring the elastic properties of the fiber.

  For the thermal annealing of the resin composition used for the M layer or the resin used for the X layer, a material made from the resin composition used for the M layer or the resin used for the X layer is used, for example, at room temperature (23 ° C.) to It is carried out by maintaining at 160 ° C. or at a temperature of room temperature (23 ° C.) to 130 ° C. for several seconds to 1 hour. Typical annealing time is 1-5 minutes at 100 ° C. The annealing time and temperature can be adjusted according to the resin composition used for the M layer or the resin used for the X layer. The annealing temperature may be in the range of 60 to 130 ° C, or about 100 ° C. In some cases, for example, the conventional continuous spinning and annealing can be performed by passing the fiber through a heating roll, and the conventional annealing technique may not be applied. Annealing should be performed under very low fiber tension from the viewpoint of imparting elasticity to the fiber so that the fiber shrinks. In the nonwoven process, the web typically passes through an S-roll to cause point bonding (strengthening) of the web. By passing the non-reinforced nonwoven fabric through a heated S-roll at a relatively high temperature, the fibers can be annealed to increase the elasticity of the nonwoven web. Similar to fiber annealing, the nonwoven web should allow shrinkage of the web in both the flow direction (MD) and its orthogonal direction (CD) under low tension to increase the elasticity of the nonwoven web. The roll temperature of the combined S-roll may be, for example, 100 to 130 ° C or about 100 ° C. The annealing temperature can be adjusted according to the resin composition.

(Extension processing)
As one aspect of the multilayer nonwoven fabric of the present invention, the elastic recovery rate can be further improved by mechanical stretching. A conventionally known method can be applied as the stretching method, and the multilayer nonwoven fabric may be partially stretched or may be stretched entirely. Moreover, it may be uniaxially stretched or biaxially stretched. As a method of stretching in the flow direction of the stretching apparatus, that is, the flow direction (MD) of the multilayer nonwoven fabric at the time of molding the multilayer nonwoven fabric, for example, a multilayer nonwoven fabric partially fused to two or more nip rolls is passed. At this time, the multilayer nonwoven fabric partially fused can be stretched by increasing the rotational speed of the nip roll in the order of the flow direction of the stretching apparatus. Further, as a stretching device, gear stretching can be performed using a gear stretching device. Moreover, a multilayer nonwoven fabric can also be used in the form laminated | stacked with other base materials like a breathable film.

  The draw ratio is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more, and preferably 200% or less, more preferably 100% or less, and even more preferably 80% or less.

  In the case of uniaxial stretching, the preferable stretching ratio is the stretching direction in the flow direction of the stretching apparatus, that is, the stretching ratio in the flow direction (MD) of the multilayer nonwoven fabric during the molding of the multilayer nonwoven fabric, or the direction orthogonal to this (CD). In the case of biaxial stretching, it is preferable that at least one of the flow direction (MD) of the stretching apparatus and the direction (CD) orthogonal thereto satisfy the above stretching ratio.

In addition, when using a gear extending | stretching apparatus as an extending | stretching apparatus, it is preferable to extend | stretch in the said CD direction. When gear stretching is performed in the CD direction, even when the transport speed of the multilayer nonwoven fabric is increased, the multilayer nonwoven fabric is less likely to be caught and broken at the gear tip, and can be molded at a higher speed than in the MD direction. Moreover, since it is excellent also in the formation property of the wave shape by gear extending | stretching, it is preferable.
From the viewpoint of moldability, the gear stretching is preferably performed at a low temperature such as 10 to 80 ° C, more preferably 15 to 70 ° C, and further preferably 20 to 60 ° C.
The preferred gear depth depends on the raw material of the M layer in the stretched multilayer nonwoven fabric and the manufacturing method. For example, in the case of the same layer structure and the same thickness, from the viewpoint of the elastic recovery rate, the raw material of the M layer When the MFR of the propylene-based resin composition is 300 g / 10 min or more and the M layer is manufactured by the MB device type 1, it is preferably 0.10 inch or less and manufactured by the MB device type 2. In this case, it is preferably 0.15 inches or less, more preferably 0.12 inches or less. For example, when the MFR of the propylene-based resin composition is less than 100 g / 10 min and the M layer is the MB apparatus type 1 Is preferably 0.12 inches or less, and when manufactured with the MB device type 2, is preferably 0.15 inches or less, and more preferably It is equal to or less than 0.12 inches. The gear pitch width is preferably 1 to 5 mm.

  By stretching in such a method, the fibers in the M layer and the M layer in the multilayer nonwoven fabric and the fibers in the X layer mainly used for the outer layer are all stretched. These fibers are plastically deformed and elongated (longer) according to the draw ratio.

The elongation at break (CD) of the multilayer nonwoven fabric and stretched multilayer nonwoven fabric of the present invention is preferably 100% or more, more preferably 140% or more, still more preferably 170% or more, still more preferably 180% or more, and even more. Preferably it is 200% or more.
The tensile strength (CD) of the multilayer nonwoven fabric and stretched multilayer nonwoven fabric of the present invention is preferably 15 N / 2.5 cm or more, more preferably 20 N / 2.5 cm or more, still more preferably 25 N / 2.5 cm or more, and even more. Preferably it is 30 N / 2.5 cm or more.

The elastic recovery rate (CD) of the multilayer nonwoven fabric of the present invention and the stretched multilayer nonwoven fabric is preferably 35% or more, more preferably 45% or more, still more preferably 60% or more, still more preferably 70% or more, and even more. Preferably it is 75% or more, Most preferably, it is 80% or more.
The hysteresis (CD) of the multilayer nonwoven fabric of the present invention and the stretched multilayer nonwoven fabric is preferably 85% or less, more preferably 80% or less, and even more preferably 75% or less.

[Fiber products]
Although it does not specifically limit as a fiber product using the multilayer nonwoven fabric of this invention, For example, the following fiber products can be mentioned. That is, disposable diaper members, elastic members for diaper covers, elastic members for sanitary products, elastic members for hygiene products, elastic tapes, adhesive plaster, elastic members for clothing, insulation materials for clothing, heat insulation materials for clothing, Protective clothing, hat, mask, gloves, supporter, elastic bandage, poultice base fabric, anti-slip base fabric, vibration absorber, finger sack, clean room air filter, electret processed electret filter, separator, insulation , Coffee bags, food packaging materials, automotive ceiling skins, soundproofing materials, cushioning materials, speaker dustproofing materials, air cleaner materials, insulator skins, backing materials, adhesive nonwoven fabric sheets, door trims and other automotive parts, copier cleaning Various cleaning materials such as wood, surface and backing materials for carpets, agricultural distribution, wood drain , Mention may be made of shoes for members such as sports shoes skin, a bag member, industrial sealing material, such as wiping material and sheets.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Production Example 1 (Production of propylene-based resin 1)
To a stainless steel reactor with a stirrer and an internal volume of 0.25 m ³ , n-heptane was 26 L / h, triisobutylaluminum was 7.7 mmol / h, dimethylanilinium tetrakispentafluorophenylborate and (1,2 ′ -Dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, triisobutylaluminum, and propylene, the catalyst component obtained in advance was continuously fed. Propylene and hydrogen were continuously supplied to keep the total pressure in the reactor at 1.0 MPa · G, and the polymerization temperature was adjusted. To the obtained polymerization solution, an antioxidant (trade name: Irganox 1010, manufactured by BASF) was added to 1000 ppm by mass, and the solvent was removed to obtain propylene-based resin 1.

Production Example 2 (Production of propylene-based resin 2)
To a stainless steel reactor with a stirrer and an internal volume of 0.25 m ³ , n-heptane was 26 L / h, triisobutylaluminum was 7.7 mmol / h, dimethylanilinium tetrakispentafluorophenylborate and (1,2 ′ -Dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, triisobutylaluminum, and propylene, the catalyst component obtained in advance was continuously fed. Propylene and hydrogen were continuously supplied to keep the total pressure in the reactor at 1.0 MPa · G, and the polymerization temperature was adjusted. To the obtained polymerization solution, an antioxidant (trade name: Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.) was added to 1000 ppm by mass, and the solvent was removed to obtain propylene-based resin 2.

  The following measurements were performed on the propylene-based resin 1 and the propylene-based resin 2 obtained in Production Examples 1 and 2. The measurement results are shown in Table 1.

(Measurement of weight average molecular weight (Mw), molecular weight distribution (Mw / Mn))
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). For the measurement, the following apparatus and conditions were used, and a weight average molecular weight in terms of polystyrene was obtained.
[GPC measuring device]
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
〔Measurement condition〕
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml
Injection volume: 160 μl
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(NMR measurement)
The ¹³ C-NMR spectrum was measured using the apparatus and conditions shown below, and the values [mmmm] and [rrrr] / (1- [mmmm]) were calculated. In addition, the attribution of the peak followed the method proposed by A. Zambelli et al. In “Macromolecules, 8, 687 (1975)”.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

〔a formula〕
M = m / S × 100
R = γ / S × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

(Measurement of melt flow rate (MFR))
According to JIS K7210, the measurement was performed under conditions of a temperature of 230 ° C. and a load of 21.18N.

(Melting point measurement)
Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co.), a melting endotherm obtained by holding 10 mg of a sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. The melting point (Tm-D) was determined from the peak top of the peak observed on the highest temperature side of the curve.

(Measurement of melting endotherm (ΔH-D))
Using a differential scanning calorimeter (trade name: DSC-7, manufactured by Perkin Elmer Co., Ltd.), holding 10 mg of a sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C./min The obtained melting endotherm was determined as ΔH-D (J / g).

(Measurement of crystallinity)
Using a differential scanning calorimeter (“DSC-7” manufactured by Perkin Elmer), 10 mg of the sample was held at 220 ° C. for 5 minutes in a nitrogen atmosphere, and the temperature was lowered to −40 ° C. at 10 ° C./min. The melting endotherm ΔH was determined from the area of the melting endotherm curve obtained by maintaining at −40 ° C. for 5 minutes and raising the temperature to 220 ° C. at 10 ° C./min, and the crystallinity (%) was calculated from the following formula. .
Crystallinity (%) = (ΔH / ΔHm ⁰ ) × 100
In the formula, ΔHm ⁰ represents the melting endotherm of a complete crystal, and is 209 J / g for polypropylene.

[Manufacture of multilayer nonwoven fabric]
Example 1
Using the propylene-based resin 1 as a raw material, a single screw extruder, a die (die width 15 inches, single hole diameter 0.5 mm, number of holes per die 366 holes (183 holes × 2 rows)), high-temperature compressed air generator, A nonwoven fabric was formed as shown below using a multilayer nonwoven fabric production apparatus (offline machine) having a melt blown nonwoven fabric apparatus (MB apparatus type 1) comprising a nonwoven fabric winding apparatus.
The raw material is melted at a resin temperature of 182 ° C., the rotational speed of the single screw extruder is 90 rpm, and the molten resin is transferred from the die to the conveyor at a discharge rate of 0.4 g / min per single hole (DCD). Is discharged under the condition of 33 cm, and the resin is compressed air at 182 ° C., the die head pressure is 19 MPa, and the basis weight of the melt blown nonwoven fabric layer (M layer) is 60 g / m ² , as shown in FIG. A spunlace nonwoven fabric (manufactured by Jacob-Form Industries, 50/50, polypropylene / polyethylene terephthalate, 30 g / m ² ) on a net conveyor with a line speed of 5.7 m / min was sprayed and laminated with the spunlace nonwoven fabric. The nonwoven fabric conveyed by the net conveyor is wound up in a roll shape by a winder, and a spunlace nonwoven fabric / melt blown nonwoven fabric layer (M layer) / spunlace nonwoven fabric (weight structure: 30/60/30 [g / m ² ] ) A three-layer nonwoven fabric having a structure was obtained. The results are shown in Table 2.

Example 2
In Example 1, on a net conveyor with a line speed of 3.7 m / min so that the rotation speed of a single screw extruder is 95 rpm, the head pressure is 21 MPa, and the basis weight of the melt blown nonwoven fabric layer is 75 g / m ² . A three-layer nonwoven fabric having a melt-blown nonwoven fabric layer (M layer) as an inner layer was obtained in the same manner as in Example 1 except that the spunlace nonwoven fabric was sprayed. The results are shown in Table 2.

Example 3
In Example 2, the same method as in Example 2 except that the melt-blown nonwoven fabric layer was sprayed on a spunlace nonwoven fabric on a net conveyor at a line speed of 3.5 m / min so that the basis weight of the melt blown nonwoven fabric layer was 90 g / m ² . A three-layer nonwoven fabric having a melt blown nonwoven fabric layer (M layer) as an inner layer was obtained. The results are shown in Table 2.

Example 4
In Example 1, the raw material used was changed to propylene-based resin 1, propylene-based resin 2 was used, the rotational speed of the single screw extruder was set to 35 rpm, the raw material was melted at a resin temperature of 227 ° C., and the single hole from the die The molten resin is discharged at a discharge rate of 0.15 g / min per unit, and the resin is used at 227 ° C. compressed air, the die head pressure is 19 MPa, and the basis weight of the melt blown nonwoven fabric layer (M layer) is 60 g / m ² . A three-layer nonwoven fabric having an elastic melt blow as an inner layer was obtained in the same manner as in Example 1 except that the spunlace nonwoven fabric was sprayed on a net conveyor having a line speed of 2.1 m / min. The results are shown in Table 2.

Example 5
In Example 4, the rotational speed of a single screw extruder was 43 rpm, and sprayed onto a spunlace nonwoven fabric on a net conveyor at a line speed of 1.7 m / min so that the basis weight of the melt blown nonwoven fabric layer was 75 g / m ^2. A three-layer nonwoven fabric having a melt blown nonwoven fabric layer (M layer) as an inner layer was obtained in the same manner as in Example 4 except that. The results are shown in Table 2.

Example 6
In Example 5, the melt blown nonwoven fabric layer was melt blown in the same manner as in Example 5 except that it was sprayed on the spunlace nonwoven fabric on the net conveyor at a line speed of 1.5 m / min so that the basis weight of the melt blown nonwoven fabric layer was 90 g / m ^2. A three-layer nonwoven fabric having a nonwoven fabric layer (M layer) as an inner layer was obtained. The results are shown in Table 2.

Example 7
In Example 4, the raw material was melted at a resin temperature of 204 ° C., and the molten resin was discharged from the die at a discharge rate of 0.12 g / min per single hole. The melt blown nonwoven fabric layer (M layer) was the same as in Example 5 except that it was sprayed onto the spunlace nonwoven fabric on the net conveyor with a line speed of 1.6 m / min so that the basis weight of the M layer was 60 g / m ^2. ) Was obtained as an inner layer. The results are shown in Table 2.

Example 8
Using the propylene-based resin 1 as a raw material, a melt blow comprising a single screw extruder, a die (die width 15 inches, single hole diameter 0.7 mm, number of holes 226 holes (one line)), a high-temperature compressed air generator, and a winder The nonwoven fabric was shape | molded as shown below using the multilayer nonwoven fabric manufacturing apparatus (offline machine) which has a nonwoven fabric apparatus (the said MB apparatus type 2).
The raw material is melted at a resin temperature of 260 ° C., the rotational speed of the single screw extruder is set to 900 rpm, and the distance from the die to the conveyor (DCD) is set at a discharge rate of 0.5 g / min per single hole from the die. The resin is discharged under the condition of 50 cm, the resin is used at a line speed such that the weight of the melt blown nonwoven fabric layer (M layer) is 40 g / m ² at a die head pressure of 1.1 to 1.3 MPa using compressed air at 290 ° C. As shown in FIG. 1, it was sprayed onto a spunlace nonwoven fabric (manufactured by Jacob-Form Industries, 50/50, polypropylene / polyethylene terephthalate, 30 g / m ² ) on a net conveyor, and laminated with the spunlace nonwoven fabric. The nonwoven fabric conveyed by the net conveyor is wound up into a roll shape by a winder, and a spunlace nonwoven fabric / melt blown nonwoven fabric layer (M layer) / spunlace nonwoven fabric (weight structure: 30/40/30 [g / m ² ] A three-layer non-woven fabric was obtained. The results are shown in Table 3.

Example 9
In Example 8, the melt-blown nonwoven fabric was the same as in Example 8, except that the spunlace nonwoven fabric on the net conveyor was sprayed at a line speed such that the basis weight of the melt-blown nonwoven fabric layer (M layer) was 60 g / m ^2. A three-layer nonwoven fabric having a layer (M layer) as an inner layer was obtained. The results are shown in Table 3.

Example 10
In Example 8, the melt blown nonwoven fabric was the same as in Example 8 except that the spunlace nonwoven fabric on the net conveyor was sprayed at a line speed such that the basis weight of the melt blown nonwoven fabric layer (M layer) was 80 g / m ^2. A three-layer nonwoven fabric having a layer (M layer) as an inner layer was obtained. The results are shown in Table 3.

Example 11
In Example 8, using a die having a die width of 15 inches, a single hole diameter of 0.4 mm, and a hole number of 400 holes (one row), the molten resin is discharged from the die at a discharge speed of 0.25 g / min per single hole, and melt blown. The melt blown nonwoven fabric layer (M layer) was formed in the same manner as in Example 8 except that the nonwoven fabric layer (M layer) was sprayed onto the spunlace nonwoven fabric on the net conveyor at a line speed such that the basis weight was 40 g / m ^2. A three-layer nonwoven fabric having an inner layer was obtained. The results are shown in Table 3.

Example 12
In Example 11, the melt-blown nonwoven fabric was coated in the same manner as in Example 11 except that the melt-blown nonwoven fabric layer (M layer) was sprayed onto the spunlace nonwoven fabric on the net conveyor at a line speed such that the basis weight was 60 g / m ^2. A three-layer nonwoven fabric having a layer (M layer) as an inner layer was obtained. The results are shown in Table 3.

Example 13
In Example 11, the melt blown nonwoven fabric was the same as in Example 11 except that the melt blown nonwoven fabric layer (M layer) was sprayed onto the spunlace nonwoven fabric on the net conveyor at a line speed such that the basis weight was 80 g / m ^2. A three-layer nonwoven fabric having a layer (M layer) as an inner layer was obtained. The results are shown in Table 3.

Example 14
In Example 8, instead of the propylene-based resin 1 used, the propylene-based resin 2 was used, the raw material was melted at a resin temperature of 295 ° C., and the molten resin was discharged from the die at a discharge rate of 0.3 g / min per single hole. The resin is used on a net conveyor at a line speed such that the weight of the melt blown nonwoven fabric layer (M layer) is 40 g / m ² at a die head pressure of 2.2 to 2.4 MPa using compressed air at 290 ° C. A three-layer nonwoven fabric having a meltblown nonwoven fabric layer (M layer) as an inner layer was obtained in the same manner as in Example 8 except that the spunlace nonwoven fabric was sprayed. The results are shown in Table 4.

Example 15
In Example 14, the melt blown nonwoven fabric was the same as in Example 14 except that the melt blown nonwoven fabric layer (M layer) was sprayed onto the spunlace nonwoven fabric on the net conveyor at a line speed such that the basis weight was 60 g / m ^2. A three-layer nonwoven fabric having a layer (M layer) as an inner layer was obtained. The results are shown in Table 4.

Example 16
In Example 14, the melt-blown nonwoven fabric was the same as in Example 14 except that the spunlace nonwoven fabric on the net conveyor was sprayed at a line speed such that the basis weight of the melt-blown nonwoven fabric layer (M layer) was 80 g / m ^2. A three-layer nonwoven fabric having a layer (M layer) as an inner layer was obtained. The results are shown in Table 4.

Example 17
In Example 11, the propylene resin 2 was used instead of the propylene resin 1 used, the raw material was melted at a resin temperature of 295 ° C., and the molten resin was discharged from the die at a discharge rate of 0.24 g / min per single hole. The resin is used on a net conveyor at a line speed such that the weight of the melt blown nonwoven fabric layer (M layer) is 40 g / m ² at a die head pressure of 2.2 to 2.4 MPa using compressed air at 290 ° C. A three-layer nonwoven fabric having a melt blown nonwoven fabric layer (M layer) as an inner layer was obtained in the same manner as in Example 11 except that the spunlace nonwoven fabric was sprayed. The results are shown in Table 4.

Example 18
In Example 17, the melt-blown nonwoven fabric was the same as in Example 17 except that the melt-blown nonwoven fabric layer (M layer) was sprayed onto the spunlace nonwoven fabric on the net conveyor at a line speed such that the basis weight was 60 g / m ^2. A three-layer nonwoven fabric having a layer (M layer) as an inner layer was obtained. The results are shown in Table 4.

Example 19
In Example 17, the melt blown nonwoven fabric was the same as in Example 17 except that the spunlace nonwoven fabric on the net conveyor was sprayed at a line speed such that the basis weight of the melt blown nonwoven fabric layer (M layer) was 80 g / m ^2. A three-layer nonwoven fabric having a layer (M layer) as an inner layer was obtained. The results are shown in Table 4.

Example 20 (molding of multilayer nonwoven fabric with S / M / M / S structure)
By the method shown below, a multilayer nonwoven fabric (S / M / M / S) composed of spunbond nonwoven fabric / meltblown nonwoven fabric layer (M layer) / meltblown nonwoven fabric layer (M layer) / spunbond nonwoven fabric was obtained.
[Formation of first layer spunbond nonwoven fabric layer 1 (S1)]
The spunbond nonwoven fabric was molded using Reicofil 4 manufactured by Reicofil. Using highly crystalline polypropylene (ExxonMobil, trade name: Exxon 3155, MFR = 36) as a raw material, melt extrusion at a resin temperature of 250 ° C., from a die having a single hole diameter of 0.6 mm (hole number 5800 holes / m) The molten resin was discharged and spun at a rate of 0.5 g / min per single hole. The spunbonded nonwoven fabric (S) was formed by discharging the fiber obtained by spinning onto a net conveyor surface moving at a cabin pressure of 2700 Pa and a line speed of 67 m / min.
[Molding of second and third melt-blown nonwoven fabric layers (M1 and M2)]
Using the propylene-based resin 1 as a raw material, it was melt-extruded at a resin temperature of 247 ° C. and melted at a rate of 0.55 g / min per single hole from a die having a single hole diameter of 0.36 mm (number of holes: 35 holes / inch). Resin was discharged. The molten resin is sprayed onto the spunbonded nonwoven fabric layer S1 formed on the net conveyor moving at the line speed of 67 m / min at a flow rate of 800 Nm ³ / h using 260 ° C. compressed air. A meltblown nonwoven fabric layer (M layer; M1) was formed. Immediately thereafter, a melt-blown nonwoven fabric layer (M layer; M2) was formed on the S1 / M1 two-layer laminate by the same method as M1 in another row of melt-blowing equipment.
[Fourth Layer Spunbond Nonwoven Layer 2 (S2) Molding]
The spunbond nonwoven fabric was molded using Reicofil 4 manufactured by Reicofil. On the three-layer laminate (S1 / M1 / M2) formed on the net conveyor moving at the line speed of 67 m / min, a die having a single hole diameter of 0.6 mm (hole number: 6800 holes / m) The spunbond nonwoven fabric that was directly molded was molded by the same method as that for the first spunbond nonwoven fabric layer (online molding) except that was used.
These are pressed with an embossing roll (setting temperature: 125 ° C., surface temperature: 108 ° C.) and an S-roll (setting temperature: 115 ° C., surface temperature: 104 ° C.) at a nip pressure of 80 N / mm. It was embossed (fibers were heat-sealed) to obtain a 4-layer nonwoven fabric having an S1 / M1 / M2 / S2 structure.
The basis weight of the obtained four-layer nonwoven fabric having the SMMS structure was 100 g / m ² , of which the total basis weight of the S layer was 76 g / m ² and the total basis weight of the M layer was 24 g / m ² . The results are shown in Table 5.

  By the method shown below, a multilayer nonwoven fabric obtained by stretching the multilayer nonwoven fabric obtained in the above example using a gear processing machine was obtained.

Example 21
The three-layer nonwoven fabric having the Sp / M / Sp structure having the melt-blown nonwoven fabric layer (M layer) obtained in Example 3 as an inner layer using a gear roll having a gear depth of 0.08 inch at normal temperature (23 ° C.). Gear stretching was performed at a processing speed of 0.2 m / min in a direction (CD) perpendicular to the flow direction of the nonwoven fabric during molding of the nonwoven fabric to obtain a stretched three-layer nonwoven fabric of Sp / M / Sp structure. The results are shown in Table 6.

Example 22
In Example 21, a stretched three-layer nonwoven fabric was obtained in the same manner as in Example 21 except that stretching was performed using a gear roll having a gear depth of 0.10 inch. The results are shown in Table 6.

Example 23
In Example 21, a stretched three-layer nonwoven fabric was obtained in the same manner as in Example 21 except that stretching was performed using a gear roll having a gear depth of 0.12 inches. The results are shown in Table 6.

Example 24
In Example 21, except that the Sp / M / Sp structure three-layer nonwoven fabric having the elastic meltblown nonwoven fabric obtained in Example 6 as an inner layer was stretched using a gear roll having a gear depth of 0.10 inch. In the same manner as in Example 21, a three-layer nonwoven fabric having an Sp / M / Sp structure subjected to stretching treatment was obtained. The results are shown in Table 6.

Example 25
A stretched three-layer nonwoven fabric was obtained in the same manner as in Example 24 except that in Example 24, stretching was performed using a gear roll having a gear depth of 0.12 inches. The results are shown in Table 6.

Example 26
A stretched three-layer nonwoven fabric was obtained in the same manner as in Example 24 except that in Example 24, stretching was performed using a gear roll having a gear depth of 0.15 inches. The results are shown in Table 6.

Example 27
In Example 21, the three-layer nonwoven fabric having the Sp / M / Sp structure having the elastic meltblown nonwoven fabric obtained in Example 13 as an inner layer was stretched using a gear roll having a gear depth of 0.10 inch. A stretched Sp / M / Sp3 layer nonwoven fabric was obtained in the same manner as in Example 21. The results are shown in Table 7.

Example 28
In Example 27, a stretched three-layer nonwoven fabric was obtained in the same manner as in Example 27 except that stretching was performed using a gear roll having a gear depth of 0.12 inches. The results are shown in Table 7.

Example 29
In Example 27, a stretched three-layer nonwoven fabric was obtained in the same manner as in Example 27 except that stretching was performed using a gear roll having a gear depth of 0.15 inches. The results are shown in Table 7.

Example 30
In Example 21, except that the Sp / M / Sp structure three-layer nonwoven fabric having the elastic meltblown nonwoven fabric obtained in Example 19 as an inner layer was stretched using a gear roll having a gear depth of 0.10 inch. A stretched Sp / M / Sp3 layer nonwoven fabric was obtained in the same manner as in Example 21. The results are shown in Table 7.

Example 31
In Example 30, a stretched three-layer nonwoven fabric was obtained in the same manner as in Example 30, except that stretching was performed using a gear roll having a gear depth of 0.12 inches. The results are shown in Table 7.

Example 32
In Example 30, a stretched three-layer nonwoven fabric was obtained in the same manner as in Example 30, except that stretching was performed using a gear roll having a gear depth of 0.15 inches. The results are shown in Table 7.

Example 33
The S / M / M / S structure four-layer nonwoven fabric having the melt-blown nonwoven fabric layer (M layer) obtained in Example 20 as an inner layer, using a gear roll with a gear depth of 0.04 inches, at room temperature (23 ° C.). Was subjected to gear stretching at a processing speed of 20 m / min in a direction (CD) perpendicular to the flow direction of the nonwoven fabric at the time of molding the nonwoven fabric to obtain a stretched three-layer nonwoven fabric of S / M / M / S structure . The results are shown in Table 8.

Example 34
A stretched four-layer nonwoven fabric was obtained in the same manner as in Example 33 except that in Example 33, stretching was performed using a gear roll having a gear depth of 0.08 inch. The results are shown in Table 8.

Example 35
A stretched four-layer nonwoven fabric was obtained in the same manner as in Example 33 except that in Example 33, stretching was performed using a gear roll having a gear depth of 0.12 inches. The results are shown in Table 8.

[Evaluation of multilayer nonwoven fabric]
(1) Measurement of basis weight A 5 cm x 5 cm sample of the obtained multilayer nonwoven fabric was cut out and measured for mass to calculate the basis weight (g / m ² ).

(2) Measurement of elongation at break and tensile strength From the obtained multilayer nonwoven fabric, a test piece having a length of 150 mm in a direction perpendicular to the machine direction (CD) and a width of 25 mm was sampled. Using a tensile tester (“Autograph AG-I” manufactured by Shimadzu Corporation), the initial length L ₀ was set to 100 mm, and a tensile test was performed at a strain rate of 300 mm / min.

(3) Elastic recovery rate, elastic hysteresis From the obtained multilayer nonwoven fabric, a test piece having a length of 150 mm and a width of 25 mm in the direction orthogonal to the machine direction (CD) was sampled. Using a tensile tester (“Autograph AG-I” manufactured by Shimadzu Corporation), the initial length L ₀ was set to 100 mm under the condition of room temperature of 23 ° C., and the strain was 0 at a strain rate of 300 mm / min. Stretching cycles that stretched from% to 100% and shrunk from 100% to 0% were performed three cycles. The length at which stress was generated during the third extension was defined as L (mm). The elastic recovery rate (%) was calculated from the following formula.
Elastic recovery rate (%) = (2-L / L ₀ ) × 100
The elastic hysteresis was calculated from the following formula for the first cycle.
Elastic hysteresis (%) = {(integral area of tension during extension−integral area of tension during return) / integral area of tension during extension} × 100

  The multilayer nonwoven fabric of the present invention is suitably used for various textile products such as disposable diapers, sanitary products, sanitary products, clothing materials, bandages and packaging materials.

1 Melt blow die (MB equipment type 1 or 2)
2 Melt blown fibers constituting M layer 3 Material constituting X layer (spunlace nonwoven fabric or spunbond nonwoven fabric)
4 Material constituting X layer (spunlace nonwoven fabric or spunbond nonwoven fabric)
5 Smooth roll (S-roll) or patterned roll (embossing roll)
6 Smooth roll (S-roll) or patterned roll (embossing roll)
7 Pore forming belt (net conveyor)
8 XMX laminate 9 Spunbond die (SB equipment)
Spunbond fiber constituting 10 S layer

Claims (7)

90 to 100% by mass of a propylene-based resin satisfying the following (a) to (g), which is a multilayer nonwoven fabric of three or more layers composed of two outer layers and an inner layer sandwiched between them. A multilayer nonwoven fabric, which is a meltblown nonwoven fabric made of a resin composition containing
(A) Weight average molecular weight (Mw) = 20,000 to 1,000,000
(B) [mmmm] = 20-60 mol%
(C) Molecular weight distribution (Mw / Mn) = 1.5-3.0
(D) [rrrr] / (1- [mmmm]) ≦ 0.1
(E) Melting point (Tm−D) = 30 to 140 ° C.
(F) Melting endotherm (ΔH−D) = 5 J / g or more and less than 50 J / g (g) Crystallinity = 1-40% The basis weight of the melt blown nonwoven fabric layer (M layer) is equal to or more than the basis weight of all the layers other than the melt blown nonwoven fabric layer (X layer), and the basis weight of the melt blown nonwoven fabric layer is 20 to 100 g. The multilayer nonwoven fabric according to claim 1, which is / m ² .   The multilayer nonwoven fabric according to claim 1 or 2, wherein the resin composition contains 95 to 100 mass% of the propylene-based resin.   The multilayer nonwoven fabric according to any one of claims 1 to 3, wherein the outer layer is a spunlace nonwoven fabric or a spunbond nonwoven fabric.   The multilayer nonwoven fabric according to any one of claims 1 to 4, which is molded by an off-line manufacturing method. Elongation at break in CD direction (CD) is not less than 100%, a tensile-strength (CD) is not less 15N / 2.5 cm or more, elastic recovery (CD) is 35% or more, claim 1-5 A multilayer nonwoven fabric according to any one of the above.   The textiles using the multilayer nonwoven fabric in any one of Claims 1-6.